JPS60106858A - Dye for recording material - Google Patents

Abstract

PURPOSE:To provide a dye for recording material which is stable and can be effectively used in ultraviolet light-sensitive materials used in combination with a halogen-contg. org. compd. and pressure-sensitive recording paper or thermal recording paper using a redox reaction, consisting of a specified leuco compd. CONSTITUTION:A dye for recording materials consists of a leuco compd. of the formula (wherein A, B, X, Y are each unsubstituted phenyl, naphthyl, indole-3- yl or substd. phenyl or naphthyl which is substd. with at least one amino group at the para position against -CH- and may have further at least one substituent selected from among lower alkyl, lower alkoxy, halogen and amino group). The dye develops rapidly and quantitatively a color when brought into contact with an electron attractive group-substd. benzoquinone derivative used in pressure- sensitive or thermal recording paper. As compd. with leuco triarylmethane compds, the dye is superior in stability in the air during storage, and hene there is little fear that the recording paper is stained by coloration before its use. Thus, the dye can dispense with any stainproofing agent.

Description

[Detailed description of the invention] The present invention relates to dyes for recording materials.

Specifically, the present invention relates to leuco compounds used in recording materials that develop color in response to various types of energy such as pressure, heat, electromagnetic waves (light), and particle beams.

With the rapid spread of office automation, large amounts of information recording paper, such as pressure-sensitive recording paper, thermal recording paper, electrostatic recording paper, and inkjet recording paper, are being used in large quantities as various recording materials. Yo .

I became angry. In addition, the amount of radiation-sensitive pattern forming materials used for various industrial or consumer purposes, such as dry film resists and resist inks for forming printed circuit boards, has been increasing in recent years.

These various recording materials are sensitive to energy such as pressure, heat, and electromagnetic waves to form images by causing chemical reactions that change the hue from colorless to colored or from colored to colorless. has achieved its purpose.

For example, in the case of information recording paper such as pressure-sensitive recording paper and heat-sensitive recording paper, chemical means for forming such a distinguishable colored image include basic leuco dyes such as phthalide or fluoran dyes, and phenol. Color reaction by contact with organic or inorganic solid acids such as resins or acidic clays is generally used.

However, upon contact, these compounds quickly form color-forming complexes, producing various hues corresponding to each compound, but the formation of this color-forming complex is reversible, and water, oils, oxygen-containing polar The equilibrium shifts due to contact with solvents or temperature changes, causing the color to fade. Therefore, there is a major drawback in that the recorded image lacks stability against the environment, and improvements have been strongly urged.

In order to improve storage stability, the present inventors developed a pressure-sensitive recording unit and a heat-sensitive recording unit (Japanese Patent Application Laid-Open Nos. 57-107882 and 58-7438) using a new redox coloring system.
9, 58-132/) 87).

According to such a novel coloring method, a colored image is irreversibly formed on the recording paper, and the above-mentioned instability of the colored image can be solved.

As the color-forming compounds used in this color-forming method, a group of even more excellent compounds is being sought.

Furthermore, other items of radiation-sensitive recording materials include ultraviolet-sensitive color-forming materials, such as dry film resists for printed wiring boards, resist inks, and other ultraviolet-detecting materials, such as germicidal lamp attenuation indicators. can be mentioned. Various coloring principles have been proposed for these UV-sensitive materials, but the most commonly used are:
This is a coloring method based on so-called free radical photography, which uses a combination of a leukotriphenylmethane compound and an organic chloride compound. However, such leucotriphenylmethane dyes, such as leuco crystal violet, generally tend to be too sensitive to air oxidation during storage, and may develop background color during long-term storage before use. Although there remained some problems in controlling color development sensitivity, further improvements were expected.

In view of the above-mentioned problems, the present inventors have made extensive studies on dyes for energy-sensitive recording materials with excellent performance. is a phenyl group, a naphthyl group, or an indole-6- group, each of which may have a substituent.
Indicates an yl group. When each of A, B, group, lower alkoxy group,
It may have a rogene atom or an amino group. ) It has been discovered that the dye for recording materials is excellent in overcoming the above-mentioned problems, and the present invention has been achieved.

