WO1983003077A1

WO1983003077A1 - Color-developing sheet for use in no-carbon recording system

Info

Publication number: WO1983003077A1
Application number: PCT/JP1983/000066
Authority: WO
Inventors: Ltd. Mitsubishi Paper Mills
Original assignee: Torii, Takahiro; Senoh, Hideaki; Tsukahara, Hirokazu
Priority date: 1982-03-03
Filing date: 1983-03-02
Publication date: 1983-09-15
Also published as: DE3368231D1; EP0105376B1; AU1330983A; EP0105376A1; EP0105376A4

Abstract

A color-developing sheet for use in a no-carbon pressure-sensitive recording system, which has a color-developer layer containing synthetic activated clay and an alkyl, aryl or aralkyl ester of p-hydroxybenzoic acid, said synthetic activated clay being produced by acid-treating a clay mineral having a laminar structure comprising regular tetrahedron of silica to such a degree that the content of SiO2? becomes 82 to 96.5 wt % based on dry weight (measured after drying at 105?oC for 3 hours), bringing the resulting clay mineral into contact in an aqueous medium with a magnesium and/or aluminum compound at least partly soluble in the medium and, when this soluble compound is other than a hydroxide, neutralizing it with an alkali or an acid to form a hydroxide, to thereby introduce a magnesium and/or aluminum component into the acid-treated clay mineral and, if desired, drying the clay mineral.

Description

Technical Field of Developing Color Shot in Fine-Bridge Recording System

The present invention relates to a color developing sheet in a marker recording system, and more particularly to a color developing sheet having an inorganic color developing agent in the same system.

冃 Fang technology

A micro cuff containing a colorless electron-donating dye (hereinafter referred to as a color former) dissolved in a high boiling point solvent. A color sheet (hereinafter sometimes referred to as CB) having a layer containing cells on its surface and a developing sheet having a layer containing an electron-accepting acidic substance (hereinafter referred to as developer) on its surface. Combination of color sheets (hereinafter referred to as CF)]? No] ?, bringing both layers into contact and applying printing pressure]) Creating an image on CF The pong pressure recording system is well known.

Examples of the color developer include natural clay minerals such as acid clay, attapulgite, and clay as inorganic color developers; and acid clay, which is a montmorillonite clay clay mineral, with mineral acid. Activated clay and organic color developing agents treated only moderately include various phenolic compounds, nopol phenolic resins, and aromatic carboxylic acids. Valent metal salts are used. Although the above-mentioned clay mineral based inorganic developer has the advantage of speeding up color development, such a developer or such a developer may be used. -The color developing effect is rather reduced when the developed developer paper is stored for a long period of time in a particularly humid atmosphere, especially at high temperature and high humidity.)), The developer particles aggregate and disperse in water. However, there were drawbacks such as deterioration of the coating and difficulty in coating. Various attempts have been made to enhance the color-forming effect of CF using inorganic developers. Among them, motor down mode Li Russia Na I bet group clay mineral, force Oh Li Na wells group clay mineral, cell bio-La I bet - path, Li co-,, ls e chi-Bok group clay mineral or c ⁰ Mi · the Yoo La wells group clay minerals such how Yo i Ni, S i 0 ₂ content of the clay mineral, on a dry basis (drying for 3 hours at 1 0 5 ° G) having a layer structure consisting of tetrahedral of shea Li Ca The resulting clay mineral is treated in an aqueous medium with magnesium and / or aluminum which is at least partially soluble in the medium, so that the weight of the clay mineral is between 82 and 90.5 wt. When the soluble compound is other than hydroxide, the acid-treated clay mineral is neutralized with aluminum or acid so that the hydroxide is formed, if the soluble compound is other than hydroxide. By introducing a magnesium and / or aluminum component into the solution]? Also by system color developers are given El This TogaTomo color development ability of clear and dark color to c F (day JP 5 7 - 5 9 9 6 (2) No.).

