JP2000289330A - Developer, water dispersion, recording sheet and development ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a developer of good dispersion stability, superior light fastness of a white paper and superior water resistance of a recording image and also its water dispersion and manufacture a recording sheet and a development ink thereof. SOLUTION: A developer containing a polyvalent metal salt of a derivative of salicyclic acid contains (a) at least one kind of 30-85 wt.% derivative of salicyclic acid composed of 1-3% mol substituted styrenes in 1 mol salicyclic acid and (b) at least one kind of 15-70 wt.% derivative of salicyclic acid composed of 4 mol substituted styrenes in 1 mol salicyclic acid. The developer contains a water dispersion and a development ink, and a recording sheet is provided with a layer containing the developer on a substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a color developer containing a polyvalent metal salt of a salicylic acid derivative, and an aqueous dispersion, a recording sheet and a color ink obtained using the same.

[0002]

2. Description of the Related Art Conventionally, for example, pressure-sensitive recording sheets include:
For example, electron-donating color-forming compounds (color formers)
An upper sheet in which microcapsules encapsulating a capsule oil in which is dissolved is coated on one surface of a support, and a color developer (electron-accepting compound) that develops a color when one surface of the support is contacted with an electron-donating color-forming compound. There is a middle sheet in which microcapsules are coated on the opposite side, and a lower sheet in which a developer is coated on one side of the support. Generally, an upper sheet-a lower sheet, or an upper sheet- Medium use sheet
Used in combination with lower seats. In addition, there is a single copy sheet in which microcapsules and a developer are applied to the same surface of a support and can be copied on one sheet.

Hitherto, salicylic acid derivatives have been known to be useful as a developer for recording materials (for example, pressure-sensitive recording materials and heat-sensitive recording materials). For example, a polyvalent metal salt of a salicylic acid derivative in which salicylic acid is disubstituted at positions 3 and 5 with α-methylbenzyl, α, α-dimethylbenzyl, cyclohexyl, etc.
No. 25174), a salicylic acid ester and a styrene are reacted to hydrolyze the obtained salicylic acid ester resin, and then a polyvalent metal salt of the salicylic acid resin obtained by reacting with a polyvalent metal compound (Japanese Patent Laid-Open No. -13378
No. 0), 5- [4 ′-(α′-methylbenzyl) -α
-Methylbenzyl] salicylic acid polyvalent metal salt and 3,5-di (α-methylbenzyl) salicylic acid polyvalent metal salt, each of which has two styrene units and a mixing ratio of 1 : 9 to 9: 1 (weight ratio) (Japanese Unexamined Patent Publication No. 62-84045), a mixture of a salicylic acid derivative having two styrene units and a salicylic acid derivative having three styrene units (Japanese Unexamined Patent Publication No. 91043
Publication), (a) a salicylic acid derivative obtained by reacting 1 mol of styrene with respect to 1 mol of salicylic acid, (b) a salicylic acid derivative obtained by reacting 2 mol of styrene with respect to 1 mol of salicylic acid, and (c) salicylic acid 1 (A) a salicylic acid derivative obtained by reacting 3 moles of styrenes with respect to 1 mole;
(A) 5 to 60% by weight, (b) 15 to 70% by weight, (c) 10 to 40% by weight, based on the total of (b) and (c)
Metal salts of salicylic acid derivatives contained in
87786) and the like.

However, a developer using such a polyvalent metal salt of a salicylic acid derivative has problems that, when handled in an aqueous dispersion, often has poor dispersion stability and causes sedimentation and aggregation. In addition, when these developers are used, the water resistance of the recorded image cannot be said to be still sufficient.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color developer having excellent dispersion stability, excellent light fastness of white paper, and excellent water fastness of a recorded image, an aqueous dispersion thereof, a recording sheet, and The purpose is to provide a color developing ink.

