WO1983002427A1

WO1983002427A1 - Pressure-sensitive recording sheet

Info

Publication number: WO1983002427A1
Application number: PCT/JP1983/000001
Authority: WO
Inventors: Ltd. Mitsubishi Paper Mills
Original assignee: Tsukahara, Hirokazu; Torii, Takahiro
Priority date: 1982-01-09
Filing date: 1983-01-07
Publication date: 1983-07-21
Also published as: JPH0326150B2; JPS58119890A

Abstract

A pressure-sensitive recording sheet having in combination a color developer comprising a silica-magnesia solid acid prepared by acid-treating acid clay to nearly completely remove aluminum ion and adjust the aromatic adsorption index to 40 or above and then introducing a substantial amount of magnesium ion thereinto and one or more of hydroxybenzoates represented by the following general formula: <IMAGE> wherein R represents alkyl, aralkyl or aryl, and -COOR is in an o- or p-position with respect to -OH, and microcapsules containing a colorless basic dye as a color former. This sheet undergoes no deterioration of the color developability with time, and provides a color image resistant against discoloration due to nitrogen oxides or light.

Description

Fine pressure recording sheet technology

The present invention relates to a pressure-sensitive recording sheet. More specifically, the present invention relates to an acid-treated clay, which is capable of almost completely removing aluminum-umion and has an aromatic adsorption index of 40 or more. After that, it is concerned with the improvement of color image storage of pressure-sensitive recording sheets that use a series of magnesium-based solid acids containing a substantial amount of magnesium ion as a color developer. It is a thing. Background technique

The pressure-sensitive recording sheet is generally composed of an electron-donating organic colorant (hereinafter referred to as a crystalline pigment), represented by a crystalline lactone, pentylcomethylene, or the like. , A color former), a montmorillonite-type clay mineral (hereinafter referred to as activated clay), which has been activated by acid treatment to increase its activity, a phenol compound, and an aromatic compound. It is based on the principle of developing a color by reaction with an electron-accepting color developer (hereinafter referred to as a color developer) such as a phosphoric acid or its metal salt. Lo cuff. The top paper with cells coated on one side of the base paper, the above-mentioned mouth-opening case and the middle coat with the color developer coated on different sides of the same base paper, appropriately combined according to the purpose of use Copying can be obtained by applying pressure with a pen or typewriter.

OMPI one O

Further, there is also a so-called self-contained paper in which the microcapsule and the developer are applied to the same surface of a base paper.

In the pressure-sensitive recording sheet, active-white clay is most commonly used as a color developer. This activated clay reacts well with the color former, and has the property of producing a deeper color, but the color developing ability has decreased over time? In addition, the color image is discolored due to nitrogen oxides and the like when left naturally. In other words, in order to make the most commonly used crystal pie, a reticulactone, which is the most common coloring agent, develop a blue-violet color with the highest concentration between the activated clay and the activated clay, the acid of activated clay is used. The strength is too strong. For this reason, there has been proposed a method of adjusting the fine clay side by adding an alkaline substance when adjusting the coating of active clay. However, over time, the effect is often lost due to the sulfuric acid band in the recrystallized base paper.

When amides are contained, not only neutralize the acid sites of the strong acid portion of the activated clay, but also the acid sites of the weak acid portion that contribute to the color development reaction. Wash and activated clay

There is a problem that the color developing function is deteriorated. The drawback of such a color developing sheet is that the acid clay is further treated with an acid to remove almost all the aluminum ion and to give an aromatic adsorption index of 40 or more. Mirion introduced Silica

f OMFI Magnesia-based solid acid (hereinafter simply referred to as “silicone / magnesia”) can be used as a color developer.] 経時 With time, the decrease in color development performance can be improved to some extent, but color development The durability of the image to discoloration by nitrogen oxides or light fading when left unattended was insufficient. Disclosure of the invention

An object of the present invention is to provide an excellent pressure-sensitive recording sheet in which the above disadvantages are improved. This object of the present invention has been attained by using a combination of a magnesium acetic acid and a hydroxybenzoic acid ester compound as a color developer. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

The ferrite, mug, and nescia used in the present invention require a step of acid-treating a monmite-type night-type clay mineral.