That is, the dye for recording materials of the present invention has the general formula (1
), specifically, JP-A-57-
= No. 107882, No. 58,743.89, No. 58-
Pressure-sensitive recording paper using a redox reaction as disclosed in No. 132687, heat-sensitive recording paper, or ultraviolet-sensitive materials used in combination with organic-containing nitrogen compounds, such as dry film resists for forming printed circuits, germicidal lamps. Effectively used as attenuation indicators, etc.

The dye for recording materials of the present invention rapidly develops a deep color in pressure-sensitive copying paper and heat-sensitive copying paper by the coloring mechanism estimated as follows when it comes into contact with the benzoquinone derivative substituted with an electron-withdrawing group. and causes quantitative coloration.

Since the coloring substance (■) obtained by such a redox coloring method has a long conjugated system, it has poor air oxidation stability during storage compared to conventional triary- and leucotriarylmethane-based compounds. Because it has excellent properties, the tendency for color staining on the paper surface before use (in the case of pressure-sensitive paper, on the surface coated with microcapsules) is significantly reduced, making it possible to eliminate the use of anti-staining agents or significantly reduce the amount used. becomes.

Moreover, irreversible color development occurs on the pressure-sensitive copying paper or heat-sensitive recording paper obtained in this way by contact with pressure or thermal energy, so the color image is very stable under the environment in which it is stored, and compared to conventional paper. Unlike the widely used colored images created by the reaction of lactone dyes with strong substances, the colors rarely fade when they come into contact with water or polar solvents. In addition, while certain lactone dyes, such as crystal violet lactone, and acid clay tend to be mixed together, such a tendency was not observed in the colored images produced by the above-mentioned coloring method using the dye of the present invention.

The above-mentioned lack of environmental stability of colored images also applies to current thermal recording paper, which is a combination of lactone dyes and phenolic solid acids. The tendency of a colored image to fade due to contact with other materials is considered to be a major problem.

However, thermal recording paper using a redox coloring system using a dye for recording materials represented by the general formula (I) of the present invention and a dibenzoylquinone derivative has problems in terms of storage stability of colored images and diversification of colored hues. It is useful to live there.

In addition, ultraviolet-sensitive materials constructed using the dye for recording materials of the present invention, particularly ultraviolet-sensitive materials used in free radical photography with organic halides, can be prepared using conventional leucotriphenylmethane compounds, such as EVA, leuco Compared to ultraviolet-sensitive systems using crystal violet, etc., it has much better heat resistance stability and indoor light stability before use, so it improves the workability of coating the ultraviolet-sensitive layer on the support and It has great advantages such as easier handling.

The dye for recording materials of the present invention is generally produced by the following method (IVI terephthaldialdehyde and (V) or (
Either by reacting an amine derivative such as the formula Vl1, or by reacting the penduhydrol derivative of the formula ■ with fV) ya (■
) It can be synthesized by reacting an amine derivative as shown in the formula.

(IV) (y) (-) (νID Various solvents are used as the reaction medium, but generally the reaction is carried out in an aqueous medium with a mineral acid as a catalyst, or in an organic solvent such as methanol. The desired product can be obtained by heating it as an acidic catalyst for a suitable period of time to cause a condensation reaction, and then making it alkaline to remove unreacted substances, and if necessary, purification such as recrystallization is performed.

The amine derivatives used in the reaction to obtain the dye for recording materials of the present invention include monomethylaniline, monoethylaniline, monobutylaniline, dimethylaniline, diethylaniline, N-methyl-o-)luidine, N-ethyl-〇- Toluidine, N-methyl-〇-anisidine, N-
Ethyl-〇-anisidine, N,N-dimethyl-In-anisidine, N,N-diethyl-In-anisidine, monobenzylaniline, N-methyl-N-benzylaniline, N-ethyl-N-benzylaniline, O- Kroll
N-benzylaniline, diphenylamine, N-methyl-diphenylamine, 2,5-dimethyl-N, N-dimethylaniline, 2,5-dimethoxy-N-benzylaniline, N-methyl-1-naphthylamine, 2-methoxy-1 -N~Methyl-naphthylamine, N,N-dimethyl-1-naphthylamine, N,N-diethyl-1-naphthylamine, 1-ethyl-2-methylindole, 1-
Butyl-2-methylindole, i-oc-y-ru-2
-Methylindole or 1-butyl-2-phenylindole.

