JPH02217286A - Color developer sheet for carbonless pressure-sensitive recording materials - Google Patents

Abstract

PURPOSE:To improve coloring power while reducing developer coating amount by employing zinc stearate to be mixed with pigment in a specific organic developer. CONSTITUTION:In a non carbon pressure sensitive recording material made of electron donative achromatic (leuco) dye and electron acceptive developer for coloring the dye, as the developer zinc stearate is employed with pigment to be mixed with aromatic carboxylic polyvalent metal salt, polyvalent metalate of salicylate resin having 500-10,000 of average molecular weight represented by general formulae [I], [II], [III] or [IV] as organic developer. In the formulae, R1, R2, R3 are independently H, 1-12C alkyl group, cycloalkyl group, aralkyl group or aryl group, and the R1 and R2 may adjacently form a ring. X is independently direct bond or 1-6C straight chain or branched bivalent CH, R4 and R5 are H, 1-12C alkyl group, cycloalkyl group, aralkyl group or aryl group, and R6 is H, 1-4C alkyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION (A) Field of Industrial Application The present invention relates to a color developer sheet for carbonless pressure-sensitive recording materials, and more particularly to the color density of the color developer sheet.

(B) Prior Art Carbonless pressure-sensitive recording materials are known, for example, U.S. Pat. No. 2,712,507, U.S. Pat.
As described in No. II3418250, etc., PGM is dissolved in a high boiling point solvent and contained in microcapsules.
Electron-donating (leuco) dye! This is a recording material that combines a coated color former sheet and a color developer sheet coated with an electron-accepting color developer, and utilizes a color reaction caused by contact between the two.

Conventionally, microencapsulation methods have been carried out by coacervation methods, in situ methods, interfacial polymerization methods, etc. (leuco) dyes include crystal violet lactone, 3-3 bis(P-dimethylaminophenyl), etc. talide, triallylmethane 7-thallide series such as 3-()-dimethylaminophenyl)-3-(2-methylindol-3-yl)-6-dimethylaminophthalide, methylene blue benzoyl, anizoyl,
Acyl derivatives such as pivaloyl: xanthine 7-thallide systems such as 3-diethylamino-6-methyl-7-chlorofluoran and 3-diethylamino-7-dibenzylaminofluorane, which are also used in the present invention. .

Examples of high boiling point solvents include alkylnaphthalenes represented by diisopropylnaphthalene, diallylakanes represented by 1-7znyl-1-silylethane, alkylbiphenyls represented by isopropylbiphenyl, and other triallyldimethanes. Aromatic hydrocarbons such as alkylbenzenes, benzylnaphthalenes, diallylalkylenes, and allylindanes: Carboxylic acid ester compounds represented by dibutyl phthalate, dioctyl maleate, etc. Phosphate esters represented by nitricresyl 7-mole-7-ate Type compounds: Vegetable oils such as castor oil, soybean oil, cottonseed oil, etc. or their modified oils: High boiling point fractions (consisting of aliphatic hydrocarbons) of natural products such as mineral oils, etc., and are also used in the present invention.

Conventionally known color developers include inorganic coloring agents such as acid clay, natural clay minerals such as attapulgite clay,
Activated clay made by treating acid clay with mineral acid, JP-A-57-15
1 semi-synthetic solid acids described in the specification of No. 996, etc., and various phenolic compounds, novolak phenol resins, polyvalent metal salts of aromatic carboxylic acids, etc. have been proposed and already used as organic color developers.

(C) Problems to be Solved by the Invention When these color developers are used as color developers in color developer sheets for carbonless pressure-sensitive recording materials, activated clay, which is an inorganic color developer, and biosynthetic solids Acid is attractive as an industrial material due to its excellent color resistance and low cost, but it has poor color density and moisture resistance and light resistance of the color image, and furthermore, the background is susceptible to oxidation by oxidation. It turns yellow depending on the substance.

On the other hand, organic color developers such as various phenolic compounds and phenolic resins manufactured by Novolac have excellent moisture resistance of colored images, but the coloring speed is slow and the background is prone to yellowing. Polyvalent metal salts of aromatic carboxylic acids produce colored images with excellent moisture resistance and little yellowing of the background, but the rate of color development is slow.

By the way, recently proposed polyvalent metal compounds of salicylic acid resins described in JP-A-63-186729 and JP-A-63-254124 have excellent coloring speed and little yellowing of the background.

However, like conventional organic color developers, it is expensive because it is a chemically synthesized product, and profits cannot be realized unless the proportion of color developer in the formulation of the coating solution for color developer sheets is reduced. do not have.

Therefore, it is an object of the present invention to develop a color developer sheet using a polyvalent metal salt of an aromatic carboxylic acid that causes less yellowing among organic colorants, and a polyvalent metal compound of a salicylic acid resin that has an excellent color development rate. An object of the present invention is to provide an excellent color developer sheet for carbonless pressure-sensitive recording materials that has high density and is also profitable.