X ^m (Y ^{2 +} , Y ^{3 +} ) ₂ ~ ₃ Z ₄ 0 ₁₀ (H0) ₂ .SH ₂ 0

Where X = Κ, Na, Ca

Υ ^{2 +} : Mg ^{2 +} , Fe ²⁺ Mn 2 + Ni ^{2 +}

Y ^{3 +} : Α £ ^{3 +} , Pe ³⁺ Cr ^{3 +} Mn ^{3 +}

Ζ: Si, Α £

The average value of m is 1/5

S is the number of interlayer water

(_Ο ΡΙ Indicated by This is described on page 80 of the Clay Handbook (edited by the Clay Society of Japan, Gihodo). Among these clay minerals, it is desirable that the acid clay should have an A content of 5 to 30 parts by weight with respect to Si 100 parts by weight. When monmorillonite-type clay mineral is treated with sulfuric acid or hydrochloric acid, firstly, ion, Mg ion, and ion are eluted. Next, ion is eluted, and the iron / magnesia used in the present invention is one that has been subjected to treatment until the ion is substantially and completely removed.

The aromatic adsorption index of the treated clay at this time must exceed 40. Here, the aromatic adsorption index is an index that reflects the degree of adsorption capacity or activity of treated clay. Also, it is used as an index that indicates the degree of the specific surface area of the treated clay for convenience. The aromatic adsorption index of 40 or more means that the activated clay used as a developer outside the present invention has an aromatic adsorption index of 2 C! ~ 40 · is very active]), which means that the specific surface area is very large, and furthermore, the crystal bioreactor This indicates that the number of acid sites in the weak acid portion contributing to the color development is increased. It also shows that the effect of the acid strength given by the sulfuric acid band in the base paper over time is unlikely to occur.

The aromatic adsorption index is determined by the following method. The ground sample is dried at 150 ° G soil 5 deg. For 3 hours and allowed to cool to room temperature in a desiccator. This dried sample

1.0 ^ ^ into a container]) 50 volumes of dehydrated toluene and dehydrated iso

(C PI A mixture of 70 volumes of octane was added to disperse the sample by adding 0.0 ??, and shaken at room temperature for 40 minutes. Then, the sample was precipitated by a centrifuge and the supernatant was collected. -Take it. Measure the refractive index of the supernatant and the original solution at 20 ° C, and calculate the aromatic adsorption index (AAI) according to the following equation.

AAI [(ng °) A - (ng °) B ] X 1 0 ⁴

Where (ng.) A: Toluene 30 volume and isooctane

Refractive index of 70 volume mixture

(ng.) B: Refractive index of the supernatant

According to the method described above]), when the aromatic adsorption index of natural clays was measured, most of them were distributed in 4 to 15 and Mon Moriro Nai, which is the original soil of activated clay In the case of g-type clay minerals, it is distributed between 8 and 15.

The aromatic adsorption index can be increased by acid-treating this monolithic clay mineral.

Treated clay excluding the A i on-the Si0 ₂ or only et al] ?, strong part of the acid sites is a state that is present only acid sites of Ho Tondona rather weak portion. However, in this state, it is difficult to develop and maintain the maximum density of the crystalline pigment. The reason for this is that the optimal acid strength to develop the highest concentration of crystallized retort lactones is not enough. It is considered to be promoted by light such as sunlight. Here, the acid point of the acid strength can be represented by the acidity of the treated clay, that is, the number of acid points having a certain acid strength. The acid point of the acid strength suitable for the color development of the crystalline Z-dioletra lactone is 0.4 m, mol or more in the range of acid strength Ηο = +0.8 to Ho = +4.8. It must exist.

Therefore, the serial magnetism used in the present invention is Fe,

Ca, Mg, between this introducing again Mg y O N'nomi the Si 0 ₂ minutes terminal structure of the removed processed clay Lee on, the range of acid strength Ho = + 0.8 or et Ho = + 4.8 0.4m mol

We can get the acid point of Z <^, then Ho = +0.8

1? There are no acid points in the strong acid part and Ho == +4.8.]? The acid point in the weak acid part is 0.4 mmol or less. ??, crystal bio It has the optimal acid strength to develop retactone.