In addition, benzhydrol derivatives include 1,4-bis-(α-oxybenzyl)benzene, 1,4-his-(
α-oxy-4'-methoxybenzyl)benzene, 1,
Examples include 4-bis-(α-oxy-4'-dimethylaminobenzyl)benzene.

Specifically, the dye for recording materials of the present invention is α.

α, α-α′-tetrakis(4′-methylaminophenyl)-1,4-xylene, α, α, α′, α′-tetrakis(4′-ethylaminophenyl)-,1,4-xylene .

α, α′, α′-tetrakis(4′-dimethylaminophenyl)-1,4-xylene, α, α, α′, α′-
Tetrakis-(4'-diethylaminophenyl)-1,
4-xylene, α, α, α′, α′-tetrakis-(3
'-Methoxy-4'-ethylaminophenyl) 1.4
-xylene, α, α, α′, α′-tetrakis (6′-
Methoxy-47-methylaminophenyl)-1,4-xylene, α.

α, α′, α′-tetrakis(3′-methyl-47-
ethylaminophenyl)-7L4-xylene, α, α,
α′.

α'-tetrakis(2'-methoxy-4'-dimethylaminophenyl)-1,4-xylene, α, α, α: α
'-tetrakis-(2-methyl-47-diethylaminophenyl)-1,4-xylene, α, α, α: α'-tetodikis-(4'-benzylaminophenyl)-1,4
-xylene, α, α, α; α′-tetrakis(4′-
methylbenzylaminophenyl)-1,4-xylene,
α, α, α', α'-Tetrakis-(4'-ethylbenzylaminophenyl)-1,4-xylene, α, α.

α', α'-Tetrakis-(4'-methylphenylaminophenyl)-1,4-xylene, α, α, α', α'
-tetrakis(3', 6'-dimethyl-47-dimethylaminophenyl)-L4-xylene, α, α, α',
α'-tetrakis-(3'-chloro-4'-hensylaminophenyl)-1,4-xylene, α, α, α',
α'-tetrakis-(3', 6r-dimethoxy-47
-dimethylaminophenyl)-1,4-xylene, α,
α, α′, α′-(3′,6′-dimethoxy-4′-benzylaminophenyl)-1,4-xylene, α, α,
α', α'-Tetrakis-(4'-methylamino-naphthyl-1')-1,4-xylene, α, α, α', α'
-tetrakis-(4'-dimethylaminonaphthyl-1'
)-1,4-xylene, α, α, α1α′-tetrakis(6′-methoxy-4′-methylaminonaphthyl-1
′)-1,4-xylene, α, α, α′.

α'-tetrakis(1'-ethyl-2'-methylindole-6fuyl) -1,,4-xin/, α, α
,α′.

α′-(1′-butyl-2′-methylindole-37
-yl)-1,4-xylene, α,α'-bis(4'-
dimethylaminophenyl)-α, α′-bis(4”-methoxyphenyl)-1,4-xylene, α, α′-bis(3′-ethyl-4′-ethylaminophenyl)-α,
α'-bis(4'-methoxyphenyl)-L4-xylene, α,α'-his-(3'-ethyl-4'-ethylaminophenyl)-α,α-bis-(4'-methoxyphenyl) -1,4-xylene, α, α'-bis-(4'-
dimethylaminophenyl)-α, α′-bis-(1′-
Ethyl-2'-methylindole-6fuyl)-1,
Examples include 4-xylene.

The dye for recording materials of the present invention is a pressure-sensitive copying paper or a heat-sensitive recording paper that uses a rapid and irreversible coloring reaction upon contact with a benzoquinone derivative, or an ultraviolet-sensitive color-forming material used in combination with an organic halogen compound. For example, it can be applied to printed circuit board forming materials, germicidal lamp indicators, etc. A recording material using the dye for recording materials of the present invention includes:
Compared to those using leucotrimethane compounds as leuco compounds, it has greater resistance to air oxidation color development and higher thermal oxidation resistance, making it easier to handle and reduce pressure. , color development by heat or ultraviolet light is quantitative and irreversible, and has excellent environmental stability. In particular, when used as pressure-sensitive copying paper or heat-sensitive recording paper, it is important to develop color images in a reversible equilibrium state between the currently widely used triphenylmethane phthalide or fluoran compounds and acidic substances, and to improve storage stability. The difference is extremely large.

When producing recording materials using these dyes of the present invention, various techniques known in the art can be used.

