WO1983002255A1

WO1983002255A1 - Pressure-sensitive recording sheet

Info

Publication number: WO1983002255A1
Application number: PCT/JP1982/000467
Authority: WO
Inventors: Ltd. Mitsubishi Paper Mills
Original assignee: Kosaka, Takao
Priority date: 1981-12-22
Filing date: 1982-12-15
Publication date: 1983-07-07
Also published as: JPS58108190A

Abstract

A pressure-sensitive recording sheet having in combination a color developer comprising a silica-magnesia compound 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 magnesium ion thereinto and a diphenol compound and microcapsules containing a colorless basic dye as a color former. This sheet provides a color image having excellent preservability.

Description

Fine sense S Recording sheet technology

The present invention relates to an E-sensitive recording sheet, and more particularly to an improvement in color image storage stability of a pressure-sensitive recording sheet.

'' Background technology

The ε-recording sheet is generally an electron-donating organic color represented by a crystalline pyrolectolactone, a benzoyl cocomethylene, a roux, etc. (Hereinafter referred to as a color forming agent), a montmorillonite-type clay mineral (hereinafter referred to as an activated clay), which has been activated with an acid to increase its activity, a phenol compound, and an aromatic card 'Micro cuff containing a color former, which utilizes color development by the reaction of an electron-accepting color developer (hereinafter referred to as a color developer) such as boronic acid or a metal salt thereof. Top paper with cell coated on one side of base paper, bottom paper with color developer coated on one side of base paper, Micro-color cell containing color former and developer coated on different sides of same base paper Combining the used middle papers as appropriate for the purpose of use, ball pen, and type. It is copied by adding it with a writer.

In addition, a so-called self-contained paper in which the above-mentioned microcapsules and a color developing agent are applied to the same side of the base paper.

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In the pressure-sensitive recording sheet, as a developer Clay is most commonly used. This activated clay reacts well with the color former, and has the property of producing a deeper color, but its color developing ability decreases over time.] Due to oxides etc.] 3 It has the disadvantage of fading. In other words, to make the most commonly used crystal pigment lactolactone among the color formers react with the activated clay to produce the highest concentration of real purple color, the acid of activated clay is used. The strength is too strong. For this reason, there has been proposed a method in which an alkaline material is added during preparation of a paint for active clay to adjust the fine clay side. But-over time ?? The alkali recrystallized ?? Sulfuric acid in the base paper

In many cases, the effect is lost. 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. There is a problem that the color development function of the clay is reduced. The disadvantage of such a developed sheet is that the acid clay is further treated to remove aluminum ion almost completely, and the aromatic adsorption index becomes 40 or more. By using a silica-magnesia compound (hereinafter simply referred to as a silica-magnesia compound) into which O is introduced as a developer]? Although the decrease in color developing ability could be improved to some extent, the fading of the developed image with nitrogen oxides etc. during natural standing was insufficient. ·

CMPI Disclosure of the invention

An object of the present invention is to improve the above-mentioned drawbacks of the prior art and to provide a photosensitive recording sheet with improved color image storage stability.

The object of the present invention has been attained by using a biphenol compound as a color developer together with the above-mentioned magnesium-magnesia compound.

That is, the gist of the present invention is that acid clay is subjected to acid treatment, and aluminum-dimion is roughly removed; ^ it is completely removed, and the aromatic adsorption index is set to 40 or more, and then magnesium is added. A developer consisting of a silicon-magnesia compound and a bisphenol compound into which an on is introduced, and a microphone π-force cell containing a color former which is a basic colorless dye. It is on the Kanou record sheet that is used in combination.

BEST MODE FOR CARRYING OUT THE INVENTION

Shi Li force Ma 'Gune shea § compound used in the present invention requires a step of acid treatment of motor down mode Li port Nai preparative clay minerals, motor down mode Li b Nai Preparative clay minerals formula x _m ( _Y 2+, y ³⁺ ) ₂ ~ ₃ Z ₄ 0 ₁₀ (H0) _2. SH ₂ 0 where X: K:, Na, Ca

