JPS62255182A - Developer composition for pressure sensitive paper - Google Patents

Abstract

PURPOSE:To improve the color fastness to the light of a coloring image, by making polyvalent metal salt of aromatic carboxylic acid contain nickel complex series quencher. CONSTITUTION:Though various kinds of aromatic carboxylate can be used as aromatic carboxylic acid, the derivative of salicylic acid is preferable and magnesium, aluminum, calcium, titanium, manganese, zinc, and tin are exemplified as polyvalent metal salt. Zinc is especially preferably used among those. Such a polyvalent metal salt of aromatic carboxylate and nickel complex series quencher are mixed together, or otherwise fused by heating by the compounding ratio of 100pts.wt. in the former to 0.1-20pts.wt., preferably 0.3-10pts.wt. in the latter.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a color developer composition for pressure-sensitive copying paper. This paper relates to the improvement of color developers.

(Prior Art) Pressure-sensitive copying paper is also called carbonless paper, and is a copying paper that develops color by mechanical or impact pressure, such as when writing or using a typewriter, and can make multiple copies at the same time. There are some called transfer type papers and others called single colored papers, but their coloring mechanism is based on the coloring reaction between an electron-donating colorless dye and an electron-accepting color developer.

11 USP 2,712,
(2) Substituted phenols and diphenols as disclosed in Japanese Patent Publication No. 40-9309, (3) p as disclosed in Japanese Patent Publication No. 42-20144. -Substituted phenol-formaldehyde polymer, (4) Japanese Patent Publication No. 49-1
Aromatic carboxylic acid metal salts disclosed in Japanese Patent Publication No. 0856 and Japanese Patent Publication No. 52-1327 have been proposed, and some of them have already been put into practical use.

The properties that a color developer sheet containing such a color developer for pressure-sensitive copying paper should have include excellent color development that remains unchanged immediately after the sheet is manufactured and after long-term storage, and excellent color development properties that remain unchanged during storage and when exposed to radiation such as sunlight. Examples include low yellowing and a solid colored image that does not easily disappear or fade due to radiation, water or plasticizers.

Conventionally proposed sheets coated with color developers have advantages and disadvantages in terms of performance. For example, inorganic solid acids are inexpensive, but they adsorb gases and moisture in the air during storage, causing yellowing of the paper surface and a decline in coloring performance, while substituted phenols have insufficient coloring properties and the density of colored images. is low. p-substituted phenol, which is most commonly used as a formaldehyde polymer
Phenylphenol-novolak resin has excellent coloring properties, but the coated paper tends to yellow when exposed to sunlight or during storage (especially nitrogen oxides in the air), and the colored image deteriorates when it comes into contact with organic solvents. The disadvantage is that it easily fades.

Recently, polyvalent metal salts of aromatic carboxylic acids, which have excellent properties in various aspects, have attracted attention as an alternative to such color developers.

Pressure-sensitive copying paper using polyvalent metal salts of aromatic carboxylic acids is
It has excellent properties such as: (1) the color image does not easily discolor or fade over time; (2) the paper surface does not easily yellow even when exposed to light or gas components in the air; (2) it has high color development ability. However,■
It has the disadvantage that the light fastness of the colored image is poor, and (2) the color developing ability is greatly reduced by light irradiation.

As a means to prevent the deterioration of color developing ability due to light irradiation, a method has been proposed that uses fine particles mixed with organic ultraviolet absorbers such as salicylic acid derivatives, hydroxybenzophenone derivatives, and hydroxyhensitriazole derivatives (
JP-A-57-191087 (Japanese Patent Application Laid-Open No. 57-191087), although this method can improve the deterioration of color developing ability due to light irradiation, it was not effective in improving the light fastness of the colored image.

(Problems to be Solved by the Invention) An object of the present invention is to provide a color developer composition for pressure-sensitive copying paper which has improved performance and which has improved the above-mentioned drawbacks.