According to the studies by the present inventors, the above-mentioned known color developer (hereinafter referred to as “synthetic activated clay”) is effective in improving the color-forming ability of CF and maintaining color-forming density under high humidity. As a drawback, this "synthetic activated clay" was used as a developer. It has been found that the light fastness of a color image in a developed sheet is rather reduced.

Disclosure of the invention

Therefore, the present inventors have sought a means for improving the light fastness of a color image in a developed color sheet using such "synthetic active clay". In the past, the addition of various known antioxidants (such as hindered phenyls) and UV absorbers had almost no effect. Expression

—General formula:

(However, in the general formula, R is an alkyl group, an aryl group or an arylalkyl group.)

In the first time it comes and the least for the one active amount of shown by Ru Ha ⁰ La one arsenide de o key sheet A Le co Lumpur E scan Te le compound of benzoic acid was added to the synthesis Katsu牲clay The light fastness of the color image is remarkably improved, and a practically excellent CF can be obtained without adverse side effects such as light yellowing on a white background (non-image area). With this knowledge, the present inventors have reached the present invention.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 and FIG. 2 are schematic views of the coating liquids prepared in Example 3 and Comparative Example 4 according to the present invention, respectively.

O PI BEST MODE FOR CARRYING OUT THE INVENTION

Preferred examples of the para-hydroxybenzoic acid ester compound used in combination with the “synthetic activated clay” are as follows:

Para-hydroxybenzyl benzoate,

No. ^0- Hydroxy shoulder, Ortho-Methyl Penzil, No. La - hydroxycarboxylic depreciation Tang, Kosan Nono ⁰ La - click furnace opening Baie Njiru, Roh La one human mud key shea weaker shoulder, Kosan'o Le door - click furnace port base down di Lumpur, Nono. La-hydroxybenzoic acid phenethyl,

Nora-hydroxy, harm, phenyl benzoate,

No. ^0- Hydroxybenzoic acid. La methyl fir, no. La-hydroxymethyl benzoate,

Para-Hydroxyethyl benzoate,

Para-hydroxybenzoic acid n-f. Mouth pill,

Nora-hydroxy shoulder, perfumic acid is0-f. Mouth pill,

Para-hydroxybenzoic acid n-butyl,

Para-hydroxybenzoic acid iso-butyl,

Nora hydroxy benzoic acid sec-tyl,

Nora-Hydroxybenzoic acid 2 — Ethylhexyl.

The synthetic activated clay used in the present invention is derived from a clay mineral having a layer structure composed of tetrahedrons having a series of forces, and

(A) Electron diffraction shows a diffraction pattern based on the crystals of the layered structure consisting of tetrahedrons of the silica, (B) According to X-ray diffraction, diffraction based on crystals having the above-mentioned layer structure. Without showing the turn,

(C) As an element other than oxygen, it contains at least silicon, magnesium, and z or aluminum.

This is a color developer for pressure-sensitive copying paper.

The developer for pressure-sensitive copying paper of the present invention satisfies the above conditions (A), (B) and (C), and furthermore

CD) In terms of atomic ratio of calcium and magnesium and / or aluminum,

[Silicon] Z [magnesium and / or aluminum

1 2 Z 1.5 to 1 2

The ratio, especially

[Casic] [Total of magnesium and / or aluminum] is 12 3 to 10

It is preferred that they are contained at the following ratio. However, the sum of magnesium and aluminum in the above ratios means that only one of mag, magnesium or aluminum is contained. If not present, the atomic ratio of either one is shown.

Those satisfying the above conditions are preferred.