[0006]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have intensively studied a color developer, an aqueous dispersion thereof, a recording sheet and a color ink, and as a result, completed the present invention. Reached. That is, the present invention relates to (1) a developer containing a polyvalent metal salt of a salicylic acid derivative, wherein the salicylic acid derivative is substituted with (a) 1 mol of salicylic acids and 1 to 3 mol of styrenes. Characterized in that it contains 30 to 85% by weight of a salicylic acid derivative and (b) 15 to 70% by weight of at least one salicylic acid derivative obtained by substituting 4 mols or more of styrene for 1 mol of salicylic acids. (2) the polyvalent metal salt of a salicylic acid derivative is a zinc salt of a salicylic acid derivative,
The developer according to (1), wherein the salicylic acid derivative is obtained by reacting salicylic acids with styrenes in the presence of a polyvalent metal oxide. 4) The molar ratio between salicylic acids and styrenes is 1: 1.5 to 1:
5.0, wherein the developer according to (2), (5) the developer according to (3), wherein the oxide of the polyvalent metal is zinc oxide, and (6) the polyvalent metal salt of a salicylic acid derivative. The salicylic acid derivative obtained by reacting salicylic acids and styrenes in the presence of an oxide of a polyvalent metal, and subsequently, the color developer according to the above (1) obtained by polyvalent metal salification, (7) The aqueous dispersion of the developer obtained by dispersing the developer according to (1) in water, (8)
On a support, a recording sheet having a layer containing a polyvalent metal salt of a salicylic acid derivative according to (1), (9) On a support, using an aqueous dispersion of the developer according to (7). The recording sheet obtained by applying the coating solution obtained in (10), a developer, a photocurable compound, a photopolymerizable agent and a developer containing a pigment, wherein the developer is described in (1) above. Developing ink that is a developer, (11) using the developing ink described in (10),
A recording sheet obtained by printing on a support.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The color developer of the present invention is a color developer containing a polyvalent metal salt of a salicylic acid derivative, wherein the salicylic acid derivative comprises (a) 1 mol of salicylic acid and 1 to 3 mol of styrene. It is characterized in that at least one salicylic acid derivative substituted with a mole and at least one salicylic acid derivative substituted with 4 mols or more of styrenes per 1 mol of the salicylic acid (b). In the developer of the present invention, among the salicylic acid derivatives, (a) a salicylic acid derivative in which 1 mol of salicylic acid is substituted with 1 to 3 mol of styrene (hereinafter, referred to as salicylic acid derivative (a)) is one salicylic acid skeleton. 1 to 3 styrenes
It is one that constitutes a molecule, and does not necessarily mean that all styrenes are added to the salicylic acid skeleton.
Further, among the salicylic acid derivatives, (b) salicylic acids 1
The same applies to a salicylic acid derivative (hereinafter, referred to as salicylic acid derivative (b)) in which 4 or more styrenes are substituted by moles.

In the color developer of the present invention, the ratio of the salicylic acid derivative (a) to the salicylic acid derivative (b) is 30 to 85% by weight for (a) and 15 to 70% by weight for (b).
Preferably, (a) is 45 to 85% by weight and (b) is 15% by weight.
To 55% by weight, more preferably 55 to 55% by weight.
85% by weight and (b) 15 to 45% by weight.

Examples of the salicylic acid derivative (a) include 3- (α-methylbenzyl) salicylic acid,
(Α, α-dimethylbenzyl) salicylic acid, 3- (4′-
Methyl-α-methylbenzyl) salicylic acid, 5- (α-
Methylbenzyl) salicylic acid, 5- (α, α-dimethylbenzyl) salicylic acid, 5- (2′-methyl-α-methylbenzyl) salicylic acid, 5- (4′-chloro-α-methylbenzyl) salicylic acid, 3-methyl -5- (α-methylbenzyl) salicylic acid, 3-methyl-5- (4′-hydroxy-α-methylbenzyl) salicylic acid, 3- (α-methylbenzyl) -6-ethylsalicylic acid, 3- (3′- Methyl-α-methylbenzyl) -6-ethylsalicylic acid,
5- (α-methylbenzyl) -6-ethylsalicylic acid,
5- (4′-methoxy-α-methylbenzyl) -6-ethylsalicylic acid, 3- (α-methylbenzyl) -5-isopropylsalicylic acid, 3- (2 ′, 4′-dimethyl-α-methylbenzyl)- 5-isopropylsalicylic acid, 3-
(Α-methylbenzyl) -5-sec-butylsalicylic acid, 3- (4′-methyl-α-methylbenzyl) -5-se
c-Butylsalicylic acid, 3- (α-methylbenzyl)-
5-tert-butylsalicylic acid, 3- (4′-chloro-α-
Methylbenzyl) -5-tert-butylsalicylic acid, 3-
(Α-methylbenzyl) -5-cyclohexylsalicylic acid, 3- (4′-methoxy-α-methylbenzyl) -5
Cyclohexylsalicylic acid, 3- (α-methylbenzyl) -5-n-octylsalicylic acid, 3- (3′-methyl-α-methylbenzyl) -5-n-octylsalicylic acid, 3- (α-methylbenzyl) -5 -Tert-octylsalicylic acid, 3- (4'-methoxy-α-methylbenzyl) -5-tert-octylsalicylic acid, 3- (α-methylbenzyl) -4-methoxysalicylic acid, 3- (4'-chloro-α -Methylbenzyl) -4-methoxysalicylic acid, 4-methoxy-5- (α-methylbenzyl) salicylic acid, 4-methoxy-5- (4′-methyl-α-methylbenzyl) salicylic acid, 3- (α-methylbenzyl) ) -6
-Methoxysalicylic acid, 3- (3′-methyl-α-methylbenzyl) -6-methoxysalicylic acid, 5- (α-methylbenzyl) -6-methoxysalicylic acid, 5- (4′-methyl-α-methylbenzyl) -6-methoxysalicylic acid,