Ύ ^{2 +} : Mg ²⁺ , Fe ^{z +} , Mn ^{2 +} N 2 + Zn 2 +

Y "Ai ³ Fe 3 + Cr 3 + Mil 30

Z: Average of Si, A & m is 1 3

O PI s is the number of interlayer water

Indicated by This is described on page 80 of Clay Handbook (edited by The Clay Society of Japan, Gihodo). Among these clay minerals, it is desirable that the acid clay has an AJ¾ of 5 to 30 parts by weight with respect to si 100 parts by weight. The Fe ion, Mg ion, and Ca ion are eluted when the monmorillonite clay mineral is treated with sulfuric acid or hydrochloric acid. Next, AJ ion is eluted, and the magnesium acetate compound used in the present invention is treated until the A ion is completely completely removed. At this time, the aromatic adsorption index of the treated clay must be over 40. Here, the aromatic adsorption index is an index that reflects the degree of adsorption capacity or activity of treated clay, and is also used as an index that conveniently indicates the specific surface area of treated clay. . The aromatic adsorption index of not less than 40¾ is not used in the present invention because the aromatic adsorption index of active clay used as a color developer is 20 to 40. Is very active.] Means that the specific surface area is very large, and the acid point of the weak acid part that contributes to the color development with the crystal bioreactone. It shows that there are many things. It also shows that the effect of acid strength on the sulfate band in the base paper over time does not occur.

The aromatic adsorption index is determined by the following method. The ground sample is dried at 150 ° C for 3 hours and allowed to cool to room temperature in a desiccator. This drying trial Add a mixture of 30 volumes of dehydrated toluene and 70 volumes of dehydrated iso-octane, and disperse the sample. After shaking at room temperature for 40 minutes, Settle the sample in a centrifuge and collect the supernatant. The refractive index of the supernatant and the original liquid was measured at 20 and the following formula was used.

(AAI).

AAI = ^{[(η¾ 0) Α- (η¾ °} ) Β X 10 4 in here A (η.): Preparative refractive index of the Le et emissions 5 0 volumes and Iso Okuda down 7 0 ml mixture

(n ² _D °) B: Refractive index of the supernatant

Is it the method described above? When the aromatic adsorption index of natural clays is measured, most of them are distributed between 4 and 15, and in the case of montmorillonite-type clay products, which are the raw material of activated clay, 8 to 15 Distributed.

It is possible to increase the 1-aromatic adsorption index by acid-treating this monolithic clay-type clay mineral.

Processing clay, except for the Ajg I on-only from Si0 _2]?, Acid point of strength ¾ part is a state we leave for there only acid point of almost Ku weak part. However, in this state, it is difficult to develop and maintain the crystal violet tract at the highest intensity. The reason for this is that the best coloration of crystal oleotactic lactones is achieved. Optimum acid strength is weaker. At an acid point, the coloration reaction can be performed sufficiently; It is thought to be promoted by light such as sunlight.

Ο: ΡΙ It is. Here, the acid point of the acid strength can be expressed by the acidity of the treated clay, that is, the number of acid points having the acid strength of a certain degree, and the crystal bioreactor tracton It is necessary that the acid point of the acid strength suitable for the color development of the color should be 0.4 mo & / ^ or more in the range of the acid strength HO = +0.8 to HO = +4.8.

Therefore, in Shi Li force-magnesiate A compound used in the present invention are Fe, Ca, Mg, and this for introducing only again Mg I on during Si0 ₂ molecular structure of Ai Lee on- removed processed clay, Acid strength of 0.4 OJ¾ can be obtained in the range of acid strength Ho = +0.8 to Ho = +4.8, then HO = +0.8]) There is no acid point in the strong acid part and HO = +4 : 8)]? The acid point of the weak acid part is less than 0.4 mmojg ^] ?, which has the optimal intensity for the coloration of crystal violet tractone. is there.

M _g nitrate magnesiate © beam introduced into the treatment clay consisting Si0 _2, Shioi匕Mak ,, roots © arm, over 'perchlorate Mak ,, roots © beam, formic acid Mak,' roots © beam, Use magnesium sulfate, magnesium, magnesium hydroxide, etc. The amount of addition may be such that Mg is added in an amount of 5 to 30 parts by weight, preferably 10 to 20 parts by weight, based on 100 parts by weight of Si. Activated clay from which A ions have been removed is added to the solution in which the above salt is dissolved, and heat treatment is performed. Alkaline to fix the Mg ion and heat at 50-500 iC, then wash with water. At this time, a short time treatment with a weak acid such as phosphoric acid may be performed, and drying at 100 to 350 mm is used in the present invention. Power · Get magnesium compound.