Si0 Mg ^{+ +} is introduced into the ₂ consisting processing clay nitrate mug roots © beam, mug chloride, roots © beam, perchlorate magnesiate U beam, formic acid magnesiate U beam, sulfate magnesiate U beam, hydroxide Use magnesium, magnesium carbonate, magnesium oxide, etc. The amount of Mg added to 100 parts by weight of Si

It may be introduced in an amount of 5 to 50 parts by weight, preferably 10 to 30 parts by weight. Activated clay from which A ions have been removed is added to the solution in which the Mg salt is dissolved, and heat treatment is performed.

To fix the Mg ion, it is heated at 30 to 00 ° C. Subsequently, it is washed with water. At this time, a short-time treatment with a weak acid such as phosphoric acid may be performed.

It is dried at 550 ° G to obtain a series of magnesium used in the present invention. However, this manufacturing method has many variations]?

QF As described above, the silica-magnesia solid acid, which is one of the developers used in the present invention, is a conventionally known activated clay, that is, a natural acid clay or an acid clay. Or those that have been subjected to only moderately acid treatment (naturally occurring metals such as magnesium, calcium, calcium, aluminum, iron, etc.) Thione is still abundant) and is a completely different kind of synthetic acid, so to speak, with a different concept from activated clay. That is, it is a synthetic silica-magnesia solid acid.

A hydroxybenzoic acid ester compound which improves the stability of a color image when used in combination with the magnesium oxide of the present invention is represented by the following general formula.

General formula Γ

C00R

(Provided, however, R represents A Le key group, § La Le key group, also device indicates § re Ichiru group, - C00R is - O Le DOO or C ⁰ la position relative 0H).

The amount of these hydroxybenzoic acid ester compounds added was 5 parts per 100 parts by weight of the silica / magnesia compound.

~ 100 parts by weight! If the amount is less than 5 parts by weight, the effect is negligible. If the amount is more than 100 parts by weight, the coloring property is deteriorated. The addition method is as follows. It may be added as it is, but from the viewpoints of color development and surface smoothness, use a small amount of a dispersing agent to reduce the amount of polish, attritor, sand grinder, etc. It is preferable to add by pulverizing with a wet pulverizer.

Among the hydroxybenzoic acid ester compounds used in the present invention, particularly effective compounds are as follows.

No. La-hydroxymethyl benzoate

Para-hydroxybenzoic acid ethyl

Para-hydroxy benzoic acid isopir π-pill

Para-hydroxy dimethyl benzoate

Nora-Hydroxy Heptyl Benzoate

Para-hydroxy benzoate

Nora-Hydroxy dodecyl benzoate

Ha ⁰ La - Non-mud key shea depreciation, harm, Kosanben di Le

Nora-hydroxybenzoic acid-4 '— black mouth pentyl

Nora-Hydroxyan, carboxylic acid-4'-methylpentyl

Para-hydroxy benzoic acid benzoate

Ortho-hydroxy benzoic acid

Ortho-hydroxy benzoic acid dodecyl

"“ La—Hydroxy safe, harmful, phenyl benzoate

Among these, especially para-hydroxybenzoic acid phenol was useful.

Examples of the basic colorless dye as the color-forming agent of the present invention include crystal phenol, phenol phenol, phenol phenol and phenol phenol.