According to the study of the present inventors, the so-called activated clay which has been mainly used in the past is less than the acid acid clay which is a montmorillonite-based clay mineral than mineral acid. Moderately processed acid-soluble cations such as iron, magnesium, magnesium, calcium, aluminum, aluminum, etc. which are naturally present are extracted and removed to some extent. Nevertheless, it is a silicic acid anhydride with a residual amount of these cations remaining, and has an acid strength of PKa-5.0, one-3.0 and PKa- + 0.8, Each of the +0.8 and PKa +4.8 acid sites (these acid sites are derived from the presence of contaminating metal cations), and the crystal nodule tracks When a colorless dye is adsorbed, electrons are transferred and the ions are turned on to form a color image. A representative example is activated clay made from Japanese acid clay, such as Silton M-140. (Manufactured and sold by Mizusawa Chemical Industry Co., Ltd.). Can be

On the other hand, a typical example of the “synthetic activated clay” used in the present invention is a product made by Mizusawa Chemical Industry Co., Ltd., which is a product of Silton SS-. Strong acid sites of -5.0 and Pa +0.8 were not observed, and instead +0.8 and PKa +4.8 and +4.8 The weak acid point of PKa +9.0 is remarkably recognized, and is different from the conventionally known and officially used activated clay. This could explain the strong chromogenic ability to bioreductones.

The CF according to the present invention is produced by a known method. That is, the para-hydroxybenzoic acid ester and the synthetic activated clay are dispersed in water together with a known adhesive, dispersant, and auxiliary agent, and the resulting mixture is coated on paper and dried. ' The CB used in common with the CF is a colorless dye that contains an electron-donating colorless dye, for example, a crystalline hydrocarbon solution of crystal noreva or iolet tractone. ° It is preferred to have a cell layer on the surface. The fact that the aryl or the aromatic nucleus of the aryl group of the above benzoic acid ester compound has a high affinity for the aromatic hydrocarbon solvent indicates that the coloring speed is high. This is one of the reasons for the improvement in color density and color density.

Next, preferred embodiments of the present invention will be specifically described with reference to representative examples. Hereinafter, all “parts” are by weight.

Example 1

Benzyl para-hydroquin benzoate 100 parts

Hydrokishechinoresenore mouth part 5 part

Water — 1 45 parts

250 copies in total

Was ground with a poll mill for 2 days.

100 parts of “Synthetic Activated Clay” (trade name: Silton SS-1) manufactured by Mizusawa Chemical Industry Co., Ltd. and the wet-ground pulverized Nora-hydroxybenzoic acid benzyl 50 parts of the liquid was dispersed in 200 parts of water in which 1 part of sodium pyrophosphate was dissolved, and 50 parts of a 10% aqueous solution of oxidized starch and 48% of SBR-latex And 50 parts of the solution were added to obtain a coating solution. This coating solution was applied on a 0 ^ base paper so as to have a dry coating amount of 7 / ^ ^2, and a CF sheet was used (sample code B).

ΟΜΡΙ Also, C instead of ^0- hydroxy benzoic acid benzyl. Methyl lahydroxybenzoate was used as a CF sheet (sample code C;).

For comparative tests, Bruno, ⁰ La - arsenide mud key sheet benzoic bae down di Le all Ku added nor of (. That is, as a color former synthetic activated clay only the even samples symbol A), or Alternatively, CF using the same amount of bisphenol A (symbol D) was also prepared.

For C B,

Cristal Noorect Tracton 4 copies Beninorello I Commethylene Bunolé 1 copy

5 1-ethylamino-ό-methyl-Ί-anilino

0.5 parts of Fluoran Jisof. Mouth pilnaphthalene 100 parts

(Product name KM C to be manufactured and sold by Kureha Chemical Industry)

A solution of an electron-donating colorless dye consisting of a solvent in a high-boiling aromatic hydrocarbon is microencapsulated according to US Pat. Cro force. To 100 parts of the cell (dry base), 25 parts of wheat starch and 150 parts of a 10% aqueous starch solution were added, and the amount of dried cloth was reduced to 59 / ^ ^{2 on} 40 base paper. The CB applied so as to be used was used.

To each of the CF samples (four types) obtained by shaking

First, apply the medium pressure calender — (buff; pressure is in the pen pressure range). Apply the CB so that the application surfaces face each other, and then apply the pressure after 1 minute, 1 hour, and 24 hours. Color intensity of each CF surface The reflectance was measured using a Nippon Denki Colorimeter and calculated from the following formula.

