JPS61149390A - Color develop sheet for pressure-sensitive recording - Google Patents

Abstract

PURPOSE:To enhance color developing speed, by using as a color developer fine particles of a mixture obtained by uniformly dispersing a salicylic acid derivative and/or a polyvalent metal salt thereof in a petroleum resin. CONSTITUTION:To obtain the fine particles of a mixture of a salicylic acid derivative and/or a polyvalent metal salt thereof with a petroleum resin, for example, the resin is melted by heating, then the derivative and/or the salt is put into the melted resin, the mixture is melted or uniformly dispersed, followed by cooling and pulverizing. The derivative and/or the salt in the resin is substantially made to be amorphous, so that the fine particles are easily dissolved in an oil in which a color former is dissolved, and reaction of molecules of the color former with molecules of the color developer is accelerated, resulting in a marked enhancement of the color developing speed.

Description

DETAILED DESCRIPTION OF THE INVENTION (AJ) Field of Industrial Application The present invention relates to a color developer sheet for pressure-sensitive recording. More specifically, it relates to a color developer sheet that reacts with a colorless organic compound to form a colored image.

However, prior art: Obtaining a colored image through a contact reaction between a screw-donating, almost colorless organic compound (hereinafter referred to as a color former) and an electron-accepting solid acid (hereinafter referred to as a color developer) is an old method. It is said from Examples of materials that specifically utilize this phenomenon include pressure-sensitive copying paper (e.g., U.S. Pat. Nos. 2,505,470 and 2,505).
489) and thermal recording paper (e.g., Special Publication No. 45-14039)
No.).

In general, inorganic solids such as activated clay, acid clay, and attapal guide have been frequently used as color developers for pressure-sensitive plate paper.

However, these clay-based inorganic f4-acids lack stability of colored images against moisture and light.

Recently, novolac type phenol-formalin resin has been put into practical use instead of this, and derivative 2 and/or its polyvalent metal salts have also come to be used as salicyl. Polyvalent metal salts of salicylic acid derivatives themselves have color developing ability, but salicylic acid derivatives can be used as coloring agents in combination with polyvalent metal balides, hydroxides, and carbonates (Japanese Patent Publication No. 1973- No. 20883). However, when these color developers are used alone, the color density is low, so it has been proposed to improve the color density by using them in combination with polystyrene, xylene resin, etc., as described in Japanese Patent Publication No. 1195/1982. However, the image coloring speed was not sufficient.

(C) Problems to be Solved by the Invention Therefore, the present inventor conducted many tests to improve color development speed using salicylic acid derivatives and/or polyvalent concomitant salts thereof.
We have discovered seven methods for producing a color developer with faster image color development speed and higher color density than ever before.

(To) Means for Solving the Problems The present invention is characterized in that fine particles of a mixture in which a salicylic acid derivative and/or its polyvalent Kasamin salt are uniformly dispersed in a petroleum resin are used as the isshiki paste. It is.

The color developer of the present invention is used by adhering it onto a flat support such as paper with an adhesive. For this purpose, clays, dispersants, etc. may be added as necessary.

Examples of the salicylic acid derivatives used in the present invention include those in which salicylic acid or the benzene nucleus of salicylic acid has 1 to 4 substituents such as alkyl, cycloalkyl, aralkyl, aryol, or halogen. can.

All of the above salicylic acid derivatives form salts with polyvalent metals, and the polyvalent metals used include zinc, magnesium, aluminum, titanium, calcium, cobalt,
These include nickel, manganese, tin, and copper. It is also possible to use a t-mixture of the derivative in the form of an acid that is not a salt and a metal compound.

The petroleum resin that can be applied in the present invention is made from naphtha,
This is thermally decomposed to create ethylene, globylene, and other C2-C4
olefin is separated and the remaining C5 to C9 olefin is polymerized in a mixed state, resulting in a molecular weight of approximately 2.0.
00 or less thermoplastic resin, which contains, for example, aliphatic water-rehydrated hydrogen resin, alicyclic hydrocarbon resin, hydrogenated resin
4) Lachrymal carbonized non-crystalline resin, aromatic hydrocarbon resin, etc.

