JP2731205B2 - Recording material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION INDUSTRIAL APPLICATION The present invention relates to at least one cycloalkene compound.
The present invention relates to a recording material characterized by using a seed.

(Prior art)

Color formers, which are colorless or light-colored basic dyes, have been used for various recording materials. The main examples thereof include a pressure-sensitive recording material, a heat-sensitive recording material, an energized heat-sensitive recording material, and a photosensitive recording material. These recording materials, today, with the development of the information industry,
Its demand is soaring.

Conventionally, as typical examples of color formers generally used for recording materials such as pressure-sensitive recording sheets, heat-sensitive recording sheets, and photosensitive recording sheets, phthalide-based compounds, fluoran-based compounds, and triphenylmethane And the like. For example, a typical example of a phthalide compound is crystal violet lactone which emits blue, and a typical example of a fluoran compound is 2- (2-chloroanilino) -6-dibutylaminofluorane which emits black, and triphenylmethane. Representative examples of the compound include leuco crystal violet which emits blue light.

Computers are widely used for these recording materials in order to streamline business processes associated with office automation or various rationalizations associated with factory automation. Optical character reading devices are used for information input at that time. Alternatively, an optical barcode reader has been developed, and accordingly, it has been increasingly used in recent years.

[Problems to be solved by the invention]

Furthermore, in recent years, an optical character reader or an optical barcode reader using a semiconductor laser or the like and using light in the near infrared region as a light source has been developed, and a recording material therefor is required. I have. However, conventional color formers do not absorb light in the near-infrared region around 700-900 nm, so recording images obtained with recording materials using conventional color formers use semiconductor lasers, etc. It is not suitable as a recorded image for an optical character reader or an optical barcode reader using light in the near infrared region as a light source.

[Means for solving the problem]

The following general formula [1] of the present invention: (Wherein R ¹ and R ² are each independently a hydrogen atom, an alkoxyalkyl group, a lower alkyl group optionally substituted with a halogen atom, a halogen atom, an alkoxy group, or a lower alkyl group. Represents a phenyl group which may be substituted with a good phenyl group, a halogen atom or a lower alkyl group, and R ¹ and R ² may form a ring together with the nitrogen atom to which they are bonded, R
³ represents a hydrogen atom, a halogen atom, a lower alkyl group, an alkoxy group, an alkoxyalkyl group or an alkoxycarbonyl group,, R ^4, R ⁵ is -CH ₂ -CH together
_{2 -, - CH 2 -CH 2} -CH 2 -, - CH 2 -CH 2 -CH 2 -CH 2 -, or _{-CH 2 -CH 2 -CH 2 -CH 2} -CH 2 - represents, and R
⁶ represents a phenylsulfonyl group, an alkoxy group, or an alkoxyalkoxy group which may be substituted with a lower alkyl group. However, R ¹ and R ² are each independently a lower alkyl group, R ³ is a hydrogen atom, and
R ^4, R ^5, taken together _{-CH 2 -CH 2 -, - CH} 2 -CH 2 -CH 2
And R ⁶ is a lower alkoxy group or a phenylsulfonyl group optionally substituted by a lower alkyl group, and R ¹ and R ² are each independently a lower alkyl group, and R ³ is A lower alkyl group substituted at the 2-position, and at the same time, R ⁴ and R ⁵ together form —CH ₂ —CH ₂ —, —CH ₂
—CH ₂ —CH ₂ —, except that R ⁶ is a lower alkoxy group or a phenylsulfonyl group which may be substituted by a lower alkyl group. ) Are inorganic acids, organic acids, phenolic compounds, and derivatives thereof, or metal salts thereof, or a color developing material such as an electron accepting substance such as an oxidizing agent, for example, acid clay. , 3,5-di-t-butylsalicylic acid, bis (3-
By bringing into contact with (chlorophenyl) thiourea, 4,4'-isopropylidenediphenol, zinc 4-nitrobenzoate, benzyl 4-hydroxybenzoate, etc., a greenish blue or greenish color tone is exhibited, and high density and vividness are achieved. It is a color former that develops color, and the recorded image obtained by using the color former, for example, a pressure-sensitive recording sheet or a heat-sensitive recording sheet, absorbs light in the near infrared region around 700 to 900 nm. As a recording material for optical character readers using near-infrared light as a light source using semiconductor lasers, etc. It is suitable.