Color density () = X 100

The reflectance of the white background was measured (Table 1). As a result, in the samples (B) and (C) of the combination according to the present invention, the concentration after one minute is particularly high.] This indicates that a dark copy can be obtained quickly when writing. This is what is very favorable for practical use.

Next, in order to obtain a color image having a saturated color density, a high-pressure calendar is applied to each combination of CB and CF (a single calendar and a single calendar). After one day or more, use a power-on arc lamp (carbon arc lamp feed meter, 1 hour treatment) or an oxidizing gas in air (1.50 ppm 10 minutes) During the exposure to NOx gas, each exposure test was performed. The color image density was measured by measuring the reflectance with a color difference meter, and the reflectance of the colored part after processing was calculated from the following equation.

Color image density) = X 1 0 0

Reflectance of colored part before processing ―

(Table 2). As a result, in the samples (B) and (C) of the combination of the present invention, the fastness against light and NOx gas is much higher than that of the synthetic activated clay alone]. It turns out that there is no inferiority to the examples. Table Ί

Medium-pressure calender-pressurized color speed and reached color density

Table 2

Robustness of high-pressure calender pressurized color image (survival rate in Kakko)

Then, perform a sunlight or nitrogen oxide gas exposure test to see the deterioration resistance (stability) of the white background of the developed color sheet. Regarding the sunlight resistance of the white background, the white background of the developer sheet was exposed to direct sunlight for 4 hours, and the reflectance () was measured with a Darloo filter of a color difference meter. Also, regarding the nitrogen oxide gas resistance of the white background, the white background of the developer sheet was exposed to 500 ppm of Νθχ gas for 20 minutes, and the color difference meter was filtered with a filter. The reflectance ()

1

It was measured. (Table 3).

From Table 3, it can be seen that the developed color sheets (B) and (c) used in the present invention have very little deterioration by light or oxidizing gas in the air (that is, the shelf life of the product is long). On the contrary, when the synthetic activated clay of a specific example is used in combination with bisphenol A (sample D :), the light is still higher than that of j? NO _∑. It was found that the gas caused severe yellowing.

As described above, the CF according to the present invention has a large color development speed (Table 1) and a robust color image.] (Table 2), and the white background is hard to yellow. (Table 5) It can be seen that a pressure-sensitive recording system is provided. Synthetic activated clay and bisphenol

In Comparative Example D in which A was used in combination, the color image was certainly very fast (Table 2), but the white background was very easy to yellow (Table 5), so it was practical and useful. δ

Colored sheet Yellowing on white background

In addition, when a crystal pallet or an ollet tractone for single flight is used for C Β, the stability of the color image (both light and 対) is further improved. did.

The bleaching with nitrogen oxides in this example depends on the test method for the color fastness to dyeing of nitrogen oxide gas of Jes L0855. 1-Nitric oxide gas is generated. Add 300 ml of sulfuric acid adjusted to a specific gravity of 1.05 into the gas generator, and add a saturated solution of sodium nitrite 10 dropwise.

Put in funnel and drop into sulfuric acid to generate nitrogen oxides, trap of 10 sodium hydroxide solution. After passing the developer sheet into a desiccator, nitric oxide gas is injected so as to reach a predetermined degree of dispersion (ppm). Exposure was observed for 20 minutes.

The CF of the present invention can further prevent yellowing due to light on a white background and a nitrogen oxide by adding an inorganic or organic ammonium salt to the color developing layer. it can. these Examples of ammonium salts of 1δ are as follows, and at least one of them is added in an amount of 1 to 100 parts by weight with respect to 100 parts of “synthetic activated clay”. By doing so, the intended purpose can be achieved.

