JPS5831790A - Recording paper - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a pressure-sensitive or heat-sensitive recording paper having a support 1ζ containing a fluorane derivative bound to an electron-donating color former. More specifically, the present invention relates to the general formula (I) 1 (wherein is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group, a nucleus substituted with methyl or halogen, and C
A phenylalkyl group, an alkenyl group having 2 to 8 carbon atoms, a 1-rukoxylalkyl group or an alkoxyalkoxyalkyl group having 1 & s to 10 carbon atoms, or a phenyl group substituted with a halogen or an alkyl group and which may be C or C. represent.

几 is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxyalkyl group or an alkoxyalkyl group having 8 to 1 G carbon atoms, or a phenylalkyl group whose nucleus is substituted with methyl or halokene (4) represents a group.

Also, 几 and 8 are -o1ζ becomes C -(Oti2)p-, -(](ICH!OCiyu(3H
41 Taher01i20H1!80HICiH C may also be used to form a group. Here, p represents the number 4.6 or 6.

Ordinary is an alkyl group having 1 to 8 carbon atoms.
lys Alkoxyalkyl group or alkoxyalkyl group having 918 to 10 carbon atoms, phenylalkyl group whose nucleus is substituted with methyl or halogen, and which may be C or C, tetrahydrof? lephryl group,
Furfuryl group, cyanoethyl group, carboamidoethyl I
or a carbalkoxyethyl group. ) is used as an electron-donating color former, C support-ζ
Pressure-sensitive or heat-sensitive recording paper.

Sho recording paper and thermosensitive recording paper, which apply a coloring reaction caused by contact between an almost uncolored electron donating substance and an almost uncolored electron accepting substance, have evolved with the development of the current information age. Demand is increasing. General/ζ-pressure rutted paper is
An electron-donating white pigment (hereinafter referred to as a color former) is mixed with an organic solvent.
After dissolving ζ, a few microns of ζ are emulsified.

Microcapsules are made from a polymeric compound such as gelatin, and the support for this is E paper coated with H-Cζ, and the lower paper coated with an electron-accepting substance (hereinafter referred to as a color developer) F-+ζ. Then, by placing the coated surfaces of the two facing each other and applying pressure such as pen pressure, the C microcapsules are destroyed.
This is a recording method in which the color forming agent in the capsule is released and transferred to the color developing agent surface, causing a coloring reaction and obtaining a copied image. The most common type of thermal recording paper is one in which a color former and a color developer are supported in a binder (for example, a polymeric material such as polyvinyl alcohol) so that they do not come into contact with each other, and a C1 support is provided. There is a recording method in which at least one of the agent and the color developer melts and comes into contact, causing a coloring reaction and obtaining a C copy image.

In recent years, there has been a demand for color formers that can produce black images due to the need to obtain copies from recording paper that has a color reaction of 1 c" ms between a color former and a color developer through pressurization or heating. As for 1ζ, it is possible to obtain a black image even by mixing several suitable coloring agents with different hues, but it is possible to obtain a black image by mixing several coloring agents with different hues. Due to the difference in light fastness, water resistance, etc., the storage condition of recording paper Bone ζ C had a k point such as a change in hue. Development of dyes that can produce black images with a single coloring agent is progressing. However, no dye has yet been found that can produce a black image that is satisfactory in terms of exposure hue, fastness, self-color development, cost, etc.

The present inventors have discovered that the fluoran derivative represented by the general formula (I) itself is a white crystal with no coloration, but when it comes into contact with an acidic substance, it develops a black tone-ζ color, and has excellent light resistance, water resistance, and
ζIt was discovered that it is a useful pigment as a coloring agent for pressure-sensitive or heat-sensitive recording paper with excellent fastness.
The invention has been completed. Pressure-sensitive recording paper creation / ζ hit C is a solvent that dissolves the coloring agent, and C is dichlorobenzene, α-(8
, 4-dimethylphenyl)-a-phenylethane, methylnaphthalene, propylnaphthalene, butylnaphthalene, benzylbenzoate, 1,4-dibenzylbenzene, etc. can be used.