Hereinafter, the present invention will be explained in detail with reference to Examples and Reference Examples. The text middle part means the weight part.

Example 1 1.6 parts of terephthaldialdehyde, 5 parts of dimethylaniline
10 Tnl of concentrated hydrochloric acid was heated and condensed with stirring for 12 hours, made alkaline with 40% NaOH aqueous solution, steam distilled to remove volatile components, and the solid was passed through and dried. Recrystallization from 0-dichlorobenzene gives α,α',α'-tetrakis-(4'-dimethylaminophenyl)-1,4-xylene as a white powder with a melting point of 241.5-24°C and 5°C. Obtained.

Example 2 Terephthaldialdehyde 1.3*L 1-ethyl-2-
65 parts of methylindole (slight excess) and 5 parts of methanol
0.1 part of concentrated hydrochloric acid was added to 0.0 part of the mixture, and the mixture was mixed, stirred, and heated on an oil bath for 4 hours. After cooling, the white solid produced was filtered, washed with methanol, dried, and then recrystallized from 0-dichlorobenzene to form a white powder with a melting point of 254-256°C.
α', α'-tetrakis-(1'-ethyl-21-methylindol-6'-yl)-1,4-xylene was obtained. The elemental analysis values of this product were as follows.

Elemental analysis value CI-I'N Calculated value open 84,97 7.41 -y, s2 Actual value open 83.49. 7.48 7.28 Example 3-10 According to Example 1, the following compound was obtained.

Table 1 shows the obtained compounds and their melting points.

Reference example-1 α, α, α′, α′-tetrakis-(
Phenylxylylethane in which 6 wt. A microcapsule suspension with an average particle diameter of 8 μm and a solid content concentration of 18 wt% was obtained.

To 100 parts of this microcapsule suspension, an average particle size of 15
Mix 5 parts of μ wheat starch powder and 5 parts of a boiled oxidized starch solution with a concentration of 20 parts to make a uniform coating liquid, and apply the coating liquid onto pressure-sensitive copying paper using a Mayer bar coater, dry coating amount. is 5
A pressure-sensitive copying paper sheet of It'/rn' was obtained. This 2
,5-di-ethoxycarbonyl-4,6-di-p-4'
) When the pressure-sensitive copying paper bottom sheet containing rusulfonyl-1,4-benzoquinone as a color developer component was used to develop a color under pressure, it quickly turned into a deep green color (maximum absorption wavelength: 605 mμ).
) was obtained. The oxidized irreversible color image obtained in this way is extremely stable against the environment, and for example,
There was no observed tendency for it to disappear upon contact with polar solvents such as plasticizers or upon heating.

In addition, compared to leucotriarylmethane compounds, it generally has better resistance to air oxidation color development during storage, and stabilizers such as There was no need to use triethanolamine or the like.

Reference Example 2-6 The same procedure as in Reference Example 1 was used except that the compounds of Examples 1-4 and 9 were used to form microcapsules, and then pressure-sensitive copying paper was obtained.

This is converted into 2,5-di-butoxy-butoxybenzene.

When the colors were developed using a typewriter in combination with pressure-sensitive copying paper bottom paper containing 6-Gp-)・lylsulfonyl-1,4-penzoginone as a color developer, the dark hues shown in Table 2 were immediately obtained. A colored image was obtained.

Table 2 All of the colored images were extremely stable in the environment, and no tendency to disappear due to contact with aqueous solvents was observed. Furthermore, no natural coloring tendency was observed on the surface of the clay paper microcapsules.

Reference Example-7 α, α, α′, α′-tetrakis-(
Xandomill treatment was carried out using 4'-dimethylaminophenyl)-1,4-xylene with a composition of 20 parts of 10% polyvinyl alcohol and 20 parts of water to obtain a 20% aqueous suspension of microparticles.

On the other hand, 2,5-dibenzoyl-1,4- as a color developer
A water-based paint having the following composition was prepared using a 20% aqueous suspension obtained by similarly treating penzoquinone (17).

parts (dry solid content) 2.5-dibenzoylquinone 20 Stearic acid amide 10 Zinc stearate 05 Precipitated calcium carbonate 50 Polyvinyl alcohol 16 The dry coating amount of the above water-based paint was applied to neutral thermal base paper. , 1 was coated with a bar coater and dried to prepare heat-sensitive recording paper.

