JPH02217285A - Color developer sheet for carbonless pressure-sensitive recording materials - Google Patents

Abstract

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

Description

Detailed Description of the Invention (A) Industrial Application Field The present invention relates to a color developer sheet for carbonless pressure-sensitive recording materials, and more particularly relates to the color density and desensitization effect of the color developer sheet. .

CB) 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. 18250, etc., a color former sheet coated with an electron-donating (leuco) dye dissolved in a high-boiling point solvent IIc and incorporated into microcapsules, and a developer coated with an electron-accepting color developer are used. This is a recording material that combines a colorant sheet and utilizes a coloring reaction caused by contact between the two.

Conventionally, microencapsulation methods have been carried out using methods such as coacervagelon method, in situ method, and interfacial polymerization method. Examples of (leuco) dyes include crystal violet lactone, 3-3 bis (P-dimethylaminophenyl), etc. Su7thalide, a-(p-dimethylaminophenyl)
-3-(2-methylindol-3-yl)-6-dimethylaminophthalide and other triallylmethane 7-thallides, methylene blue and other acyl visiting systems such as benzoyl, anizoyl and pivaloyl; 3-diethylamino-
There are xanthine 7-thallides such as 6-methyl-7-chlorofluoran and 3-diethylamino-7-dibenzylaminofluoran, which are also used in the present invention.

Examples of high boiling point solvents include alkylnaphthalenes such as diisopropylna-7talene, diallylakanes such as Ll-phenyl-1-xylylethane, alkyl biphenyls such as isopropylbiphenyl, other triallyl dimethanes, and alkylbenzenes. , aromatic hydrocarbons such as benzylnaphthalenes, diallylalkylenes, and allylindanes. 7 Acid x
Sterle compounds; Phosphate ester compounds represented by tricresyl 7-mole 7-ate; Vegetable oils such as castor oil, soybean oil, and cottonseed oil or modified oils; High-boiling fractions of natural products such as mineral oil (from aliphatic hydrocarbons) ), which are also used in the present invention.

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

(C) Problem 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 semi-synthetic solid acid Although the colored image has excellent plasticizer resistance, the color density and the moisture resistance and light resistance of the colored image are poor, and the background yellows due to the window element oxide. On the other hand, organic color developers such as various phenolic compounds and novolac type phenolic resins 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, the recently proposed polyvalent metal compound of salicylic acid resin described in JP-A-63-186729 and JP-A-63-254124 has excellent coloring speed and little yellowing of the background, but it The so-called desensitizing effect, which is the effect of printing a desensitizing ink and preliminarily covering areas not required for color development to prevent color development, has the same problems as conventional color developers.

As a method to improve this problem, we conducted experiments such as reducing the amount of developer applied on the developer sheet to improve the desensitizing effect, or increasing the amount of desensitizing ink. The color development speed and density decrease, and the latter is because the ink transfers to the sheets [dye (color former) sheet, color developer sheet] that are overlapped with the desensitized ink printing area, causing problems such as poor color development. Lacks practicality.

Therefore, an object of the present invention is to provide a color developer sheet using a polyvalent metal salt of an aromatic carboxylic acid that causes less yellowing among organic color developers, and a polyvalent metal compound of salicyl'rRM resin that has an excellent color development speed. An object of the present invention is to provide a color developer sheet for a carbonless pressure-sensitive recording material, which has a high color density and an excellent desensitization effect.

(D) Means for Solving the Problems As a result of intensive research and experiments, the inventors have found that excellent color development speed and density can be obtained even with a small amount of color developer applied, and the desensitization effect is also improved. We have succeeded in developing a color developer sheet for carbonless pressure-sensitive recording materials.

That is, the present inventors found that the color developer is an aromatic carboxylic acid polyvalent metal salt, and further has the following general formula [I], (II), [II] or [IV) (wherein R1, R2, ns are independently hydrogen atoms,
It represents an alkyl group, cycloalkyl group, aralkyl group, or aryl group having 1 to 12 carbon atoms, and R1 and R12 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;
represents an alkyl group, cycloalkyl group, aralkyl group or aryl group.

R6 represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms) Ultrafine silicon particles are added to a pigment mixed with a polyvalent metallized salicylic acid resin having an average weight molecular weight of 500 to 10,000 as an organic color developer. The present invention was based on the knowledge that by using an acid, a color developer sheet for carbonless pressure-sensitive recording materials which has a high color density and an excellent desensitizing effect can be obtained.