Encapsulation methods include the core cell pageron method using gelatin, the method of forming a film from the outer phase, and the interfacial polymerization method that utilizes a skin-forming reaction between the inner and outer phases.

In addition, the acidic substance C refers to clays such as acid clay, activated clay, and attabalgide, one or more phenols such as resorcinol, paraphenylphenol, phenol, cresol, and butylphenol, and novolac-type polymerization of H. There are also metal salts of benzoin, salicylic acid, and its derivatives.

The compound represented by the general formula (I) of the present invention is, for example, synthesized by C as follows.

First, a compound represented by the general formula (U) 1 (in the formula, 几 and 几 have the above-mentioned meanings), and a compound represented by the general formula (III) B represents hydrogen or an alkyl group having 1 to 4 carbon atoms.) Using a dehydration condensation agent, C1-
The reaction is allowed to take place at 6 to 90°C for several hours to several tens of hours. Next, the precipitate is injected into water, and the precipitate produced is separated in a furnace, treated with plucari, and then heated to form white crystals that have been colored by C. get it. When this is separated in a furnace, dried, and recrystallized, the fluoran derivative represented by the general formula (I) becomes a white crystal.
can get.

Another synthesis method is to combine the compound represented by the general formula (1) and the aminophenol derivative represented by the general formula (fV) (wherein B has the above meaning) using a dehydration condensation agent. (React at about -5 to 90°C for several hours to several tens of hours.

Next, the compound represented by the general formula (2) (wherein B and B have the meanings given in 1) is obtained by injecting ζ into water, neutralizing with alkali, and separating in a furnace.

Next, a compound represented by the general formula (D) is dissolved in an organic solvent,
By alkylation with basic halides, sulfuric esters, trifluorenes, phonic esters, methanesulfonic esters, phosphoric esters, or acrylonitrile, acrylic esters, acrylamide, etc., white crystals with a slight C1 color can be obtained. By recrystallizing this, a fluoran derivative represented by general formula (I) is obtained in the form of white crystals.

When synthesizing the compound of the general formula (I) or the general formula (V) from the compound represented by the general formula ([I) and the compound of the general formula surface or the general formula surface, the dehydrating agent C is sulfuric acid. ,
Phosphoric acid, polyphosphoric acid, etc. are used, but advantageously 85% to 1
00% strength sulfuric acid is used.

Also, CG as a recrystallization solvent! n-hexane, toluene, monochlorobenzene, chloroform, methylisobutyltetone, methylcellosolve, isobutanol, isopropanol, dioxane or. Ethylene glycol dimethyl ether and the like are used.

One or more of the color formers obtained in this manner are used in combination with C1 or other color formers to produce C pressure-sensitive or heat-sensitive recording paper by a conventional method.

The fluoran derivative represented by the general formula (I) used in the present invention is a compound that is not specifically described in the literature, and is colored by the color developer ζ and exhibits a deep black color.

The recording paper obtained using this color former has excellent storage stability, color development, light fastness, and water resistance. Sun
First, when pressure-sensitive paper or thermal paper using this color former is compared with one using a known black color-forming compound, the pressure-sensitive paper C shows less discoloration due to light than the capsule-coated paper, and also shows less color development. The image has excellent light fastness.Thermal paper - Tooi C has the major advantage that there is less discoloration due to the temperature and humidity of uncolored paper, and less discoloration due to temperature and humidity of the colored image, and less discoloration and fading due to photoelectricity. Has characteristics. Furthermore, when applied to multi-color thermosensitive recording paper, the color development is clear when heated, multi-color development occurs without color mixing, and the storage stability is also stable.

Next, some examples of the fluoran compounds of the general formula (I) used in the present invention are shown in a table. The hue indicates the color developed with a thin layer of silica gel.

-1Q- Next, the present invention will be specifically explained using examples. In the examples, the part represents the heavy hoe part.