A voltage of 20 volts and a pulse width of 1.4+n5 ec was applied to this recording paper using a dot printer having a thermal head to obtain a green thermosensitive colored image. This color image is deep green, and the thickest absorption wavelengths are 430 mμ and 635Illμ.
The color image obtained in this way has excellent solvent resistance and light resistance, and is suitable for P
O8 heat-sensitive labels are useful for uses such as heat-sensitive commuter passes.

Reference Example 8-11 The compounds of Examples 2, 5, 6, and 10 were treated in the same manner as in Reference Example 7 to obtain heat-sensitive recording paper and to develop color.

The hues are shown in Table-6.

Table 6 All of them developed a deep hair color and had excellent environmental fastness.

Reference Example-12 Dipentaerythritol hexaacrylate 30 parts Hydroquinone (polymerization inhibitor) o, i Part 4-phenoxy-dichloroacetophenone 6 parts Mixable iQ/
The phenol obtained by adding vinegar and ethyl acid to adjust the viscosity was applied to a 1 mm thick polyester film to give a dry thickness of 30μ, dried at 105℃ for 10 minutes, and then dried. The membrane was made of 1 mil thick polyethylene film.

1-E: Remove the polyethylene film of the first resist, which was made using Lean Germany, and cover the exposed surface of the first resist with a button laminate (manufactured by Universal Oil Grodak). It was laminated on a clean steel surface and pressed with a rubber cover roll to make it denser.

Conductive 141: A high-contrast fluoro whose pattern is a transparent area with an opaque background is closely attached to the top (JAG film made by Arclight), and then a super high pressure mercury lamp (Oak made rupture) is used to conduct 150 mj/cnj of last week's When irradiated with ultraviolet rays, the UV-exposed areas were completely cured and developed a deep green color.

It was easily identified that each turn of the colored layer (of the turn mask film) was formed on the laminate.

After applying chlorocene effect to the unexposed areas and etching with a ferric chloride solution, a copper wiring pattern with the same pattern was obtained.

On the other hand, α, α, α′, α′-tetrakis-(4′
-Dimethylaminophenyl)-1,,4-xylene is replaced with leucocrystalline olenote (4,4',4''-trisdimethylaminotriphenylmethane), which is officially used for the purpose. The blue color of
2.5-dimethoxy-4-pendylaminopheni/l/
) −1. A solution 52 obtained by dissolving 710 parts of 4-4' sire was added to 99 parts of a styrene-acrylic copolymer emulsion with a solid content of 459 parts consisting of 65 parts of styrene as a matrix, 60 parts of butyl acrylate, and 5 parts of methacrylic acid. In advance, Zymanorub UV-1084 (manufactured by American Rhino/Nami I Co., Ltd.) as an ultraviolet absorber was added to the ultraviolet absorber-containing emulsion H-907 in a total of 1 press to remove free radicals. A yarn 11 composition containing 4-phenoquine-dichloroacetophenone + iooy was obtained.

Kono composition'l (Il 'a visit'F)ii Mino 0 0
Solid coating on f//I+12 high quality paper.
Apply so that rrj is 20i//+n2 and dry at 105℃ for 15 minutes (UV sensitivity/-
I got 1.

The purple one-ray sensitive sheet was used as a germicidal lamp manufactured by Sankyo Denki 1 (1), which has a wavelength of 254 mμ.
15) When I used A1 and irradiated it for 10 seconds at a distance of 1 cm, the ultraviolet irradiated surface turned green in a sensitive and non-n1 reversed manner. It is useful as a.

α, α, α′, α′-tetragysu (2′, 5′-
dimethoxy-4'-dimethylamine phenyl)-1.4
- When dimethylaminotriphenylmethane (1-dimethylaminotriphenylmethane) was used for xylene, the coating liquid had a strong tendency to color over time, and the coated paper also showed a tendency to color during storage under indoor light.

patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1) General formula (1) (wherein A, B, X, and Y each represent a phenyl group, a naphthyl group, or an indole-6-
When both 1-0A and B1X1Y are phenyl or naphthyl groups, it has at least one substituted amino group at the para position of -Cl-1-, and one or more substituents. lower alkyl group, lower alkoxy group,)
・It may have a rogen atom or an amine group.・) is a dye for recording materials.