3- (α-methylbenzyl) -5-ethoxysalicylic acid, 3- (4′-methoxy-α-methylbenzyl) -5-ethoxysalicylic acid, 3- (α-methylbenzyl) -6-isopropoxysalicylic acid , 3- (2 ', 4'
-Dimethyl-α-methylbenzyl) -6-isopropoxysalicylic acid, 5- (α-methylbenzyl) -6-isopropoxysalicylic acid, 5- (4′-chloro-α-methylbenzyl) -6-isopropoxysalicylic acid, 3- (α
-Methylbenzyl) -4-n-hexyloxysalicylic acid, 4-n-hexyloxy-5- (α-methylbenzyl) salicylic acid, 3- (α-methylbenzyl) -4-n
-Decyloxysalicylic acid, 3- (4'-methoxy-α-
Methylbenzyl) -4-n-decyloxysalicylic acid,
4-n-decyloxy-5- (α-methylbenzyl) salicylic acid, 4-n-decyloxy-5- (3′-methyl-
α-methylbenzyl) salicylic acid, 3- (α-methylbenzyl) -5-fluorosalicylic acid, 3- (2 ′, 4′-dimethyl-α-methylbenzyl) -5-fluorosalicylic acid, 3-chloro-5- ( α-methylbenzyl) salicylic acid, 3-chloro-5- (4′-hydroxy-α-methylbenzyl) salicylic acid, 3- (α-methylbenzyl) -4
-Chlorosalicylic acid, 3- (4'-methoxy-α-methylbenzyl) -4-chlorosalicylic acid, 4-chloro-5-
(Α-methylbenzyl) salicylic acid, 4-chloro-5-
(4′-methyl-α-methylbenzyl) salicylic acid, 3-
(Α-methylbenzyl) -5-chlorosalicylic acid, 3-
(3′-methyl-α-methylbenzyl) -5-chlorosalicylic acid, 3- (α-methylbenzyl) -5-bromosalicylic acid, 3- (2′-methyl-α-methylbenzyl) -5
-A salicylic acid derivative in which styrenes are substituted by 1 mol with salicylic acids such as bromosalicylic acid [hereinafter, the salicylic acid derivative is referred to as (a-1)],

3,5-di (α-methylbenzyl) salicylic acid, 3,5-di (α, α-dimethylbenzyl) salicylic acid, 3,5-di (4′-methyl-α-methylbenzyl)
Salicylic acid, 3,5-di (3′-methyl-α-methylbenzyl) salicylic acid, 3,5-di (2′-methyl-α-methylbenzyl) salicylic acid, 3,5-di (4′-chloro-α
-Methylbenzyl) salicylic acid, 3,5-di (2 ', 4'-
Dimethyl-α-methylbenzyl) salicylic acid, 3,5-
Di (4′-hydroxy-α-methylbenzyl) salicylic acid, 3- [4 ′-(α′-methylbenzyl) -α-methylbenzyl] salicylic acid, 3- (1 ′, 3′-diphenylbutyl) salicylic acid, 5 -[4 '-(α'-methylbenzyl)
-Α-methylbenzyl] salicylic acid, 5- (1 ′, 3′-diphenylbutyl) salicylic acid, 3- (α-methylbenzyl) -5- (α, α-dimethylbenzyl) salicylic acid, and styrenes. Salicylic acid derivative substituted by 2 mol [hereinafter, the salicylic acid derivative is referred to as (a-2)],