As described above, the present invention does not consider color formers used in conventional pressure-sensitive recording materials, heat-sensitive recording materials, or photosensitive recording materials, and recording materials using these color formers. Another object of the present invention is to provide a recording material characterized by using at least one of color formers having characteristics not obtained.

In the present invention, as typical examples of a color-sensitive material used to obtain a pressure-sensitive recording material, a heat-sensitive recording material, and a photosensitive recording material, bentonite, zeolite, acid clay, activated clay, silica gel, zinc oxide, zinc chloride, Aluminum chloride, zinc bromide, or 3-t-butylsalicylic acid,
Salicylic acid derivatives such as zinc 3,5-di-t-butylsalicylate, salicylanilide, thiourea derivatives such as bis (3-chlorophenyl) thiourea, phenol derivatives such as 4-t-butylphenol, naphthol derivatives,
Novolak type phenolic resins, benzophenone derivatives such as 4-hydroxybenzophenone, benzoic acid derivatives such as 4-nitrobenzoic acid, zinc 4-nitrobenzoate, ethyl 4-hydroxybenzoate, 1-hydroxy-2-naphthoic acid, 2-hydroxybenzoic acid Naphthoic acid derivatives such as zinc hydroxy-6-naphthoate, phenylsulfone derivatives such as 4-hydroxydiphenylsulfone, organic acids such as maleic acid, succinic acid, malic acid and stearic acid, biimidazole, hexaphenylbiimidazole, and four odors And the like.

In the present invention, in producing the pressure-sensitive recording material and the heat-sensitive recording material, one type selected from these color formers may be used alone, or two or more types may be mixed and used. , Crystal violet lactone, 2- (2-chloroanilino) -6-dibutylaminofluoran, 2-anilino-3-methyl-6- (N
-Ethyl-N-tetrahydrofurfurylamino) fluoran, 2-anilino-3-methyl-6-dibutylaminofluoran, 2-anilino-3-methyl-6-diethylaminofluoran, 2-anilino-3-methyl-6 −
(N-methyl-N-cyclohexylamino) fluoran, 2-anilino-3-methyl-6- (N-ethyl-N
-Isoamylamino) fluoran, 2-N, N-dibenzylamino-6-diethylaminofluoran, benzoylleucomethylene blue, leucocrystal violet, and other known color formers. By mixing, the color developability, storability, stability and the like of the image may be further improved.

In the present invention, as a typical example of a solvent for a color former used to obtain a pressure-sensitive recording material, Hisol SAS-296 (a product of Nippon Petrochemical Co., Ltd.) and KMC-113
(Products of Kureha Chemical Co., Ltd.), but various solvents such as monoisopropylbiphenyl, alkylbenzene, alkylbiphenyl, alkylnaphthalene, diarylethane, hydrogenated terphenyl, and chlorinated paraffin solvents are used alone. Or a mixture of them.

In the present invention, as an encapsulation method used to obtain a pressure-sensitive recording material, a coacervation method, an interfacial polymerization method, an in-situ method, or the like can be used.

In the present invention, as typical examples of the binder used to obtain the thermosensitive recording material, polyvinyl alcohol, methyl cellulose, cellulose derivatives such as methoxycellulose, gum arabic, gelatin, casein,
Examples include starch and its derivatives, polyvinyl acetate, polyacrylic acid, polyvinylpyrrolidone, polyurethane, polyacrylamide, acrylamide / acrylate copolymer, and styrene-maleic anhydride copolymer.

Further, in order to further improve the light resistance of the recorded image, storage stability, and the like, higher fatty acid esters, higher fatty acid amides, phthalic esters, terephthalic esters, benzylbiphenyls, alkylphenols, benzenesulfonamides, Various additives such as antioxidants, deterioration inhibitors, and ultraviolet absorbers such as alkylbenzenesulfonamides and terphenyls can be used in combination.

The above general formula [1] having excellent properties as described above.
Is a cycloalkene compound represented by
2. It can be synthesized by the following well-known typical methods described in JP-A-55-45785 and JP-A-60-231766.

That is, the cycloalkanone derivative represented by the general formula [4] is obtained by converting the benzaldehyde derivative represented by the general formula [2] and the cycloalkanone represented by the general formula [3] to a base such as sodium hydroxide. Using a catalyst, several tens at 20-80 ° C
It can be synthesized by dehydration condensation for a few minutes to several hundred hours.

