JPS6013840B2 - color developer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color developer that develops color by reacting with a colorless or light-colored compound used in pressure-sensitive recording, heat-sensitive recording, and the like.

Conventionally, oil-soluble electron-accepting condensates, uncondensed products, and chelate ligands have been used as color developers for multiple copying and recording, and aromatic compounds with good color development have been put into practical use.

Those aromatic compounds commonly have -OH or -COO
It is well known that there are some species that have two or more of both, or have two or more of both.

Furthermore, these -OH, one COO days are etherified,
It may be esterified or used as a metal salt, both of which are well known. Since -OH or 1 COO of aromatic compounds gives strong acidity, aromatic compounds with these naturally become strong acidic substances, and when coated on a recording paper base material such as paper, the paper will deteriorate over time. Changes may cause strength deterioration, reaction with various coating formulations may cause yellowing or browning, and in some cases, loss of color development.

Therefore, all or a part of -OH, one COO day, has been blocked by etherification, esterification or metal chlorination for practical use.

However, depending on the color-forming mechanism, these blockages may cause the color-forming ability to be lost and become useless as a color developer.When metal chlorides, especially salts with monovalent metals or -NH4, are used, the basicity of these salts may cause the initial color to change. The agent itself becomes colored, leading to unfavorable results.

Therefore, the present inventors focused on organic bases and investigated aliphatic and aromatic amines, but found that all of them either lost their coloring ability or caused coloration in the complexion agent itself, which was disadvantageous.

The present inventors then conducted repeated studies on basic compounds such as carbonic acid derivatives, and found that salts made from guanidine, derivatives thereof, or basic compounds having a triazine nucleus do not cause the above-mentioned disadvantages. That is, according to the present invention, a salt formed from a condensate of an aromatic compound having one OH and/or one COO and formaldehyde, and a basic compound having a guanidine, a derivative thereof or a triazine nucleus. A color developer is provided.

The condensates of formaldehyde and aromatic compounds having -OH and/or one COO used in the present invention include, for example, condensates made from formaldehyde and compounds having -OH such as phenols, and condensates of benzoic acids. -CO condensates made from formaldehyde and compounds with -COO such as or -CO such as salicylic acids
It means a condensate made from a compound containing O and -OH and formaldehyde, and includes a single substance, a mixture, and a co-condensate thereof (hereinafter simply referred to as a condensate).

Also, three -OH and one -CO such as gallic acid
Cocondensates with O days may also be included in the cocondensate.
All of these are conventionally known as color developers for colorless dyes and metal ligands for forming colored chelate compounds. The gist of the present invention is to utilize the above-mentioned condensate as a guanidine derivative or a triazine nucleus.

In order to obtain a guanidine salt, it is generally advantageous to react with a guanidine salt, particularly guanidine carbonate, which is easily obtained as a stable compound, rather than reacting isolated guanidine with a condensate.

Guanyluria (C2 is O
N4), guanone (C4 day 90 is 3), etc., form salts with good properties with condensates, and the salts themselves do not color, are stable, and have excellent color developing ability.

A typical basic compound having a triazine nucleus is melamine (C3 is N6).

A salt with a condensate can be obtained directly from melamine, and it becomes an extremely stable salt that does not cause coloration and has good head coloring ability. Other basic compounds having a triazine nucleus include ammeline (C3 day 50N5) and ammelide (C3 ratio 02N4), among which ammeline is particularly preferred. In addition, Melam (C64N,.), Melam
Rem (C, 6 days, 6N, o), Melon (C, 8 days, 9N)
27), benzoguanamine (C9 days, N5), etc. are stable basic compounds, and like melamine, they form condensates and salts, and are effective as color developers.

The color developer of the present invention i.e. -OH and/or -COO
A compound that reacts as a color developer to form a color (hereinafter referred to as (referred to as color developer) include triphenylmethane phthalide series, fluoran series, phenothiazine series, indolyl phthalide series, ryuko auramine series, spiropyran series, triphenylmethane series, triazene series, naphtholactam series, and benzopyrans. Ti, Mo, W, Ni,
Inorganic compounds and organic compounds such as Co, preferably Fe
Chelate coloring agents such as fatty acid salts, naphthenates, oxides of V, quaternary ammonium salts, and various other known agents are used.

The pigment of the present invention is well compatible with these color formers and can be used to make various types of recording paper.

The salt of the present invention, that is, the salt of the above-mentioned formaldehyde condensate and a basic compound such as guanidine or melamine, must necessarily be present in the complexion agent as a normal salt in chemical equivalent terms. Depending on the purpose of use, one or the other can be used in excess. In other words, it can be present in the color developer as a compound such as an acidic salt or a basic salt. In particular, when obtaining a water-based paint with a color developer, the basic substance of the present invention is blended in excess, and a coating liquid with excellent coating suitability on the alkaline side can be obtained.

The complexion agent of the present invention is blended with various compounding agents suitable for the purpose of use in solvent paints, hot melt paints, or inks for various printing methods such as letterpress, offset, gravure, and flexography. If a condensate that has not become a salt is blended, it will react with various blending agents and cause undesirable phenomena such as precipitation and coagulation. In addition, strong acids such as mineral acids may remain in the condensate that has not become a salt, and the condensate and the acid as an impurity elute various compounding agents, especially iron in pigments. Condensation products and chelate colorants may be created, resulting in coloring of paints and inks, making it impossible to obtain a white paint layer. If the color developer of the present invention is used, such a phenomenon can be prevented, a white coating layer can be easily obtained, and the coating layer will not economically yellow or brown due to light.