_ O? I __ Chilem. Roo, Malakite Tog, Lean Racton, Load Min B Lactum, 3-Dialkyl Amino-7-Zol Alky Amino Full Well-known compounds such as oranes and 5-methyl-2,2-spiropi (benzene,-[f] -chromene) can be used alone or in combination. In the present invention, it is preferable that the crystal bioreactor tracton be used alone. '

In the present invention, as a developer layer of silica / magnesia and a hydroxybenzoic acid ester compound, kaolin, clay, and tar are further used as bulking agents. Can be applied in combination with calcium, calcium carbonate, zinc oxide, sodium hydroxide, magnesium hydroxide, magnesium carbonate, silica, etc. Styrene as a binder to be applied to the base paper

-Latex-based binders such as phenolic-based latex and acrylic-based latex, oxidized starch, ethereal starch , Carboxymethylcellulose, hydroxyethyl phenolic cellulose, methylphenol phenolic cellulose, polyvinyl phenolic cellulose, case Water-soluble polymer binders such as iron, gelatin, soybean tannin, alginic acid, etc. can be used alone or in combination. One addition amount is 10 to 40 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight of magnesium magnesia and hydroxybenzoic acid ester conjugate. 30 parts by weight.

The color former is dissolved in a solvent to form a micro cuff. Cellify and apply to base paper. As the solvent, natural or synthetic oil alone or „_

_ CMFI Can be used in combination with one. Examples of solvents are cottonseed oil, kerosene, and c. Raffin, naphthenic oil, alkyridibebi-no-re, anore-kino-rei-do, terfena-no-re, tri-no-re-metan, chlorinated ha. Raffin and others can be mentioned.

An oil with a color former dissolved is used as a cuff. As a method for cell formation, a known microcapsule method can be applied. 'For example, US Patent

U.S. Patent No. 5,41,8,250, U.S. Pat.No. 2,800,057, U.S. Pat.No. 2,800,058, U.S. Pat. No. 3,0600,504, and a method by polymer precipitation. The microcapsule containing the color former is applied to a sheet such as paper along with various additives, plying agents, antioxidants, antifouling agents and surfactants. .

The pressure-sensitive recording sheet according to the present invention has such effects that the color developing ability does not decrease over time and that it has excellent resistance to discoloration and fading due to nitrogen oxides and light.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail with reference to typical examples, but the present invention is not limited to the examples. Hereinafter, “parts” means “parts by weight”.

' Example

Motor down motor case shown the Li π Na wells clay minerals (1 1 0 ° C dry matter in weight percent as a reference, ignition loss _{5.8, Si0 2 7 8 · 0} , A £ 2 s 1 3 · 0 , Fe ₂ 0 ₃ 1 • 9, CaO 0.9, MgO 2.)) are treated with sulfuric acid to obtain Α, Fe, Ca,- 1 t

Excluding Mg ion, a treated clay having an aromatic adsorption index of 5ό was obtained. The this processing clay heat treatment placed in chloride Ma grayed roots c anhydrous solution, to obtain a Si0 ₂ 8 7.5, MgO 1 2.5 Ca et ¾ Ru Shi Li force Ma Gune sheet A compound. The acid strength was examined by the Bensei method (the method described in J. Am. Chem. Soe., 78.549 (1950)). As a result, the acid strength was from 110 = +0.8 to 110 = + Acid point of 0.50 mmol / "^ in the range of 4.8, acid strength of Ho = +4.8 to 0.27 mmol / ^ in the range of Ho = +9] ?, acid strength Ho = +0.8 The following acid points were 0.

Ha ⁰ La - arsenide mud key sheet benzoic Sanpe down di le 1 0 0

Hydroxylene seno-leose 5 parts water '145' was crushed with wool mill for 2 days.

100 parts of the silica-magnesia compound obtained above and wet-milled para-hydroxybenzyl benzoate solution

50 'parts were dispersed in 200 parts of water in which 1 part of sodium pyrophosphate was dissolved, and 50 parts of 10% oxidized starch and 48% of SBR-latex 5 0 parts were added to make a coating solution. Coating solution of this to the 5 0 9 / ^ 7 on a dry weight in the base paper of ^{^z} 9 m ^z, coated Ni Let 's Ru, it was a sensible colored paper.

As coloring paper (CB paper), there are commercially available products that include crystal pie, lettactone, and pen ^^-yllomethylethylene blue as the main component of the coloring agent. Mitsubishi NCR paper N-40 paper (blue) was used. Table 1 shows these colors.

ΟΜΡΙ Stack paper and color paper on top of each other. The results of a light irradiation test after color development through a single render are shown. (Hereinafter, color density and white background density are all expressed as reflection densities).