Ammonia acetate, ammonium formate, ammonium η-butyrate, ammonium oxalate, diammonium citrate, quanium phosphate Sanya down mode -. © arm, tartaric two A Nmo two ©-time, saw blade click San'a down mode two ©-time, academic and San'a down mode two ©-time, horse mackerel ^non-zero Nsan'a down mode - © Ammonium, ammonium disodium, ammonium phthalate, ammonium benzoate, ammonium salts of organic acids such as ammonium chloride; ammonium chloride Monium, ammonium sulfate, ammonium nitrate, ammonium carbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium persulfate, lithium sulfate Example 2 Inorganic acid ammonium, such as ammonium phosphate, diammonium phosphate, triammonium phosphate, etc.

After adding 0.5 part of sodium pyrophosphate to 120 parts of water and dissolving it, "Synthetic Activated Clay" which is an inorganic color developer (manufactured by Mizusawa Chemical Co., Ltd. ss-1) 10 parts by weight were added gradually with stirring and dispersed, and then the following dispersion of para-phenyl pi-benzoic acid benzoate was added.

ベンジル Benzyl para-hydroxybenzoate 100 parts

Hydro-Kishechinoresenore Pi 5 Water 1 4 5 parts

250 parts in total

Was ground in a ball mill for 2 days

Ο ΡΙ 5 0 parts stirred added, to which 1 0 Per Se down gate oxide Devon Pung (Nippon Food fei Ltd., MS - 5 8 0 0 :) aqueous 1 0 0 parts 4 8 C ⁰ Ichise down bets scan switch Les down-porcine di e down La Te-click scan (Asahida cormorant made, DOW 0 7 0) After the added 2 0 parts of dispersion, 2 5 Nono ⁰ - Se emissions door chloride Ryo down mode two © anhydrous solution Was added and the mixture was sufficiently stirred, and the pH was adjusted to 8.5 with a caustic soda to obtain a coating solution. The coating solution was applied to 40 ^ no ™ ² high-quality paper 'using a Nichifu-Nife coater so that the coating amount was 5.5 ^ / ^ (solid content).

Comparative Example 1

Water in 120 parts of water. Sodium phosphate is added to 0.5 part and dissolved, then 100 parts of “Synthetic activated clay (SS-1)” is gradually added with stirring and dispersed, and then 10 parts 100 parts of an aqueous solution of oxidized starch (MS-580), 487-cent styrene, and 2 parts of Tajene latex (Dow 670) After adding 0 parts and stirring thoroughly, the pH was adjusted to 8.5 with a caustic soda to obtain a coating solution. Apply this coating liquid

4 0 g / r ^ coating weight on a high-quality羝of was coated with 5.5 9 / -m ² d to the jar by Ru and (solids) A one Na Lee full co-COMPUTER.

Comparative Example 2 '' After adding 0.5 parts of sodium phosphate and dissolving, 100 parts of "semi-synthetic solid (ss-1)" was stirred and gradually added and dispersed. 50 parts of a hydroxybenzoic acid benzyl dispersion was added to the mixture, and the mixture was stirred. (MS-5800) Aqueous solution 100 parts 4 8 no. Apply 20 parts of 1st styrene 'butadiene latex (DOW 670) to the mixture, stir well, and adjust the pH to 8.5 with a caustic soda. Liquid. Apply this coating solution to 4 (9 / ^ ^z ) high-quality paper at an amount of 5.5

(Solid content:) ', applied with an air knife coater

The developed sheet obtained as described above was tested and measured by the following methods. The color of the color developing sheet was developed by passing the color developing sheet through the power render with a pressure of 9ό ^ cm ² together with the color former sheet. The reflectance (percent) was measured with a meter (hereinafter referred to as a color difference meter), and the following values were measured. Colored part reflectance

Color density (percent) = X100

White background reflectance

(Reflectance 1 hour after passing through the calender ^) Color image © Sunlight resistance. Combine with the above color former sheet (colorless dye ner sheet) and pass through the calendar. The developed sheet was exposed to direct sunlight for 1 hour, and the residual density was measured for reflectance (percent) using a color difference meter, and the following values were obtained. Reflectance of colored area after sun exposure

Sunlight resistance (percent) = 100 Reflectance of white background after exposure to sunlight Moisture resistance of color image

The developer sheet developed through the above calendar is humidified in a 50 x 95 iH constant temperature and humidity chamber for 4 days. The residual density was measured for reflectance (percent) using a color difference meter. The following values were obtained.