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
-Phenylbenzyl ester, m-xylylene bis4-
Hydroxybenzoic acid ester, 4-hydroxybenzoic acid 7enethyl, 4-hydroxybenzoic acid-p-cumylbenzyl, 4-hydroxybenzoic acid-cinnamyl ester,
4-Hydroxybenzoic acid benzyl ester, 4-hydroxybenzoic acid-m-70 lobenzyl ester, 4-hydroxybenzoic acid-cumyl ester, 4,4'-hydroxy-2,2'-diptylphenyl sulfone, β-7 Enethyl orselinate, cinnamyl orselinate, orselic acid-σ-chlorophenoxyethyl ester 5/
L5/-methylenebis-2,4-dihydroxybenzyl acid benzyl ester, cedar-phenylphenoxyethyl orselinate, m-phenylphenoxyethyl orselinate, 2,4-dihydroxybenzoic acid-β-37-t
-butyl-4'-hydroxyphenoxyethyl ester, bisphenol A bisl-hydroxybenzoic acid ester, 5-β-l-methoxyphenoxyethoxy-2-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid-nermethylpenzyl ether, 2.4-dihydroxybenzoic acid-β-phenoxyethyl ester, 2.4-dihydroxy-6-methylbenzoic acid-methylbenzyl ester, bis-4-hydroxyphenylacetic acid WR:yenoxychedel ester, 4.4' -Diacetyldiphenylurea, 3-7 "enylnalidel ff11.5-J' = a-methylbenzyl-a-methylbenzylteritic acid, 5-l-methoxyphenol diethyloxysalicylic acid, 5-7 enoxyethoxysalicylic acid, 5-benzyl-a-methylbenzylsalicylic acid, 3-xylyl-5-(a,a-dimethylbenzyl)salicylic acid, 3-5-di(a-methylbenzyl)salicylic acid, 2-hydroxy-1-α- Examples include ethylbenzyl-3-su7toic acid.Calcium, magnesium, copper, zinc, tin, barium, cobalt and the like are used as polyvalent metal salts, but 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 No. 4124, for example, specifically, the following - Monana (V) (in the formula, R+1, R2, RJ
I and B10 are each independently a hydrogen atom, carbon number 1-1
2 represents an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group, and R2 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
represents a linear 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 - Monana [■] ( In the formula, R4 and R5 represent a hydrogen atom or a methyl group,
A styrene derivative represented by R6 represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms is subjected to a Friedel-Crach reaction, and the resulting resin composition and polyvalent metal salts of calcium, magnesium, aluminum, and copper are combined. , a salicylic acid resin polyvalent metal compound produced by reacting oxides, hydroxides, carbonates, and organic carboxylates such as 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 added to the following -Momona [■] in the presence of a 7-Riederkrat catalyst (wherein R4 and R5 are hydrogen atoms or carbon atoms ranging from 1 to 12 carbon atoms). represents an alkyl group, aralkyl group, aryl group, or cycloalkyl group, and X represents a halogen atom), and the resulting resin composition was reacted with the above polyvalent metal salt in the same manner. It is a polyvalent metal compound of salicylic acid resin produced by reaction. 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 1 O, 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 methylstyrene, 3- produced by reacting with styrene
Examples include zinc salt of phenylsalicylic 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 the 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(
5-(α) produced by reacting zinc salt of 4-methylbenzyl) salicylic acid resin,
, α-dimethylpenzyl) salicylic acid fat-resistant zinc salt, 2
．． Examples include zinc salt of 3-tert-butyl-5-7enyl salicylic acid resin produced by reacting 4-dimethylbenzyl chloride.

The pigment used in the present invention is ultrafine silicic acid.

There are many methods for producing fine-particle silicic acid, one of which is a dry method in which fine-particle silicic anhydride is precipitated by a gas phase reaction and collected. For example, silicon metal is obtained by igniting anhydrous silicic acid with coke in an electric furnace, and this is it! Hydrogen tetrachloride is heated and vaporized to form a full hydrogen layer, and then mixed with air. ! A method of baking, a method of gas-phase reaction with silicon tetrachloride, ammonia, and water, a method of decomposition of silicic acid, a method of organic silicon #R1 arsenal vapor! Examples include a method of combustion with compressed air, and a method of oxidizing silicon oxide. The other is microparticle water utilization from aqueous solution #R.
This is a wet method in which the precipitates are washed, dehydrated, dried, and crushed.