3- [4 '-(α'-methylbenzyl) -α
-Methylbenzyl] -5- (α-methylbenzyl) salicylic acid, 3- (α-methylbenzyl) -5- [4′-
(Α′-methylbenzyl) -α-methylbenzyl] salicylic acid, 3- (4′-methyl-α-methylbenzyl) -5
-[4 '-(α'-methylbenzyl) -α-methylbenzyl] salicylic acid, 3- (α, α-dimethylbenzyl)-
5- [4 '-(α'-methylbenzyl) -α-methylbenzyl] salicylic acid, 3- [4'-(α'-methylbenzyl) -α-methylbenzyl] -5- (α, α-dimethylbenzyl) ) Salicylic acid, 3- (α-methylbenzyl)-
5- (1 ′, 3′-diphenylbutyl) salicylic acid, 3-
Styrenes are added to salicylic acids such as (1 ', 3'-diphenylbutyl) -5- (α-methylbenzyl) salicylic acid
Molarly substituted salicylic acid derivatives [hereinafter, the salicylic acid derivatives are referred to as (a-3)]. The salicylic acid derivatives (a-1), (a-2) and (a-3) may be used alone or in combination.

The salicylic acid derivative (b) according to the present invention is a salicylic acid derivative in which 1 mol of salicylic acid is substituted by 4 mol or more of styrene, preferably a salicylic acid derivative in which 4 to 20 mol of styrene is substituted. ,
More preferably, it is a salicylic acid derivative in which styrenes are substituted by 4 to 10 mol. The salicylic acid derivative (b) may be used alone or in combination.

In the present invention, the salicylic acids which are the raw materials of the salicylic acid derivative include, for example, salicylic acid, 3
-Methylsalicylic acid, 6-ethylsalicylic acid, 5-isopropylsalicylic acid, 5-sec-butylsalicylic acid, 5
-Tert-butylsalicylic acid, 5-tert-amylsalicylic acid, 5-cyclohexylsalicylic acid, 5-n-octylsalicylic acid, 5-tert-octylsalicylic acid, 4-methoxysalicylic acid, 6-methoxysalicylic acid, 5-ethoxysalicylic acid, 6-iso Propoxysalicylic acid, 4-n
-Hexyloxysalicylic acid, 4-n-decyloxysalicylic acid, 5-fluorosalicylic acid, 3-chlorosalicylic acid, 4-chlorosalicylic acid, 5-chlorosalicylic acid,
5-bromosalicylic acid and the like. These salicylic acids may be used alone or in combination of two or more. Some salicylic acids are commercially available and can be obtained, for example, from a phenol derivative by a Kolbe-Schmidt reaction. Particularly preferred is salicylic acid.

In the present invention, styrenes which are the raw materials of the salicylic acid derivative include, for example, styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-chlorostyrene, 2,4
-Dimethylstyrene, p-hydroxystyrene, p-methoxystyrene and the like. Styrenes may be used alone or in combination. Particularly preferred is styrene.

In the color developer of the present invention, specific examples of the polyvalent metal salt of a salicylic acid derivative include, for example, magnesium, zinc, nickel, aluminum, calcium, barium, tin, copper, lead, molybdenum, and tungsten of a salicylic acid derivative. , Zirconium, strontium, manganese, cobalt, titanium, iron salts, preferably magnesium, zinc, nickel, aluminum, calcium salts, more preferably zinc, aluminum, calcium salts Particularly preferred is a zinc salt of a salicylic acid derivative.

The method for preparing the polyvalent metal salt of the salicylic acid derivative in the color developer of the present invention is not particularly limited. In general, for example, separately prepared salicylic acid derivatives (a) and (b) A method of mixing each with a desired ratio and then salting with a polyvalent metal, and separately preparing salicylic acid derivatives (a) and (b)
A method in which salicylic acids and styrenes are mixed in a desired ratio after salification with polyvalent metals so that the salicylic acid derivatives (a) and (b) have a desired ratio in the presence of a specific catalyst. , And then a polyvalent metal salification. Alternatively, the salicylic acid derivatives (a) and (b) used in the above method can be obtained, for example, from the corresponding phenol derivative by a Kolbe-Schmidt reaction. The salicylic acid derivatives (a) and (b) are obtained by reacting salicylic acids and styrenes in the presence of a catalyst, and then separating the resulting mixture from the reaction mixture using, for example, column chromatography. You can also.