As a blank of the developing paper, only silica / magnesia is used as a developing agent (that is, only a hydroxybenzoic acid ester compound is used from the developing paper of the above example). As a comparative example, an alternative to the hydroxybenzoic acid ester compound of the color developing paper of the above example was used as a comparative example.

A sample using the same amount of bisphenol A was prepared and used for the test.

From Table 1, it can be seen that, in the case of the present invention, the super-power-rendering one-color is compared with the case where only silica magnesia is used as the color developer (blank). Contact with its own concentration improvement, moreover Ru this and force ^Σ Wa forces mixed after light irradiation has been largely prevented.

Next, Table 2 shows the degree of yellowing caused by exposure to NOx gas or sunlight on white paper.

The developed paper of the present invention exhibits the same yellowing durability as that of the blank, whereas the comparative example (combined use of magnesia and Pisphenol A) is significantly yellowing.] Thus, the inventive step of the present invention is recognized.

Table 5 shows the NOx fastness of the colored part. In the present invention, the NOx fastness of a color image is remarkably improved.

Table 4 shows color development with a medium intensity calendar.

O PI

'- Although the 1 δ rise speed is shown, in the example of the present invention, the rise of the color development]? Speed is high, and the saturation concentration is also high, and it is very good. Table 1

Super fading Rendering color fading

^ Carbon arc lamp feed meter

Time irradiation

cvn Two

Yellowing on white

* Exposure in NOx gas (300 ppm) for 2 分間 minutes ^ Exposure to direct sunlight for 4 hours No. 5 3 ^

Discoloration of super calender colored area by NOx gas

* Exposure in NOx gas (150 ppm) for 10 minutes Table 4

Color development speed with medium intensity power render

Snow. The one-shot rendering color is the value measured by a Macbeth densitometer (reflection density) when color is developed with a pressure of 501 1cm by combining color-developed paper and colored paper. For fading with nitrogen oxides, generate nitrogen oxide gas according to JISL 0855, a method for testing the color fastness to nitrogen oxide gas (fill the gas reservoir with water and then use the specific gravity for the gas generator). Place sulfuric acid adjusted to 1.05 in a dropping funnel, drop it into sulfuric acid to generate nitrogen oxides, and pass through a trap of 10% sodium hydroxide solution. After storing the developer sheet in a desiccator, nitric oxide gas was injected to a specified concentration (ppm) and exposed for 10 or 20 minutes. I saw fading.

Although the details are omitted, the color biomarker (CB) is the one that uses the crystal bioreactone alone. The micro cuff is dissolved in a solvent. ), The stability of the color image (sunlight,

NOx) further improved.

Claims

1. Acid treatment of acid clay to remove aluminum ion almost completely, and to set the aromatic adsorption index to 40 or more, and then reduce the actual mass of magnesium ion Introduced magnesium and magnesium-based solid acid and the following general formula

Sales

C00R

Of H0

(However, R represents an alkyl group, an aryl group, or an aryl group, and -C00R represents an ortho or para position with respect to -0H). Mic mouth cuff containing a color developer consisting of one or more of doxybenzoic acid esters and a color former that is a basic colorless dye. A pressure-sensitive recording sheet combining cells and.

2. The pressure-sensitive recording sheet according to claim 1, wherein the basic colorless dye is crystalline bioreductoltone alone.

. [delta] arsenide mud key sheet benzoic San'e scan Te Le is Nono ⁰ La - arsenide mud key sheet pressure-sensitive recording sheet over bets preceding claim scope of acid base in g Le a is claimed.

The amount of 4-hydroxybenzoic acid ester 'E' compound added is 5 to 100 parts by weight based on 100 parts by weight of silica-magnesia solid acid. Claim 1 of the pressure-sensitive recording

f

CMPI WIPO Sheet

5. The pressure-sensitive recording paper according to claim 1, comprising a color-developed paper coated with a color developer and a color paper coated with a color-developing agent.

圧 The pressure-sensitive recording paper according to item 1, wherein the developer and the color former are applied on the same surface of the base paper.

. C? I wi? O ~