For example, specifically, a method of decomposing an alkali metal silicate with a mineral acid, a method of decomposing it with an alkali metal silicate and ammonium salt, a method of reacting an alkaline metal salt with an alkaline earth salt to form an alkaline earth salt, this! A method of decomposing with mineral acids such as sulfuric acid, hydrochloric acid, nitric acid, etc. A method of adding sodium silicate while passing carbon dioxide gas to the separated mother liquor of baking soda in the ammonia-soda method, A method of decomposing sodium silicate with an ion exchange resin, a method of decomposing natural Or phosphoric acid fertilizer by-product Kei f! 1. There is a method of decomposing salts with mineral acids.

In the present invention, fine particle silicic acid obtained by any of the above production methods can be used, but from the viewpoint of economy such as cost and coating liquid preparation properties, fine particle water obtained by a wet method using sodium silicate is particularly preferable. It is Japanese silicic acid.

The ultrafine silicic acid particles of the present invention are ultrafine silicic acid particles with a very small average particle diameter of 0.1 to 5 μm.

The fine particle silicic acid of the present invention is effective with any organic color developer, but the polyvalent metal compound of salicyl-plated resin exhibits an excellent effect.

The ultrafine silicic acid particles of the present invention may be mixed with other preparations if desired. Specific examples of pigments include calcium oxide, calcium carbonate, magnesium oxide, magnesium carbonate, magnesium hydroxide, Merck, kaolin, calcined kaolin, and titanium oxide.

The content of ultrafine silicic acid particles in the pigment is 5% by weight or more, preferably 10 to 503i% by weight. If the amount is less than 5% by weight, no significant effect on improving color density can be obtained.

Specific examples of the monochrome agent and pigment binder used in the present invention include starch, starch derivatives such as phosphoric acid ester starch, cationized starch, dialdehyde starch, casein, gelatin, polyvinyl alcohol, methyl cellulose, ethyl cellulose, Water bath polymers such as carboxymethyl cellulose, hydroxyethyl cellulose, polyethylene oxide, polyvinylpyrrolidone, vinyl acetate maleic acid copolymer, styrene maleic anhydride copolymer, sodium polyacrylate, sodium alginate, polyacrylamide, styrene butadiene, Examples include latex emulsions that are hydrophobic polymers such as acrylic and vinyl acetate.

In the present invention, a color developer, a pigment, an adhesive, and optionally an antifoaming agent and an anti-dusting agent are used to form a coating liquid for a single color agent sheet, and the coating liquid is coated onto a support such as paper by air, a blade, a roll, etc. m cloth method, the absolute dry weight solid content is 1.
Apply 5 to 15 t/rl.

A particularly preferable coating amount is 3 to 10 fβ in view of printability such as ink receptivity.

(E) Function The single-color developer sheet of the present invention has a high color density and is excellent in desensitizing effect, but when considering this principle, the color developer sheet '! The fine particle silicic acid coexisting with the monochromatic agent on the surface of 11111 is a porous material, and has a large oil absorption amount and specific surface area. This means that when printing is overlaid (pressurized) with a color former sheet coated with microcapsules containing (leuco) dye dissolved in oil, the microcapsules are destroyed and the built-in (leuco) dye-dissolving oil flows out, causing color development. Stimulates a color reaction with the agent. The translocation of this spilled oil to the color developer sheet is increased by the fine particle silicic acid having a high oil absorption, and the color density is improved. Furthermore, since it has porosity, the molten material that has reacted with the color developer to form a color enters the pores, and most of the molten material remains on the surface of the coating layer, resulting in a higher color density. As for the desensitizing effect, the amount of desensitizing ink transferred may also increase, but this is more important because most of the ink is absorbed and remains in the pores of the fine silicic acid particles on the surface of the m layer. This results in a desensitizing effect. To further improve the coloring density and desensitizing effect, use fine particle silicon as in the present invention! It is intended to make the particles smaller, so-called ultrafine particles.

(1'') Examples Preferred embodiments and excellent effects of the present invention will be specifically explained below using the most typical examples. All parts below are by weight.

Example 1 Zinc salt of monomethylbenzyl salicylic acid resin 100
Part: 10% polyvinyl alcohol aqueous solution: 50 parts: Water: 250 parts The above mixed WL was dispersed in a ball mill for 24 hours to obtain a 25% color developer dispersion (A).