Reflectance of colored part after humidity control

Moisture resistance (C ⁰ - cents) = X 1 0 0 white background reflectance耐漦of nitrogen gas after詾湿developer that was developed by passing mosquitoes les down Dark-in (N0shiguma gas) of the The sheet was exposed to 600 ppm of NO s gas for 1 ζ min, and the residual concentration was measured for reflectance (percent) using a color difference meter to obtain the following values.

反射 Reflectance of colored part after gas exposure Nitrogen oxide gas resistance (C-cent) = 100

反射 Reflectance of white background after gas exposure Sunlight resistance of white background (non-image area) White background of color developer sheet is exposed to direct sunlight for 5 hours, and the color difference meter The reflectance (percent) was measured with a router.

Nitrogen oxide gas on a white background (exposed the white background of the heat-sensitive coloring agent sheet to 100 ppm of Νθχ gas for 30 minutes, and reflected with a blue filter of a colorimeter. Rate (percent) was measured.

Table 4 shows the fading resistance of the color image. The following values are reflectivity! ), The smaller the value, the higher the concentration. Four

Table 5 shows the yellowing resistance of the white background. The following values are the reflectivity of the pull-filter. The higher the value, the less yellowing. Table 0

As shown in Tables 4 and 5 above, para-hydric oxybenzoic acid ester compounds and ammonium salt compounds were added to the colorless developer developing sheet of the present invention. 9) In particular, the color image is excellent in sunlight resistance, moisture resistance, and oxidation gas resistance, and almost completely prevents yellowing due to sunlight and nitric oxide gas on a white background. To provide the inventor, etc. with a truly excellent product as a color developing sheet for image recording materials. I was able to.

The coating solution containing synthetically activated clay used in the production of CΈ according to the present invention is extremely high in viscosity, and has high workability when applied to paper. It drops significantly.

In terms of specific surface area, this is because the activated clay, which is a well-known and publicly used clay mineral-based developer, has an aromatic adsorption index of 30. The specific surface area is clearly large, with an aromatic adsorption index of 58, so that a large amount of water is required in the preparation of the coating solution, and it is clear that the liquidity is poor. Therefore, a large amount of water is required at the time of preparing the coating liquid, and the coating liquid has a high viscosity and has a tendency to become gelled. When applied with a ruco-tar, m-p-co, etc., a character break (streak :) occurs on the surface of the coated sheet, resulting in poor smoothness. May be exposed and the practical value of the product may decrease.

This disadvantage has been solved by the present inventors] by adding an inorganic filler to the coating solution.

That pie as a flow improver in a High Concentration of coating solution (solid content 4 0 wt or more) B off I la wells (AJ £ ₂ O _S.

ASi0 _₂ .2H ₂ 0) force Oh Li Na wells (AJ¾ ₂ 0 ₃ · ₂ Si_〇 _₂ · _{2Η 2} 0), C B A support wells (Aja ₂ 03'2 Si02 -4H20), Se Li Size Lee Doo _{_{_{(2 0. A ^ 2 0 3}}} - 6 Si0 2 .2H 2 0), mode emission mode Li port Na wells _{(AJ¾ 4 [Mg] (Si} 8 0 20 (.0Η) 4 .ΣΗ 2 0: ) Which Cray, 1-Aluminum hydroxide, aleurone, choke, heavy carbon dioxide

-From inorganic fillers such as calcium carbonate, such as precipitated calcium carbonate, which is simulated and light, ultra-fine, and ultra-fine activated, sub-sublime, diacid titanium, etc. Use at least one selected from the following groups and use it together with “synthetic activated clay”.