Further, the cycloalkanium perchlorate derivative represented by the general formula [5] is obtained by reducing the cycloalkanone derivative represented by the general formula [4] in the presence of a catalyst such as palladium carbon, or using lithium hydride. aluminum, more preferably after reduction by a reducing agent such as sodium borohydride, acids (wherein the perchlorate at 20 to 100 ° C., X ^-
Represents a conjugated chlorine. ) Can be synthesized.

Furthermore, the cycloalkanium perchlorate derivative represented by the general formula [5] is prepared by adding an alcohol represented by the general formula [6] or benzenesulfinic acid at 20 to 100 ° C. in an alcohol solvent such as methanol. With an alkali metal salt of a sulfinic acid (wherein the alkali metal is represented by M).

In addition, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the general formulas (2) to (6) have the same meaning as defined in the general formula [1].

The cycloalkene compound thus obtained is specifically described as follows.

[Examples] Next, the present invention will be described in more detail with reference to examples. In the following, “parts” means “parts by weight” and “%” means “% by weight”.

Example 1 1- [α-Methoxy- (2-ethoxy-4-N, N-diethylamino) benzyl) -3- (2-ethoxy-4-N, N was added to KMC-113 (product of Kureha Chemical Co., Ltd.). -Diethylaminobenzylidene) dissolved in cyclohexene 3%
In 3.5 parts, 12.6 parts of Coronate L (product of Nippon Polyurethane Industry Co., Ltd.) and 5 ml of ethyl acetate were added with stirring, and then 3.5 parts of polyvinyl alcohol and 1.6 parts of gelatin were added.
8 parts, 1,4-di (2-hydroxyethoxy) benzene 2.86
And a mixture of 54.96 parts of water, and add 6 with a homomixer.
The mixture was emulsified under the conditions of 000 rpm, further added with 50 ml of water, heated at 60 ° C and polymerized, and 1- [α-methoxy- (2-ethoxy-4-N, N-diethylamino) benzyl] -3- (2-
A microcapsule slurry of ethoxy-4-N, N-diethylaminobenzylidene) cyclohexene dissolved oil was prepared.

Put this microcapsule slurry on one side of plain paper,
Using a wire bar coater, it was applied so as to have a uniform film thickness and dried to prepare CB paper.

The CB paper thus obtained is brought into close contact with a representative commercially available pressure-sensitive color developing sheet, a clay-based, resin-based, salicylic acid derivative metal salt-based color developing sheet, and a 28 mmφ using a hydraulic press. When a pressure of 500 kg / cm ² was applied to each of the samples, green-blue or blue-green color recording images were obtained.

When the reflection and absorption characteristics of the recorded image thus obtained were measured using a spectrophotometer U-3410 (manufactured by Hitachi, Ltd.), a strong electromagnetic absorption in the near infrared region of 700 nm to 1100 nm was obtained. Had.

Examples 2 to 5 1- [α-methoxy- (2-ethoxy-4-N, N-diethylamino) benzyl] -3- (2-ethoxy-4-
Instead of N, N-diethylaminobenzylidene) cyclohexene, 1- [α-methoxy- (4-piperidino) benzyl] -3- (4-piperidinobenzylidene) cyclohexene, 1- [α-methoxy- (4-pyrrolidino) ) Benzyl] -3- (4-pyrrolidino benzylidene) cyclohexene, 1- [α-methoxy- (4-piperidino) benzyl] -3- (4-piperidinobenzylidene) cyclopentene, or 1- [α-methoxy CB paper was prepared in the same manner as in Example 1 except that-(4-piperidino) benzyl] -3- (4-pyrrolidinobenzylidene) cyclopentene was used.

The CB paper thus obtained is brought into close contact with a representative commercially available pressure-sensitive color developing sheet, a clay-based, resin-based, salicylic acid derivative metal salt-based color developing sheet, and a 28 mmφ using a hydraulic press. When a pressure of 500 kg / cm ² was applied to each of the samples, green-blue or blue-green color recording images were obtained.

When the reflection and absorption characteristics of the recorded images thus obtained were measured, all of them had strong electromagnetic wave absorption in the near infrared region.

Example 6 1- [α-phenylsulfonyl- (2-ethoxy-
4-N, N-diethylamino) benzyl] -3- (2-ethoxy-4-N, N-diethylaminobenzylidene) cyclohexene together with 20 parts of a 10% aqueous solution of polyvinyl alcohol in a ball mill for 24 hours at room temperature The mixture was dispersed and mixed to obtain a colorless slurry as "liquid A". The particle size of the solid material in this slurry was about 3 microns.