Add 10 parts of 10% sodium hexametaphosphate to 57 parts of water, and add Super Particle Aqueous Silicic Acid (manufactured by Mizusawa Chemical Industry, Mizukasil P-802, oil absorption (boiled linseed oil) 24011).
g/1oot, specific surface area (BET method) 200m//f,
After adding 5 parts of kaolin (M, manufactured by Hiba Co., Ltd., Hydrasperse), and 50 parts of calcium carbonate (Brilliant-15, manufactured by Shiraishi Calcium Co., Ltd.) and dispersing it, the above 25 %a coloring agent 1 t [(A) 40 parts, 10% oxidized starch aqueous solution (MS-3800 manufactured by Solar Eclipse)
100 parts and 25 parts of 48% carboxylated styrene-butadiene copolymer latex (DL-620 manufactured by Syo Kasei Co., Ltd.) were added to prepare a coating liquid. This coating liquid was applied to a high-quality paper with a basis weight of 409β using a blade coater so that the coating amount was 5V (absolutely dry solid content), and dried to prepare a color developer sheet.

Example 2 15 parts of 10% sodium hexametaphosphate was added to 105 parts of water, and ultrafine aqueous silicic acid (Mizukasil P-802) was added.
), 25 parts of kaolin (Hydrasperse), and calcium carbonate (Brilliant)-15) After adding and dispersing 251B, the above 255il1 colorant dispersion (A) 40
parts, 1 (l oxidized starch aqueous solution (MS-3800) 10
011S, sterene butadiene at 48% strength
A coating liquid was prepared by adding 37.5 parts of co-mono-merized latex (DI, -620). This coating liquid was used in Example 1. A one-color agent sheet was prepared by coating and drying in the same manner as described above.

Example 3 Method for preparing 25% Peng coloring agent dispersion (B) 3,510% produced by reacting benzyl chloride
Polyvinyl alcohol aqueous solution 50 parts water
250 parts of the above mixture was dispersed in a ball mill for 24 hours, and 2596 color developer dispersion (B
).

Example 1. 25% of coloring agent dispersion (A)''Ik: above 2
A color developer sheet was prepared in the same manner except that the same amount of the 5th color developer dispersion (B) was used as the coating liquid.

Example 4゜Example 2. A developer sheet (1) was prepared in the same manner except that the same amount of the 2596-color developer dispersion (A) was replaced with the 25-color developer dispersion (B) to obtain a fabric solution.

Example 5 25% - Method for preparing colorant dispersion (C) 3.5 Zinc salt of di(α-methylbenzyl)salicylic acid 1
00 parts 10% polyvinyl alcohol aqueous solution 5
0 parts Water 250 parts The above mixture was dispersed in a t-ball mill for 24 hours to obtain a 25% color developer dispersion (C).

Example 2. 25% color developer dispersion (A)! 25S above
Color developer dispersion (C) Color developer dispersion (C) Color developer dispersion (C) Color developer dispersion (C) in the same manner except that the same amount of K was replaced with the coating solution! Created.

Comparative example 1゜Example 1. A color developer sheet was prepared in the same manner except that the coating solution was replaced with 5 parts of ultrafine aqueous silicic acid and 5 parts of kaolin (Hydrasperse).

Comparative example 2゜Example 1. Except for replacing 5 parts of ultrafine particle aqueous silicic acid with 5 parts of kaolin (Hydrasperse), and further replacing 25 parts of color developer dispersion (A) with 25 parts of color developer dispersion CB) in the same amount as the coating solution. A developer sheet was prepared in the same manner.

Comparative example 3゜Example 2. Ultrafine particle hydrated silicone [50 parts t was replaced with 50 parts of kaolin (Hydrasperse), and the same amount was replaced with 25% developer dispersion (A) and 25% hemochromic agent dispersion (C) to make a coating solution. A developer sheet was prepared in the same manner except for the following.

Measurement method during the test The developer sheet created was tested using the method below!
The results are shown in Table 1. It was shown to.

O Color development density Color developer sheet All commercially available Mitsubishi NCR paper Blue color development top paper (N-40) and calender to develop color 1
The color density after time was measured using a color difference meter as shown below. The smaller the number, the higher the color density.

0 desensitization effect Fuji photo offset desensitization ink (product name: FN
-103)'. Observe the degree of color development and decolorization of the desensitized ink printed area when printing with a dot printer together with the printed color developer Sheetra (commercially available Mitsubishi NCR paper Brablack coloring soil paper-40), and mark the degree as ○ or Δ. And so. (O mark: completely erased, Δ mark: slightly colored) (G) Effect of the invention As is clear from the examples, one of the organic color developers of the present invention is particularly In the polyvalent metal compound of salicylic acid resin, ultrafine hydrated silicon particles are added to the pigment to be mixed! By using 1121', a color developer sheet for a carbonless pressure-sensitive recording material was obtained which had a high color density and an excellent desensitizing effect.

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 type. A color developer sheet for a carbonless pressure-sensitive recording material, which is a color developer and contains ultrafine silicic acid particles 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.