As a bisphenol compound which is used in combination with the silica / magnesia compound of the present invention to improve discoloration with nitrogen oxides, 4,4′-isopropyl Redundant phenol, 4,-Cyclohexyl red phenol, 4, 4'-Gludoxy phenyl sulphone, 4 , 4, 4-butyl alcohol (3-methyl-copper, 1-t-foil, 4-butyl alcohol), 4, 4 '-butylidene-bis (3-methyl--t- Bisphenol represented by butylphenol) and 2,2'-methylbenzene (4-methyl-ό-t-f, chilphenol) Among them, the most preferred is 4, 4'-Isov. The mouth is pyridene phenol. The amount of bisphenol compound added is silica. It is 5 to 3 Q parts by weight per 100 parts by weight of magnesium compound.]? Less than 5 parts by weight has little effect If the content is more than 30 parts by weight, the color developability deteriorates. The addition method is as follows: a fine powder that has passed through a 32.5-mesh filter, may be added as it is; a small amount of a dispersing aid is used in terms of color development and surface smoothness. However, it is preferable to add by pulverizing with a wet pulverizer such as a pole mill, an attritor, a sandok, or a binder.

Examples of the basic colorless dye as the color-forming agent of the present invention include crystal noble dyes, penzylloycomethyrene, and non-aqueous dyes. , Mara Kite Talk, Lean Lacton, Rotamin B lactam, 5-Dial ァ-ノ-7-- Oranes, 5 — Methyl -2,2-S

~ (O FI Ichi

- Known compounds such as lobi (benzo- [f] -chromene) may be used alone or in combination. However, in the present invention, the compound is preferably used in the form of a crystal pie. Tracton alone is good. In the present invention, the developer layer of the silica / magnesia compound and the bisphenol compound may further include kaolin, crepe, talc, and carbonate as extender pigments. It can be applied using a combination of calcium, zinc oxide, aluminum hydroxide, magnesium oxide, magnesium carbonate, silica, etc. Latex such as styrene-butadiene-based latex, acrylic-based latex, etc.

-Box binders, oxidized starch, etherified starch,

Carbo, Ximethyl Cellulose, Hydroxyl Cellulose, Methylcellulose, Polyvinyl Alcohol, Casey Water-soluble polymer binders such as carbohydrate, gelatin, soy protein, and sodium alginate can be used alone or in combination. The addition amount of these binders is 10 to 40 parts by weight, preferably 20 to 100 parts by weight of the silica-magnesia conjugate and the bisphenol compound. To 50 parts by weight. The color former is dissolved in a solvent, and the mic is converted to a 7 ° cell and applied to the base paper. As the solvent, natural or synthetic oils can be used alone or in combination. Examples of solvents are cottonseed oil, kerosene, paraffin, naphthenic oil, alkylylidene biphenyl, phenolic diphenyl, triphenylene Tan, chlorinated paraffin, etc. can be mentioned. Microcassizing oil in which color former has been dissolved

ί Οί, ίΡΙ As the method, a well-known microphone mouth capsule method can be applied. For example, as a method for producing a 7 ° cell with a micro force, US Pat. No. 2,800,457 and US Pat. A method using a polymer, a method based on polymer precipitation as shown in US Pat. Nos. 5,418,250 and 3,004,304, and the like. Micro cuff containing a color former. The cell is applied to a sheet, such as paper, with various additives, binders, antioxidants, antifoulants, and surfactants.

The EE recording sheet according to the present invention has such effects that the color developing ability does not decrease over time and that the color recording resistance to nitrogen oxides and the like is excellent.

The present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Below,

The deviation also indicates “parts by weight”.

Example-1 '

Motor down mode Li b when the Nai preparative clay minerals (1 1 0 TC dried product shows a weight to standards, ignition loss _{5.8, sio g 7 8 · 0} , Α £ 2 Ο 3 1 5.0, Fe 2 _{_{o 3 1 · 9, c a}} o 0.9, and M _g o 2.0) a sulfuric acid treatment, a £, Fe, Ca,; give M _g i on--out removal, aromatic adsorption index 5 6 processing clay . The process clay was heated placed in chloride magnesium © anhydrous solution, SI0 ₂ 8 7.5, to give a _g o 1 2.5 or we made Shi Li Ka Mak, 'roots § compound. The acid strength was determined by the Bensei method (<< I. Am. Cliem.

soc., 7 8, 5490 (1950)) As a result, the acid point of 0.50 mmoja ^ in the range of acid strength HO = +0.8 to HO = +4.8, 0.27 mmo £ で in the range of acid strength Ho = +4.8 to HO = +9 The acid point of i? The acid strength of HO = + 0.8 or less was 0.

4, 4 '-Isof. Mouth pyridene phenol 1 0 0 Head 'Mouth'

Water 1 4 5

Was ground with a poll mill for 2 days.