(D) Means for Solving the Problem The inventors conducted research experiments earnestly! As a result of our efforts, we have developed a color developer sheet for carbonless pressure-sensitive recording materials that provides excellent color development speed and density even with a small amount of color developer. It was successfully developed.

That is, the present inventors have discovered that the color developer is an aromatic carbonaceous polyvalent metal salt, and furthermore, the following -Momonana [D, [...], (I [[) or [■]] (wherein, R1, 几2. Rr3 is each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group,
It represents an aralkyl group or an aryl group, and R1 and R2 may be adjacent to each other to form a ring. X independently represents a direct bond or a linear or branched divalent hydrocarbon having 1 to 5 carbon atoms; R4 and R5 are hydrogen atoms;
2 represents an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group.

6 represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms) A polyvalent metallized salicylic acid resin having an average weight molecular weight of 500 to 10,000 is used as an organic color developer,
The present invention was developed based on the knowledge that by using zinc stearate in the pigment to be mixed, an excellent color developer sheet for carbonless pressure-sensitive recording materials with a small amount of color developer applied and a high degree of color development can be obtained. Ta.

Polyvalent metal salts of aromatic carboxylic acids as color developers used in the present invention are disclosed in Japanese Patent Publications Nos. 49-10856 and 51-2517.
4, No. 52-1327, No. 52-7372, etc., but for example, specifically,
Tolyl hydroxybenzoate, 4-hydroxybenzoic acid α
-Phenylbenzylesterk,m-xylylenebis4-
Hydroxybenzoic acid ester, 4-hydroxybenzoic acid 7enethyl, 4-hydroxybenzoic acid-P-cumylbenzyl, 4-hydroxybenzoic acid-cinnamyl ester,
4-Hydroxybenzoic acid benzyl ester, 4-H)'
"+ V-benzoic acid-m-70 lobenzyl ester, 4-hydroxybenzoic acid-cumyl ester, 4,4'-hydroxy-2/, 2/-diptyl 7-enyl sulfone, β-phenethyl orseinate, cinnamon milorcelinate,
orcerin me t-chlorophenoxyethyl ester,
5.5'-Methylenebis-2,4-dihydroxybenzyl acid benzyl ester, Ω-phenylphenoxyethyl orselinate, m-phenylphenoxyethyl orselinate, 2,4-dihydroxybenzoic acid-β-a/
t-Butyl-4'-hydroxyphenoxyethyl ester, bisphenol A bis I-hydroxybenzoic m ester, 5-β-! -methoxyphenoxyethoxy-2
-Hydroxybenzoic acid, 2,4-dihydroxybenzoic acid-p-methylbenzyl ether, 2,4-dihydroxybenzoic acid-β-phenoxyether ester, 2,4-dihydroxy-6-methylbenzoic acid emljf-methylpenzyl ester ν, bis-4-hydroxyphenylacetic acid phenoxyethyl ester, 4,4'-diacetyldiphenylurea, 3-phenylsalicyl[,5-1)-α-methylbenzyl-a-methylbenzylsalicylic acid, 5-p
-Methoxyphenoxyethyloxysalicylic acid, 5-phenoxyethoxysalicylic acid, 5-p-benzyl-a
-Methylbenzylsalicylic acid, 3-xylyl-5-(a
, a-dimethylbenzylcosalicylic acid, 3fi5t di(
a-methylbenzyl)salicylic acid, 2-hydroxy-1
-a-ethylbenzyl-3-su7toic acid and the like. Calcium, magnesium, copper, zinc, tin, barium, cobalt, etc. are used as polyvalent metal salts, and zinc is particularly effective.

The polyvalent metal compound of salicylic acid resin as a color developer used in the present invention is disclosed in JP-A-63-186729 and JP-A-63-25.
Although it is described in detail in Japanese Patent Application No. 4124, for example, specifically, the following - Monana [v] (in the formula, 几1, R2, R5 and B/ are each independently a hydrogen atom, a carbon number 1- -12
represents an alkyl group, cycloalkyl group, aralkyl group or aryol group, and R1 and R2 may be adjacent to each other to form a ring.