In the present invention, the combination ratio of the “synthetic activated clay” and the inorganic filler is preferably from 50% by weight to 70% by weight to 95% by weight to 5% by weight, particularly preferably 50% by weight to 50% by weight. Weight to 85% by weight to 15% by weight. "Synthetic active clay" If the power is less than 30% by weight, the coloring performance is remarkably deteriorated. If it is not practical, if it is more than 90% by weight, a high concentration and low viscosity coating liquid cannot be obtained.

As shown in the present invention, an inorganic filler such as the above-mentioned clays, aluminum hydroxide, calcium carbonate, zinc oxide, zinc white, A coating solution containing an effective amount of at least one of titanium and the like added together has an extremely high fluidity, and the pallet: 7 ° fiber is not exposed even on a sheet coated with a pine tree.輊量coating (versus the paper - the teeth 5 ^ Z w ² below) to enable. As a result, the amount of desensitizing ink used during printing is small and ink drying is fast, so speedy printing of printing presses. One of the major advantages of the present invention is that it has a great advantage in cost down in terms of productivity improvement and energy saving due to small application amount. That's it.

ΟΜΓΙ

κ grace In the following examples, the color former sheet is commercially available.

As a CB for Bon Copy Paper, "Mitsubishi NCR-For 40 Blue" (Dye is Crystal Violent Tractone (GVl and Benzyl P-methylene) BLMB) 3) was used.

Comparative Example 3

After completely dissolving 0.5 parts by weight of sodium hexam- inate in 90 parts by weight of water, 10% denfoxide was added. 50 parts by weight of an aqueous solution of an aqueous solution were mixed with 15 parts by weight of a powder of oligarite (manufactured by Engelhard Co.), and aluminum hydroxide of the powder (Showa Denko 5 parts by weight) and 10 parts by weight of powdered slightly precipitated calcium carbonate (manufactured by Shiraishi calcium) were gradually added with stirring, and dispersed well. Activated clay ”(Mitsuzawa Chemical Industry Co., Ltd. ss

-1) 60 parts by weight were gradually added and dispersed well, then the styrene and tagen latex were added in 2 Q parts by weight (solid content), and the mixture was stirred well and dispersed. The coating liquid was adjusted to pH 8.5 using a Nocent Case Soda. Apply this coating solution 40

/ ² base paper with a blade coater so that the coating amount is 4.5 g / ^mz (solid content) to obtain a developer sheet.

*

Example 3

A solution prepared by completely dissolving 0.5 parts by weight of sodium hexametharate in 90 parts by weight of water and then mixing 50 parts by weight of a 10% aqueous solution of dendrite-phenylene oxide. Same as Comparative Example 3 The same amount of the same inorganic filler was added, and the mixture was stirred and dispersed well. Then, “Synthetic activated clay” (manufactured by Mizusawa Chemical Industry Co., Ltd.) (ss-1) was added gradually to about 0 parts by weight, and the mixture was dispersed well and then added to the para-hide. Pencil benzoyl benzoate 100 parts

H ρ mouth-

Water 1 4 5 layers:: part

250 total: parts

Is milled for 2 days with a pole mill. 50 parts by weight of the above-mentioned wet-ground p-hydroxybenzoic acid dispersion were added, and the mixture was stirred well, and then the styrene and the Tajene latex were added to 2.0 parts. parts by weight (solids) added by rather stirred dispersed after 2 0 Pas one cell down preparative mosquito cell I source - and the Eta _[rho at da and a 8.5 coating liquid. Apply this coating solution to 40 ^ Ζ

The base paper was coated with a blade coater so that the coating amount was 4.5 ^ Ζ ^ ² (solid content) to form a developer sheet.

Comparative Example 4

After completely dissolving 0.5 parts by weight of sodium hexamethacrylate in 90 parts by weight of water, 10% denfoxide is obtained.