(Means for Solving the Problems) The present inventors have completed the present invention as a result of intensive studies to achieve the above object.

That is, the present invention is a color developer composition for pressure-sensitive copying paper containing (1) a polyvalent metal salt of an aromatic carboxylic acid, and (2) a nickel complex-based quencher.

Various aromatic carboxylic acids can be used as the aromatic carboxylic acid used in the present invention. Specifically, benzoic acid, p-
tert-butylbenzoic acid, trichlorobenzoic acid, terephthalic acid, 3-sec-butyl-4-hydroxybenzoic acid, 3-cyclohexyl-4-hydroxybenzoic acid, 3
．． 5-dimethyl-4-hydroxybenzoic acid, salicylic acid, 3-methylsalicylic acid, 3-isopropylsalicylic acid, 5-tert-butylsalicylic acid, 3-phenylsalicylic a, 3-(α-methylhensyl)salicylic acid, 3
-(α,α-dimethylbenzyl)salicylic acid, 3,5-
Di-tert-octylsalicylic acid, 3.5-DiLe
r t-butylnaricilic acid, 3-phenyl-5-(α,
α-dimethylhensyl)salicylic acid, 3. Cyclohexyl-5-(α,α-dimethylbenzyl)salicylic acid, 3
-(4'-α゛, α゛, α゛-dimethylbenzyl-5
-(α,α-dimethylbenzyl)salicylic acid, 3,5-
Di(α-methylbenzyl)salicylic acid, 3゜5-di(α
, α-dimethylbenzyl)salicylic acid, 3-(α-methylhensyl)-5-(α3 α-dimethylhensyl)salicylic acid, and the like. Among these, salicylic acid derivatives are more preferably used.

Examples of polyvalent metal salts of aromatic carboxylic acids that can be used include magnesium, aluminum, calcium, titanium, manganese, zinc, and tin. Among these, zinc is particularly preferably used.

The color developer composition of the present invention contains a nickel complex-based quencher together with such a polyvalent metal salt of an aromatic carboxylic acid.

Examples of nickel complex-based quenchers include nickel diethyldithiocarbamate, nickel diethyldithiocarbamate, nickel diethyldithiocarbamate, nickel isopropyl xanthate, (2,2-thiobis(
4-1-octylphenolate))-n-butylaminenickel(II), (2,2-thiobis(4-t-octylphenolate))-2-ethylaminenickel(
II), (2,2-sulfonebis(4-nonylphenolate))-nickel (■), bis(1,2-dithiophenolate)nickel-tetra-〇-ethylammonium, bis(1-methyl- 3,4-dithiophenolate) nickel-tetra-n-butylammonium, bis(3,4,6-trichloro-1,2-dithiophenolate)nickel-tetra-n-butylammonium, bis(l-thio- 2-naphtholate) nickel-tetra-
n-Butylammonium, bis(4-chloro-0-phenylenediamino)nickel, bis(diiminosuccinonitrilo)nickel, bis(cis-1,2-bis(p-
methoxyphenyl)ethylene-1,2-dithiolate)
Examples include nickel, oil-soluble nickel complexes or salts such as nickel paratoluenesulfonate or nickel dodecylhenzenesulfonate.

According to the present invention, (1) a polyvalent metal salt of an aromatic carboxylic acid (hereinafter referred to as (2) component), and (2) a nickel complex-based quencher (hereinafter referred to as (2)
Various methods can be used to produce a color developer composition for pressure-sensitive copying paper containing the following components.

Namely, (1), a method of heating and blending the ■component and the ■component; (2) a method of dissolving the ■component and the ■component in a common solvent and then removing the solvent; (2) A method in which the component is heated and mixed with a third substance that is compatible with the component, or (4) a method in which the component is mixed in powder form.