x and x' are each independently a direct bond or a carbon number of 1 to
5 straight chain or branched divalent hydrocarbon group, n
is 1 or 0),
In the presence of a strong acid catalyst such as hydrochloric acid or sulfuric acid, the following - Monna [V[
) (wherein R4 and R5 represent a hydrogen atom or a methyl group,
A styrene derivative represented by R6 is a water bulk atom or a lower alkyl group having 1 to 4 carbon atoms is subjected to a Friedel-Craf reaction, and the resulting resin composition and polyvalent metal salts of calcium, magnesium, aluminum, Salicylic acid resin polyvalent metal compound produced by reacting with oxides, hydroxides, carbonates and organic carboxylates of copper, zinc, tin, barium, cobalt and nickel in an aqueous medium and/or by heating and melting. , Furthermore, the salicylic acid derivative represented by the above-mentioned -Momona (V) is treated with the following -Momona [VII] (in the formula, l1114, Rs is a hydrogen atom or a carbon number of 1 to 12 represents an alkyl group, aralkyl group, aryl group or cycloalkyl group,
X represents a halogen atom. This is a polyvalent metalized salicylic acid resin produced by reacting benzyl halide 8@ represented by ) and reacting the resulting resin composition with the above polyvalent metal salt in the same manner. A particularly effective polyvalent metal is zinc.

The amount of the above styrene derivative used is 0.2 to 20 mol, preferably 0.5 to 10 mol, per 1 mol of the salicylic acid derivative.
It is a mole. The weight average molecular weight of the resin produced within this range of usage is 500 to 10,000.

Specific examples of polyvalent metallized salicylic acid resins produced by reacting with styrene derivatives used in the present invention include zinc salts of 3,5-di(4-methylbenzyl)salicylic acid resins produced by reacting with styrene; Zinc salt of 5-(4-methylbenzyl)salicylic acid resin produced by reacting with 0-methylstyrene, 3- produced by reacting with styrene
Examples include zinc salt of 7-enylsalicylic acid resin.

The amount of the above benzyl halides used is 0.2 to 20 mol, preferably 0.5 to 20 mol, per 1 mol of salicylic acid derivative.
It is 10 moles. The weight average molecular weight of the resin produced within this range of usage is 500 to 10,000.

Specifically, the salicylic acid resin polyvalent metal compound produced by reacting with benzyl halides used in the present invention is as follows:
3,5-di(
s-(4-methylbenzyl) produced by reacting the zinc salt of salicylic acid resin and P-methylbenzyl chloride
Zinc salt of ahα-dimethylbenzyl) salicylic acid resin,
Examples include zinc salt of 3-tert-butyl-5-7enyl salicylic acid resin produced by reacting 2,4-dimethylpenzyl chloride.

The pigment used in this invention is zinc stearate.

The zinc stearate of the present invention is effective even in organic color developers with h deviations, but it is polyvalent metallized salicylic acid resins that exhibit excellent effects in terms of percentage.

The zinc stearate of the present invention is used in combination with other pigments.

Examples of pigments include clay, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, satin white, titanium oxide, zinc oxide, urea resin, plastic pigment, Merck, alumina, and the like.

The proportion of zinc stearate in the pigment is 0.5% by weight or more, preferably 3 to 30% by weight. If the amount is less than 0.5% by weight, no significant effect in improving color density can be obtained.

Examples of the color developer and pigment binder used in the present invention include starch, starch derivatives such as phosphate ester starch, cationized starch, and dialdehyde starch, casein, gelatin, polyvinyl alcohol, methyl cellulose, and ethyl cellulose. , carboxymethylcellulose, hydroxyethylcellulose1. I? lJ ethylene oxide, polyvinylpyrrolidone, vinyl acetate maleic acid copolymer, styrene maleic anhydride copolymer,
Examples include water-soluble polymers such as sodium polyacrylate, sodium alginate, and polyacrylamide, and latex emulsion carbonate, which is a styrene-butadiene-based, acrylic-based, and vinyl acetate-based hydrophobic polymer.

In the present invention, a color developer, a pigment, a binder, and if desired, an antifoaming agent, a preservative, a water repellent such as a wax emulsion, etc. are used as a coating solution for a pigment sheet, and the coating solution is applied to a support such as paper by air, Apply using a coater such as a blade or roll at a rate of 1.5 to 10 t/lri in absolute dry weight solid content. Is the particularly preferable coating amount 3 to 5? /d.

(E) Examples Preferred embodiments and excellent effects of the present invention will be specifically explained below using the most typical examples. In addition, all parts below represent parts by weight.

Example 1 100 parts of zinc salt of monomethylbenzyl) salicyl-bearing resin 50 parts of aqueous tivolivinyl alcohol solution The above mixed solution was dispersed in a ball mill for 24 hours, and 25 Lll
This was prepared as a coloring agent dispersion (A).

5 parts of 10% sodium hexametaphosphate were added to 55 parts of water, followed by 1.3 parts of 40 zinc stearate emulsified dispersion (manufactured by Middle East Yushi Co., Ltd., 5Z-40) and kaolin (M).

Made by Huba, Hydraspers) 49.5! , Calcium carbonate (Shiraishi Calcium, Brilliant-15) 5
After adding 0 parts and dispersing 1 part, add 40 parts of the above 25% color developer dispersion (A) and 10% oxidized starch aqueous solution (manufactured by Nikko,
MS-3800) 100 parts, 48% carboxylated styrene-butadiene copolymer latex (Fushikasei, DL-
620) All 25 parts were added and coated; it was made into f5 liquid.