Specific examples of aliphatic hydrocarbon resins (petroleum resins) include those shown below, and specific examples of alicyclic hydrocarbon resins (petroleum resins) include those shown below. ) Hydrogenated alicyclic hydrocarbon resin (petroleum resin) is a hydrogenated alicyclic hydrocarbon resin (petroleum resin), and a specific example of an aromatic hydrocarbon resin (petroleum resin) is Toho Hi-Resin (' 4
I (formation unknown).

All of these are included in the present invention.
No. 5 shows a remarkable effect of improving color developing ability compared to the known M polymer.

There are several ways to obtain mixed particles of salicylic acid derivatives and/or their polyvalent metal salts and petroleum resins.

For example, a petroleum resin is heated and melted, a salicylic acid derivative and/or its polyvalent metal salt is added thereto, dissolved or uniformly dispersed, and after cooling, the resin is crushed to form fine particles. In addition, a salicylic acid derivative and/or its polyvalent metal salt may be dissolved or uniformly dispersed in a solution of petroleum resin dissolved in an organic solvent by heating if necessary, and used as a developer ink raw material. After evaporating the organic solvent,
It can also be obtained by grinding into imitative particles.

In order to fully exhibit the effects of the present invention, the weight percentage of the salicylic acid derivative and/or its polyvalent metal salt to the petroleum resin is preferably 10% or more and 90% or less.

In the present invention, the salicylic acid derivative and/or its polyvalent metal salt in the petroleum resin is substantially amorphous, and therefore is easily soluble in the oil in which the color former is completely dissolved, and is easily visible with the color former molecules. It is presumed that the reaction of coloring agent molecules is accelerated, thereby significantly improving the rate of color development. However,
It is unclear why petroleum resins are superior to the organic polymer compounds specifically described in No. 1195. Or it may be because petroleum resins are complex mixtures of organic polymer compounds with slightly different chemical structures. This is probably because it has a high alpha character.

■　Example The present invention will be explained in more detail by way of examples.

In addition, all "parts" in the examples represent "parts by weight."

Example 1 Aliphatic petroleum resin, trade name Markaletstu-100
50 parts of B (manufactured by Maruzen Petrochemical Co., Ltd.) are heated and melted at 150°C, and 20 parts of zinc 3,5-di-tert-butylsalicylate is added thereto and stirred thoroughly to uniformly disperse.

After cooling and solidifying, it was ground in a mortar, dispersed in 280 parts of a 1% polyvinyl alcohol aqueous solution, and finely ground in a ball mill for 2 days. To this was added 30 parts of calcium carbonate, 10 parts of 5% aqueous sodium phosphate fl solution, 3.8 parts of 40% aqueous sodium polyacrylate solution, and 6 g parts of 48% SBR latex to prepare a coating liquid.

This coating solution was coated on high-quality paper with a dry coating weight of 4η and dried at 105°C to obtain a color developer sheet.

Example 2 Same as Example 1 except that a hydrogenated alicyclic petroleum resin, trade name Alcon P90 (manufactured by Arayo Kagaku Co., Ltd.) was used instead of the aliphatic petroleum resin in Example 1. I made it.

Example 3 3-7. The same procedure as Example 1 was carried out except that zinc enylsalicylate was used.

Example 4 Except that zinc 3-phenylsalicylate was used in place of zinc 3.5-di-tert-butylsalicylate in Example 1, and Alcon P90 was used in place of the aliphatic petroleum resin.
The same procedure as in Example 1 was carried out.

Example 5 Example 1 except that 18 parts of 3,5-di-tert-butylsalicylic acid and 6 parts of zinc oxide were used instead of 20 parts of zinc 3,5-di-tert-butylsalicylate in Example 1. Same as 1.

Comparative Example 1 20 t of zinc 3.5-di-tert-butylsalicylate
It was dispersed in 280 parts of tll-1%yt'lJ bi=A/7le w-# aqueous fi and pulverized in a ball mill for 2 days. To this, 80 parts of calcium carbonate, 10 parts of 5% sodium pyrophosphate, 3.8 parts of 40% sodium polyacrylate,
A coating solution was prepared by adding 65 parts of 48% SBR latex, and a color developing sheet was prepared in the same manner as in Example 1.