Among these methods, method (3), that is, a method in which components (1) and (2) are heated and mixed together with a compatible third substance is most commonly used. Examples of polymers that are compatible with component Examples include polymers, butadiene-based polymers, vinyl acetate-based polymers, (meth)acrylic acid ester-based polymers, and the like.

In the color developer composition of the present invention, the mixing ratio of component (1) and component (2) is from 0.1 to 100 parts by weight of component (2).
The amount is 20 parts by weight, preferably 0.3 to 10 parts by weight.

When producing a color developer sheet using the color developer composition of the present invention, in addition to the color developer composition of the present invention, known color developers,
That is, there is no problem in using it in combination with inorganic solids such as activated clay, organic polymers such as phenol-formaldehyde resin, etc. Furthermore, zinc, magnesium, aluminum,
One or more oxides, hydroxides or carbonates of polyvalent metals selected from the group consisting of lead, titanium, calcium, cobalt, nickel, manganese and barium may be used in combination.

The method for preparing a color developer sheet using the color developer composition for pressure-sensitive copying paper of the present invention includes (1) applying an aqueous paint using an aqueous suspension of the color developer composition to a support such as paper; how to apply it,
(2) A method in which a color developer composition is strained during paper making, and (3) a method in which a color developer composition dissolved or suspended in an organic solvent is coated on a support can be used.

When preparing a paint, kaolin clay, calcium carbonate, starch, synthetic and natural latex, etc. are distributed to create a paint with appropriate clay and coating suitability. The proportion of the color developer component in the paint is 5 to 70χ in the total solid content.
If the proportion of the color developer component is less than 5%, sufficient color development cannot be achieved, and if it is more than 70%, the paper properties of the color developer sheet will deteriorate. The amount of paint applied is 0.5 by dry weight.
g/cn1 or more, preferably 1-Log/cn.

The color developer composition for pressure-sensitive copying paper of the present invention requires only a small amount of developer component and paint to be applied, and the concentration, viscosity, etc. of the paint can be changed over a relatively wide range, so it can be coated on-machine. , off-machine coating is possible, which brings great benefits not only in terms of performance but also in terms of the pressure-sensitive paper manufacturing process.

(Operations and Effects) The present invention provides a color developer composition for pressure-sensitive copying paper, which comprises a polyvalent metal salt of an aromatic carboxylic acid containing a nickel complex quencher.

The color developer sheet using the color developer composition for pressure-sensitive paper of the present invention does not cause yellowing due to light or gases such as nitrogen oxides in the air (
In addition, the color image is stable against light and plasticizers, and the color developing ability of the color developer does not deteriorate even when exposed to light, further reducing photoyellowing.

These properties make it possible to expand its use to applications for which conventional products are unsuitable, and its practical significance is extremely large.

(Example) Hereinafter, the method of the present invention will be explained in detail with reference to Examples.

Example I 100 parts by weight of 3.5-di(α,α゛-dimethylpencil)salicylic acid zinc salt, 20 parts by weight of low molecular weight polystyrene (Sanyo Kasei Hymer 5T-95) and bis-(1
2 parts by weight of nickel-tetra-n-butylammonium (1,000-2-naphthorate) were heated and mixed at 180° C. and then cooled to obtain a light brown resinous composition (8).

Example 2 In 1600 parts by weight of toluene, 1000 ffi parts of α-thimerstyrecene combination (average molecular weight: 1100) was dissolved, and further 600 parts of 3-cyclohexyl-5-(α, α゛-dimethylhensyl) salicylic acid zinc salt was dissolved. Parts by weight and [2,
2-thiobis(4-tert-octylphenol-1.
)〕-〕n-butylamine nickel ■) (Product name Cyasolder 1084--manufactured by American Cyanamid Company) 2
0 parts were dissolved. The solvent was evaporated to obtain a light-colored resinous composition (B).