On the other hand, 7.5 parts of bisphenol A was dispersed and mixed with 40 parts of a 10% aqueous polyvinyl alcohol solution and 10 parts of deionized water at room temperature for 24 hours using a ball mill.
A slurry was prepared as a “liquid”. The particle size of the solid material in this slurry was about 5 microns.

The above "Solution A" and "Solution B" were mixed, stirred at room temperature for 1 hour, uniformly dispersed and mixed to prepare a mixed slurry. This mixed slurry was applied to one side of plain paper of 50 g / m ² using a wire bar coater so as to have a uniform film thickness, air-dried at room temperature, and a thermosensitive recording sheet having a substantially colorless thermosensitive layer It was created.

When the heat-sensitive recording sheet thus prepared was colored using a thermal gradient tester, a yellow-green color recording image was obtained. When the reflection and absorption characteristics of this recorded image were measured, it was found that the recorded image had strong electromagnetic wave absorption in the near infrared region.

Examples 7 to 10 1- [α-phenylsulfonyl- (2-ethoxy-
4-N, N-diethylamino) benzyl] -3- (2-ethoxy-4-N, N-diethylaminobenzylidene) cyclohexene, instead of 1- [α-phenylsulfonyl- (4-piperidino) benzyl] -3- (4-piperidinobenzylidene) cyclohexene, 1- [α-phenylsulfonyl- (4-pyrrolidino) benzyl] -3-
(4-pyrrolidinobenzylidene) cyclohexene, 1-
[Α-phenylsulfonyl- (4-pyrrolidino) benzyl] -3- (4-piperidinobenzylidene) cyclopentene or 1- [α-phenylsulfonyl-
Example 6 except that (4-pyrrolidino) benzyl] -3- (4-pyrrolidinobenzylidene) cyclopentene was used.
To prepare a heat-sensitive recording sheet having an almost colorless heat-sensitive layer.

When the heat-sensitive recording sheet thus prepared was colored using a thermal gradient tester, a yellow-green color recorded image was obtained in each case. When the reflection and absorption characteristics of this recorded image were measured, all of them had strong electromagnetic wave absorption in the near infrared region.

〔The invention's effect〕

As described above, the present invention has strong absorption in the near-infrared region in a colored state, and when used in a pressure-sensitive recording sheet, has extremely excellent solubility in capsule oil, and also exhibits coloring performance and storage performance. Excellent in various properties, or
When used for a heat-sensitive recording sheet, the present invention provides a recording material using a cycloalkene compound having extremely excellent sensitivity characteristics. Further, the present invention meets the demands of a new market, and has the effect of expanding the range of use of recording materials.

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Claims (1)

(57) [Claims] 1. The following general formula [1] (Wherein R ¹ and R ² are each independently a hydrogen atom, an alkoxyalkyl group, a lower alkyl group optionally substituted with a halogen atom, a halogen atom, an alkoxy group, or a lower alkyl group. Represents a phenyl group which may be substituted with a good phenyl group, a halogen atom or a lower alkyl group, and R ¹ and R ² may form a ring together with the nitrogen atom to which they are bonded, R
³ represents a hydrogen atom, a halogen atom, a lower alkyl group, an alkoxy group, an alkoxyalkyl group or an alkoxycarbonyl group,, R ^4, R ⁵ is -CH ₂ -CH together
_{2 -, - CH 2 -CH 2} -CH 2 -, - CH 2 -CH 2 -CH 2 -CH 2 -, or _{-CH 2 -CH 2 -CH 2 -CH 2} -CH 2 - represents, and R
⁶ represents a phenylsulfonyl group, an alkoxy group, or an alkoxyalkoxy group which may be substituted with a lower alkyl group. However, R ¹ and R ² are each independently a lower alkyl group, R ³ is a hydrogen atom, and
R ^4, R ^5, taken together _{-CH 2 -CH 2 -, - CH} 2 -CH 2 -CH 2
And R ⁶ is a lower alkoxy group or a phenylsulfonyl group optionally substituted by a lower alkyl group, and R ¹ and R ² are each independently a lower alkyl group, and R ³ is A lower alkyl group substituted at the 2-position, and at the same time, R ⁴ and R ⁵ together form —CH ₂ —CH ₂ —, —CH ₂
—CH ₂ —CH ₂ —, except that R ⁶ is a lower alkoxy group or a phenylsulfonyl group which may be substituted by a lower alkyl group. A recording material using a cycloalkene compound represented by the formula (1) as a coloring agent.