Example 1 2.0 parts of a fluoran compound represented by the structural formula below was dissolved in α-(8,4-dimethylphenyl)-α-phenylethane (1001 + ζ), 20 parts of gum arabic, and 16 parts of water.
Add 0 parts of the solution and emulsify. 20 parts of acid-treated gelatin and 160 parts of water were added thereto, acetic acid was added under constant stirring to adjust the pH to 5, and then 50 parts of water was added to allow the coacel page oxidation to proceed. Add 1-carboxylic acid to Cp I (4,
4 parts, 4 parts of 87% formalin is added to form C dura mater.

The following operations are performed at 60c and ζC. Next - the system here is 10
The mixture was cooled to ℃ to promote gelation of the -thick liquid to remove the stiffness effect, add an aqueous soda solution to RPL (9+), and leave for several hours to form a capsule emulsion.Next. To this capsule emulsion was added 80 parts of fine cellulose powder and 10% ζ.
Mix 100 parts of dissolved oxidized starch aqueous solution, apply on paper 1ζ and dry C to make E paper.

When this upper sheet was layered with the lower sheet and pressure from a pen or typewriter was applied, a black color developed. In other words, when using paper whose surface is coated with phenylphenol 11 or when using paper whose surface is coated with acid-treated activated clay, black color is obtained. Clear letters appeared.

The pressure-sensitive paper mentioned above has a good shelf life and quick color development, and the colored characters can withstand light for a long time.
Pressure-sensitive recording paper C was prepared in the same manner as in Example 1.

When printing pressure is applied to the pressure-sensitive paper, black 1ζ develops.
child.

This pressure-sensitive paper had good storage stability, fast color development, and excellent light resistance and water resistance of the angular characters.

Example 8 80 parts of the fluoran compound represented by the above structural formula was mixed with 16
Disperse C using a sand mill in 0 parts of 1.0% polyvinyl alcohol aqueous solution and 65% water (component composition)
.

86 parts of bisphenol A, 10 parts of polyvinyl alcohol
% aqueous solution 10 IIS is similarly dispersed in 65 parts of water (referred to as component B). Mix 8 parts of component and 67 parts of component B, and make a ladder sheet that becomes approximately 5 f/- when dried. of human ζ
The resulting sheet could be used alone as a pressure-sensitive paper, and a stained black image was obtained when used as a thermal copying paper.

The thermal paper shown in the photo is a clean paper with no self-coloring property.
In addition, the coloring speed is fast, and the coloring characters have excellent light resistance and water resistance.

Example 4 A CS thermal paper was prepared in the same manner as in C1 Example 8 using the fluoran compound represented by the above structural formula.

This thermal paper did not have self-coloring property, the coloring speed was fast, and the light resistance and water resistance of the colored characters were excellent.

Example 6 Thermal paper was prepared in the same manner as in Example 8 using a fluoran compound having the structure E.

This thermal paper has properties similar to those of the thermal paper of Example 8, and C
there was.

Example 6 A strained C thermal paper was prepared in the same manner as in Example 8 using a fluoran compound having the structure shown below. This thermal paper is
It had properties similar to those of the thermal paper of Example 8.

Claims (1)

[Claims] General formula CI). ! [In the formula, a is an alkyl group having 1 to 8 carbon atoms, a phenylal*'' group in which the cycloalkyl group may be substituted with nuclear methyl or halogen, an alkenyl group having 2 to 8 carbon atoms, and an alkenyl group having 8 to 10 carbon atoms. The alkoxyalkyl group or alkoxyalkoxyalkyl group, Mashichi is a halogen or alkyl group at the nucleus! Ratio is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxyalkyl group having 8 to 10 carbon atoms or an alkoxyalkoxyalkyl group, or a phenylalkyl group in which the nucleus is substituted with methyl or halogen and C or C is also suitable. (EH
g-@r: は=Ok12CH280BzCkl
C may also form a z-group. Here, p represents the number 4.5 or 6. Is R an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group, or an alkoxyalkyl group having 8 to 10 carbon atoms?
or an alkoxyalkoxyalkyl group, an alkenyl group having 2 to 8 carbon atoms, a phenylalkyl group substituted with nuclear methyl or a halogen, which may be C or C, a tetrahydrofurfuryl group, a furfuryl group, a cyanoethyl group, a carboamidoethyl group, or a carboxyl group. Represents an alkoxyethyl group. )Recording paper.