100 parts by weight of “synthetic active clay (ss-1)” was gradually added to a solution obtained by mixing 50 parts by weight of an aqueous solution of sodium chloride, and the mixture was stirred well, and then the styrene, styrene, It was E down La Te click vinegar 2 0 parts by weight of _Η Ρ in (solid) good Ku stirring dispersed the Chi 2 0 path over cell down door force cell Lee Seo one da and 8.5 coating liquid. Apply this coating liquid

The amount of cloth applied to the base paper of 409 / is 4.5 9 / ^ ^ζ (solid content ^ r ^ TTT It was applied with a blade coater to obtain a developer sheet so that

Test method

The 7t coating solution and the developer sheet thus obtained were tested and measured by the following methods. (1) Coating liquid

Ί) Viscosity

Using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.), the value (cps: centipoise) after 1 minute at 00 rpm was measured using π-tar 4. Further, the viscosity curves of Example 1 and Comparative Example 1 were determined using a Harcures II type No., a shear-vis commuter (manufactured by Nihon Rigaku Kogyo Co., Ltd.).

(2) Developer sheet

) Color density

Combine the chain-colorant sheet with the above color former at 9 ό / cnfi pressure and reflect it with a Nippon Denki Colorimeter with the colorimeter of a developer sheet colored through a power render. The rate ^ was measured and the following values were measured. Colored part reflectance

Color density-X 1 0 0

White background reflectance

(Reflectance one hour after passing through the calendar)

TP mouth

(1) Coating liquid

Table III shows the viscosity, solid content, and state of the coating liquid used in Example 3 and Comparative Examples 3 and 4. Examples 5 and The viscosity curves of the coating solutions of Comparative Example 4 and Comparative Example 4 are shown in FIGS. 1 and 2, respectively. No. £>

In Table 3], compared to Comparative Example 4, Example 3 of the present invention has substantially the same solid content, but has a drastically reduced viscosity and very good fluidity. In addition, in FIG. 1 and FIG. 2, it is apparent that Comparative Example 4 has a higher viscosity at a higher rotation speed than that of Example 3 and a high viscosity even at a low rotation speed. It has gelled.

(2) Developer sheet

Table 7_ shows the densities developed through the above calendar. In Comparative Example 4, the color density was slightly lower, and the removal was consistent with the visual result that there were many uncolored portions and many white spots. '

7 Table

_OMH As shown in Tables II and III, and Figures 1 and 2, inorganic synthetic fillers such as clays, aluminum hydroxide, carbonic acid rubber, etc. are added to "synthetic activated clay". The developer sheet is excellent in flowability by using it in combination, and it is possible to apply the amount of syrup without any problem. It was possible to obtain something that did not end up exposing the fiber. In addition, By adding la-hydroxybenzoic acid pen, an even more excellent developer sheet was obtained.

Claims

• 1. The clay mineral having a layer structure consisting of tetrahedral of shea Li force, Si0 ₂ content in the gas and dried for 3 hours at 1 0 5 1C

And the resulting clay mineral is treated in an aqueous medium with at least a portion of said clay mineral in an aqueous medium.

One person

Contact with an electrically soluble magnesium and / or aluminum compound, and if the soluble compound is other than a hydroxide, an aluminum alloy is formed to form a hydroxide. Or neutralized with an acid to produce magnesium and surroundings in the acid-treated clay mineral.

And / or by introducing an aluminum component, if desired]? Synthetic activated clay and a formula produced by drying.

(Wherein, R represents a group selected from the group consisting of an alkyl group, an aryl group and an aryl group). A color sheet in a pressure-sensitive pressure-sensitive recording system characterized by having on its surface a layer of a color developer containing a benzoic acid ester compound.

2. The developing sheet according to claim 1, wherein the para-hydroxybenzoic acid ester compound is para-hydroxybenzoic acid benzyl.

5. The developing sheet according to claim 1, wherein the layer of the developing agent further comprises an ammonium salt.

4. The color developing sheet according to claim 5, wherein the ammonium salt compound is ammonium chloride.

5. The color developing sheet according to claim 3, wherein the layer of the color developing agent further contains an inorganic filler.

ό. Claims 1, 2, 3, 4, or 5 wherein the electron donor is used in combination with a coloring sheet in which the electron donor is a crystal pi-cret tracton. Developed sheet.

OMPI