Example 3 3-α,α“-dimethyl-\ndylsalicylic acid zinc salt 1
00 parts by weight, 1-1 copolymer of butyl acrylate
00 parts by weight and 3 parts of 2.7 K dibutylthiobamate were mixed and heated to 200°C to obtain a pale green yellow resinous composition (
C) was obtained.

Example 4 A light-colored resinous composition was prepared in the same manner as in Example 1, except that the same amount of nickel dodecylbenzenesulfonate was used in place of his-(I-thio-2=naphthorate)nickel-tetra-n-butylammonium. Product (D) was obtained.

Comparative Examples 1 to 3 Light-colored resinous compositions (E) to (
G) was obtained.

Comparative Example 4 [2,2-thiobis(4-tert-octylphenolate)]-lobylamine nickel (n) was replaced with 2
-(2゛-Hydroxy-3,5゛-di-t-butylphenyl)benzotriazole, trade name Tinuvin 320-
Example except that the same amount of Nippon Ciba Gaiki Co., Ltd.) was used.
A light-colored resinous composition (11) was obtained in the same manner as in Example 2.

Test Examples The color developer compositions obtained in Examples and Comparative Examples were wet-pulverized in the presence of a small amount of polymeric anionic surfactant to form an aqueous suspension with a solid content of 40% by weight (average particle Diameter 2.5μ
).

Next, an aqueous coating liquid (solid content: 30% by weight) having the following composition was prepared using this suspension.

Weight ratio of solids Light calcium carbonate 100 Color developer composition 15 Starch binder 8 Synthetic rubber latex 8 This aqueous coating liquid was coated with 40 g of this water-based coating using a Mayer bar coater.
A developer sheet was prepared by applying and drying the mixture to a m2 high-quality paper so that the dry coating amount was 6 g/rrr.

A performance test was conducted using these color developing sheets.

The performance was measured using the following method.

(1) 0 color development rate and density (conducted in a thermostatic chamber at 20°C and 65xl?H) Commercially available top paper for blue coloring containing crystal violet lactone (CVL) as the main pressure-sensitive dye (NW-4 manufactured by Kanzaki Paper Co., Ltd.)
07), the color developing sheet (lower paper) obtained in the example
Place both coated surfaces facing each other and place them on top of each other, and use an electronic typewriter to engrave and develop the color.

The reflectance 30 seconds and 24 hours after stamping is measured using a TSS type Hunter colorimeter (using an amber filter) and displayed as a Y value.

(2) Light fastness of 3 colored images (The color developing sheet developed using method 11 was exposed directly to outdoor sunlight for 10 hours) The colored image after the test was measured using a Hunter colorimeter (using an amba filter). The color was measured and displayed.

The smaller the difference before and after the test, the less fading of the colored image due to light, which is preferable.

(3) Degree of deterioration of color developing ability due to light The color developing sheet prepared in the previous section was exposed directly to sunlight outdoors for 10 hours),
Thereafter, a typewriter color development test was conducted in exactly the same manner as in (1) to determine the degree of remaining color development ability.

○ The coloring ability is sufficiently maintained.

△　The coloring ability is considerably reduced.

×　All (Losses coloring ability.

(4) Exposure to outdoor sunlight for 10 hours using the same method as for deterioration of the original image of the developer sheet (3))
To investigate the yellowing tendency of the color developer sheet surface, the color was measured using reflectance values (using a blue filter) before and after the test. The thicker the reflectance (and the smaller the difference before and after the test, the less the tendency for the original image of the color developer sheet to change.

The results are shown in Table-1.

(below margin)

Claims (1)

[Claims] 1) (1) a polyvalent metal salt of an aromatic carboxylic acid, and (2) a polyvalent metal salt of an aromatic carboxylic acid;
) A color developer composition for pressure-sensitive copying paper containing a nickel complex-based quencher. 2) The color developer composition for pressure-sensitive copying paper according to claim 1, wherein the polyvalent metal salt of aromatic carboxylic acid is a polyvalent metal salt of a salicylic acid derivative.