Comparative Example 2 The same procedure as in Example 1 was carried out, except that polystyrene, trade name Picolastic A-75 (manufactured by Exxon Corporation), was used instead of the aliphatic petroleum resin in Example 1.

Comparative Example 3 The same procedure as in Example 1 was carried out, except that a xylene resin, Nikanol S-100 (manufactured by Mitsubishi Gas Chemical Co., Ltd.), was used instead of the aliphatic petroleum resin in Example 1.

Comparative Example 4 The same procedure as Comparative Example 1 was carried out except that zinc 3-phenylsalicylate was used instead of zinc 3,5-di-tert-butylsalicylate.

Comparative Example 5 Instead of the aliphatic petroleum resin of Example 3, Picolastic A-75. The procedure was the same as in Example 3 except that i was used.

Comparative Example 6 In place of the aliphatic petroleum resin of Example 3, dicanol 8
The same procedure as in Example 3 was carried out except that -1001- was used.

Comparative Example 7 Comparative Example except that 3,5-di-tert-butylsalicylic FIt18tflS and 6 parts of lead oxide were used instead of 20 parts of zinc 3,5-di-tert-butylsalicylate in Comparative Example 1. Same as 1.

Comparative Example 8 The same procedure as in Example 5 was carried out except that Biplastic-75 was used in place of the aliphatic petroleum resin in Example 5.

In both Examples and Comparative Examples, the coating amount of zinc 3.5-di-tert-butylsalicylate and zinc 3-phenylsalicylate was 0.59 f/d, and the coating amount of 3.5-di-tert-butylsalicylic acid was 0.゜52v~.

In order to evaluate the line color sheet of the present invention, commercially available Mitsubishi NCR Paper Blue was stacked on each of the color developer sheets obtained in this manner so that the coated surfaces faced each other, and calender pressure was applied. Fully colored and round.

Table 1 shows the color density and their ratio (%
) held a meeting.

(Left below) Table 1. In color developer test results Table 1, BZ is zinc 3,5-di-tert-butylsalicylate, Pz is zinc 3-phenylsalicylate, and B is
3,5-di-tert-butylsalicylic acid is shown. In addition, A is aliphatic petroleum resin, HCA is starch added FJ ¥1
Cyclic petroleum resin, PS indicates polystyrene resin, and X indicates xylene resin.

Table 1 shows that when the color developer is a salicyl cough derivative or its polyvalent metal salt alone, the coloring density is low, but when used in combination with polystyrene, both the coloring density and the coloring speed are the same as above. However, as shown in Example 9, it can be seen that the use of petroleum resin significantly improves the color density and color development speed.

Effects of the Invention As described above, the color developing sheet produced according to the present invention has a faster coloring speed than conventional sheets and a deeper coloring degree, so even immediately after printing, a good image quality can be obtained, making it easy to read in practical terms. It has characteristics that make it easier.

(Issuance of procedural amendments) February 7, 1985 Commissioner of the Patent Office Shiga Palm print 2, Name of the invention is misleading, Negative color sheet 3, Relationship with the person making the amendment case Patent application office Tokyo 4-2 Shiratama-chome, Maruno, Chiyoda-ku, Tokyo Name (598) Mitsubishi Paper Mills Co., Ltd. 4 Address of agent Address: Mitsubishi Paper Mills Co., Ltd. 3-4-2 Marunouchi, Chiyoda-ku, Tokyo 100 Telephone number: (213) 3641 Showa Year Date 6: Number of inventions increased by amendment -l 7: Subject of amendment (1) On page 3, line 13 of the specification, "on a flat plate" is amended to "on a flat plate".

Claims (1)

[Claims] 1. A color developer sheet for pressure-sensitive recording, characterized in that fine particles of a mixture of a salicylic acid derivative and/or its polyvalent metal salt uniformly dispersed in a petroleum resin are used as a color developer.