100 parts of the silica and magnesium compound obtained earlier and 4,4'-isof wet milled. 50 parts of a pyridene diphenol solution are dispersed in 200 parts of water in which 1 part of π-phosphoric acid soda is dissolved, and 50 parts of '10% starch starch, 4 8

50 parts of SBH-Latex was added to make a coating solution. This coating liquid 5 0 ^ Z m to ² of the base paper on a dry weight 7 ^ Z ia ² Let 's that in the Ni coating, was Arawashoku羝.

方ジイ 7 口 7 7 7 7 7 ° 7 7 ° 7 7 7 7 7 7 7 4 4 4 4 Chillable-0.0 was dissolved. A micro cuff using a color filter oil described in U.S. Pat. No. 2,800,457, which utilizes coacetation. According to cell manufacturing method]? Micro force: 7 ° cell. Micro cuff obtained. Cell dispersion (micro cuff cuff; cell solid content is 10h) Add 200 parts of oxidized starch 20 parts of wheat starch 4 parts of wheat starch to make paint 509 / base paper 5 was applied on a dry basis to obtain colored paper.

特性 Table 1 shows the characteristics when colored paper and colored paper are combined. You.

Comparative Example-1

Same as in Example-1 except that 4,4'-isopropyl densified phenol is not added.

Example-2

The same as in Example 1 except that the color developing agent was crystal violent lactone alone.

Example-3

Example-2, 4, 4 '-Isof. The same as above, except that 4,4'-thiobis (3-methyl-ό-t-―butylphenol) was used instead of the mouth pyridene phenol.

Example-4

Example 4 and 4 '-isof in 2. Mouth of pyridene phenol]? Is replaced by 2,2'-methyl benzene (4-methyl

Butyl phenol).

Comparative Example-2 '

Example-2, 4, 4 '-Isof. The same except that the amount of pyridene phenol was 2 parts by weight with respect to the magnesium / magnesia catalyst.

Comparative Example-3

Example-2 The same except that the amount of pyridene phenol is 40 parts by weight with respect to the magnesium catalyst.

ο: /? ι * Nitrogen oxidation of color developing paper

Immediately after color development Two months after object exposure

Concentration Concentration Example-1 0.9 5 0.7 0 0.9 2

a 2 1.0 5 0.8 2-1.0 5

O Z 1.0 5 0.7 6 1U

ff 4 1.0 0 0.7 4 1.0 0 Comparative example-1 0.9 9 0.5 2 0.8 6

tf 1 1.0 4; 0.5 6 0.9 1

ff 3 0.7 9 0.7 2 0.79 The color development shows the value measured with a Macbeth densitometer, combining the color developing paper and the color developing paper and developing the color at 5 Ok ^ Zcm ² .

* Fade with nitrogen oxides is based on Jis L0855's Dye Fastness Test for Nitric Oxide Gas ^ 3] Generates Nitric Oxide Gas (fill the gas reservoir with water, then Sulfuric acid adjusted to a specific gravity of 1.03 is put into the gas generator, and a saturated solution of sodium nitrite is put into a dropping funnel, and is dropped into sulfuric acid to remove nitrogen oxides. Generated, trapped in 10% sodium hydroxide solution and stored in a gas reservoir), put the developer sheet into the desiccator, and then purged with nitric oxide gas. The solution was injected so as to have a concentration of 1000 ppm, exposed for 10 minutes, and its fading was observed. Table 1 shows that the examples of the present invention are

O ίΡΙ The color developing ability does not decrease with time, and it is excellent in resistance to discoloration and discoloration with nitrogen oxides. The color of the comparative example was insufficient, and the color development density was insufficient. It is a substance with reduced color ability and insufficient discoloration resistance with nitrogen oxides.

ΟΜΓΙ

'.' '

Claims

The scope of the claims

1. The acid clay is treated with acid to remove almost all aluminum-ion and the aromatic adsorption index is set to 40 or more, and then Mac and Nezium ion are introduced. A developer consisting of silica-macr, a nesium compound and a bisphenol compound; and a microcass cell containing a color former which is a basic colorless dye. The feeling record sheet which is used in combination.

2. The sensational record sheet according to claim 1, wherein the basic colorless dye is a single crystal violet latton.

-h 0

5. The method according to claim 1 or 2, wherein the amount of the bisphenol-containing compound is 5 to 30 parts by weight with respect to 100 parts by weight of the silica-magnesium compound. E-record sheet.

4. The bisphenol compound is 4, 4'-isof. The pressure-sensitive recording sheet according to any one of claims 1 to 3, wherein the pressure-sensitive recording sheet is a pyridene phenol.

CMFI

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