Various compounding agents corresponding to the purpose and the color developer of the present invention are used in the above-mentioned paints and inks, but natural white earths, zeolites, bentonites, and artificial metals, which are generally used as color developers for colorless paints, are used. Inorganic color developers such as citrate and silica can also be used in combination.

Further, an inorganic-organic white pigment is often used in combination in order to effectively receive the color former solution transferred from the color former capsule during printing. By doing so, fine absorption pores are provided to the color developing layer, giving it receptivity and absorption.
Effective against increased cephalochromia. As a binder, natural or synthetic polymeric materials, oligomers, etc. are blended, and in some cases tin, animal or vegetable drying or semi-drying oils and fats are blended, and sometimes natural or synthetic resins and waxes are blended. It becomes paint or ink.

In addition, various compounding agents such as fluorescent dyes, ultraviolet absorbers, antioxidants, bag oil desiccants, and polymers as thickeners are used in combination depending on the purpose.

- In addition, the color developer of the present invention can be used in combination when using an acrylic compound using a photocuring method or a radiation curing method in order to dry the constituent film within a short time.

Furthermore, the complexion agent of the present invention can also be encapsulated by a known method and used as a paint. In the case of thermal recording paper, it is desirable to incorporate the color developer of the present invention as a water-based paint.

Next, the present invention will be specifically explained with reference to Examples. Parts are by weight. Example 1 138 parts of salicylic acid, 1 part of rt-butylphenol
After keeping 5 parts of 37% formaldehyde aqueous solution and 10 parts of hydrochloric acid at 100° C. for 10 hours, the resulting composite was washed with water, dried, and pulverized.

Two parts of the obtained white condensate powder and 5 parts of melamine were poured into water to form a slurry, and the slurry was pulverized using a sand mixer to complete the neutralization reaction.

Four parts of aluminum hydroxide, two parts of calcium carbonate, and five parts of silica were added to the resulting slurry, and the slurry was again run in a sand mixer.

Next, 10 parts of polyvinyl alcohol was added as an aqueous solution to obtain a coating liquid with a solid content of 20%. The liquid value was 7.5. Spread this liquid on a 40g pillow of high-quality paper using an air knife.
A color developer coated paper was obtained by coating with a solid content.

Comparative Example 1 Aqueous ammonia was added to the condensate powder obtained in the same manner as in Example 1 to make a slurry with a pH of 7.5, and complexion agent coated paper was prepared in the same manner as in Example 1 except that melamine was not added. Obtained.

Example 2 Add 4 parts of guanidine carbonate to 15 parts of the condensate powder obtained in Example 1, mix in a kneader, add 24 parts of linseed oil and stir, and then add 1 part of stearic acid. Knead briefly, transfer to a roll mill, mix well with 56 parts of aluminum hydroxide, and finally add 0.0% manganese naphthenate as a desiccant. A uniform ink-like finish was achieved by adding a pen.

When a portion of this was dissolved in alcohol and the pH was measured, it was found to be 7.5. This was printed on 4th grade high-quality paper using a rubber plate of a letterpress printing machine to obtain developer-coated paper.

A similar pigment-coated paper was also obtained by substituting the same amount of guanyluria for guanidine carbonate.

Comparative Example 2 Spot printing was carried out in the same manner as in Example 2 except that guanidine carbonate was not added to obtain developer-coated paper.

At this time, the resulting spot-coated surface had poor drying and setting properties, and the surface sticky feeling did not disappear even after a period of time.

This is because the desiccant manganese naphthenate was decomposed by the acidity of the condensate. Test Examples The results of the performance comparison test of head coloring agent coated paper obtained in the above examples and comparative examples are as follows.
It was as shown in the table.

The coloring agent-coated paper used for coloring the print was obtained as follows. crystal violet lactone 6
Diarylethane (SAS-290 Nisseki Chemical) 94
After dissolving the gelatin capsule solution in a conventional manner, one part of polypynyl alcohol was added to prepare a coating solution.

The coating weight was approx. /, and the base paper used was 4/4 high quality paper. Table 1〇〇Good〇 Yan Good The obtained ink-like color developer was spot-printed on the color former-coated paper surface described in the test example using a rubber plate at a rate of 1 g/spot.

The resulting spot-printed surface was a self-coloring pressure-sensitive recording paper, and it was possible to overlay multiple images, and the density of the colored print was extremely high. Example 4 A color developer obtained in the same manner as in Example 2 except that 24 parts of linseed oil was replaced with rapeseed oil and 0.2 parts of manganese naphthenate was removed was used in the color former coating described in the test example. Spot printing was performed on the paper surface using a rubber plate at a rate of 1.5 g/.

The resulting spot-printed surface is a self-coloring pressure-sensitive paper, but the coloring component has transferability, and when printing was performed with the unprocessed high-quality paper facing the opposite surface, a clear printed image was obtained on the opposite surface. Example 5 6 parts of crystal violet lactone and 94 parts of diallyltane used in the color former coated paper described in the test example
Part, PSD-150 (fluoran-based, Shinnichi Kani Kako) 4
1 part, 2 parts of crystal violet, 1 part of ferric naphthenate
Color former coated paper was obtained in the same manner as in the test example except that 93 parts of diallylethane and 93 parts of diallylethane were used as gelatin capsule liquid.

Claims (1)

[Claims] 1 A condensate of an aromatic compound having -OH and/or -COOH and formaldehyde, and a basic compound having a guanidine, its derivative or a triazine nucleus,
A color developer characterized by containing a salt formed from.