This coating solution was applied with a blade coater to a high-quality paper having a basis weight of 40 tβ so that the absolute dry solid content coating amount was 3.5 f/m' and dried to prepare a color developer sheet.

Example 2 5 parts of 10% sodium hexametaphosphate was added to 70 parts of water to prepare a 40% zinc stearate emulsion dispersion m (SZ-40
), 35 parts of kaolin (Hydrasperse), and 35 parts of calcium carbonate (Brilliant)-15 were added, followed by 40 parts of the above 25% color developer dispersion (A),
100 parts of 10% oxidized starch aqueous solution (MS-3800) and 37.5 parts of 48% carboxylated styrene-butadiene copolymer latex (DL-620) were added to prepare a coating liquid. This coating solution was applied in the same manner as in Example 1 and dried to prepare a developer sheet.

Example 3 50 parts of 1096 polyvinyl alcohol aqueous solution produced by reacting benzyl chloride The above mixture was dispersed in a ball mill for 24 hours to obtain 251 color developer dispersion (B).
And so.

Example 1. 25 parts developer dispersion (A) 't' above 2
Color developer dispersion liquid (B) $C A color developer sheeter was prepared in the same manner except that the same packaging was replaced with M cloth liquid.

Example 4 A developer sheet was prepared in the same manner as in Example 2, except that the same amount of the 25-part color disintegrator dispersion (A) was replaced with the 25-part color developer dispersion (B) as the coating solution.

Example 5 Method for preparing 2518 colorant dispersion (C) 3.5 Zinc salt of di(a-methylbenzyl)salicylic acid 1
00 parts 10% polyvinyl alcohol aqueous solution W 7.50 parts The above mixture was dispersed in a ball mill for 24 hours to obtain a coloring agent dispersion (C).

Example 2. 2518 Colorant Dispersion (A) 't-Above 2
Color developer dispersion liquid (C) was used in the same manner except that the same amount of the coating liquid was used.

Comparative example 1゜Example 1. 40% zinc stearate emulsified dispersion of 1.3
Color developer sheet in the same manner except that 0.5 parts of kaolin (Hydrasperse) was used as the coating solution! Created.

Comparative example 2゜Example 1. 40% zinc stearate emulsified dispersion of 1.3
Part t Kaolin (Hydrasperse) o, sWK.

A color developer j-toner was prepared in the same manner except that 25 parts of the color developer dispersion (A) was replaced with 25 parts of the color developer dispersion (B) and the same amount of K was used as a tray solution.

Comparative example 3゜Example 2. 75 parts of the 40% zinc stearate emulsified dispersion was replaced with 30 parts of kaolin (Hydrasperse), 45 parts of water was added, and 25% of the 25% color developer dispersion (A) was added.
A color developer sheet was prepared in the same manner except that the same amount of TollA colorant dispersion liquid (C)K was replaced with the coating liquid.

Test/Measurement Method The prepared color developer sheet was tested in one of the following methods.
◆Measurements were made and the results are shown in Table 1. It was shown to.

○Color development density Color development agent C) Y Commercially available Mitsubishi NCR paper Bushi Blue color development top paper N, 40) was passed through a calendar to develop the color, and after 1 hour, the color density was measured using a color difference meter.

The smaller the numerical value, the higher the color density.

(F) Effects of the Invention As is clear from the present invention, among the organic color developers of the present invention, especially in the polyvalent metal compound of salicylic acid resin, the color developer is applied by using zinc stearate in the pigment to be mixed. An excellent color developer sheet for carbonless pressure-sensitive recording materials was obtained, which had a small amount and high color density.

Claims (1)

[Scope of Claims] 1) A carbonless pressure-sensitive recording material comprising an electron-donating colorless (leuco) dye and an electron-accepting color developer capable of coloring the colorless (leuco) dye, wherein the color developer is an organic developer. A color developer sheet for a carbonless pressure-sensitive recording material, which is a colorant and contains zinc stearate as a pigment. 2) The organic color developer has the following general formula [I], [II], [
III] or [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III] ▲ Mathematical formulas, chemical formulas, tables, etc. There are tables, etc. ▼ [IV] (In the formula, R_1, R_2, and R_3 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aralkyl group, or an aryl group, and R_1 and R_2
may be adjacent to each other to form a ring. X is independently a direct bond or a straight chain or branched chain having 1 to 5 carbon atoms
R_4 and R_5 represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aralkyl group, or an aryl group. R_6 represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, with an average weight molecular weight of 500 to 10,000
The color developer sheet for a carbonless pressure-sensitive recording material according to claim 1, which is a polyvalent metallized salicylic acid resin.