When the salicylic acid derivatives (a) and (b) of the present invention are prepared by the above-mentioned method, it is preferable to use a polyvalent metal oxide as a catalyst during the reaction between salicylic acids and styrenes. . The polyvalent metal oxide used is preferably a divalent, trivalent or tetravalent metal oxide, and more preferably a divalent metal oxide. For example, zinc oxide, magnesium oxide, calcium oxide, barium oxide, nickel oxide, tin oxide,
Copper oxide, lead oxide, molybdenum oxide, tungsten oxide,
Zirconium oxide, strontium oxide, manganese oxide, cobalt oxide, titanium oxide, aluminum oxide, iron oxide, and the like can be given. Preferably, zinc oxide, magnesium oxide, calcium oxide, barium oxide, nickel oxide, manganese oxide, cobalt oxide, aluminum oxide, more preferably zinc oxide, magnesium oxide, calcium oxide, particularly preferably zinc oxide It is. The oxides of polyvalent metals may be used alone or in combination. The form of the oxide of the polyvalent metal is not particularly limited, and examples thereof include a powder form, a granular form, a linear form, and the like, and preferably a powder form.

The amount of the polyvalent metal oxide to be used is not particularly limited, but is generally about 1 to 50 parts by weight, preferably 3 to 50 parts by weight, per 100 parts by weight of salicylic acids.
It is about 30 parts by weight. In the reaction between salicylic acids and styrenes, other catalysts may be used in addition to the polyvalent metal oxide, if desired. Other catalysts include, for example, mineral acids such as hydrochloric acid and sulfuric acid, metal halides such as zinc chloride and aluminum chloride, and aliphatic sulfonic acids such as methanesulfonic acid and ethanesulfonic acid, for example, p-toluenesulfonic acid , Aromatic sulfonic acids such as benzenesulfonic acid, for example, acetic acid,
Polyvalent metal salts of aliphatic carboxylic acids such as propionic acid, for example, aromatic carboxylic acids such as benzoic acid and 2-methylbenzoic acid, for example, zinc acetate and zinc stearate, for example, zinc salicylate And polyvalent metal salts of aromatic carboxylic acids such as zinc 3,3,5-di (α-methylbenzyl) salicylate. The amount of the catalyst other than the oxide of the polyvalent metal is
Generally, it is not more than 30% by weight.

The reaction between salicylic acids and styrenes is not particularly limited. For example, a method of adding styrenes to salicylic acids and an oxide of a polyvalent metal, a part of a predetermined amount of styrenes, And the method of adding the remaining amount of styrenes to the oxides of polyvalent metals, and the method of adding a mixture of salicylic acids and styrenes to the oxides of polyvalent metals, and the like. . This reaction can be generally carried out under atmospheric pressure or under pressure, and can be carried out under an inert gas (for example, nitrogen gas,
(Helium gas, argon gas).

The amount of styrene used in the reaction is generally at least 1.0 mol, preferably 1.0 to 6.0 mol, more preferably 1.3 to 1 mol per mol of salicylic acid. 5.5 mol, particularly preferably 1.5 to
5.0 mol. The reaction temperature is generally between 80 and 180
° C, preferably 110-160 ° C. The reaction time varies depending on, for example, the reaction temperature.
It is about 10 minutes, preferably about 1 to 5 hours.

In the reaction between salicylic acids and styrenes, a suitable organic solvent may be used, if desired. Examples of the organic solvent include hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, 1-methylnaphthalene, octane, and decane, chloroform, tetrachloroethylene, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,2-trichloroethane, 1,
1,2,2-tetrachloroethane, chlorobenzene, o
-Halogenated hydrocarbon solvents such as dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, o-chlorotoluene, m-chlorotoluene and p-chlorotoluene; and ester solvents such as ethyl acetate, butyl acetate and amyl acetate. , Butanol, pentanol, hexanol,
Alcohol solvents such as cyclohexanol and the like can be mentioned. The organic solvents may be used alone or in combination. The amount of the organic solvent used is not particularly limited, but is generally about 500 parts by weight or less based on 100 parts by weight of salicylic acids, preferably,
It is about 300 parts by weight or less.

The method for producing the polyvalent metal salt of the salicylic acid derivative according to the present invention is not particularly limited.
Known methods can be applied. For example, a method of melting a salicylic acid derivative and a polyvalent metal compound (eg, an oxide, hydroxide, carbonate, silicate, or organic carboxylate of a polyvalent metal) to produce (melting method) A salt of a water-soluble salicylic acid derivative such as an alkali metal salt, an amine salt or an ammonium salt of a salicylic acid derivative, and a water-soluble polyvalent metal compound (for example, a sulfate such as zinc sulfate, magnesium sulfate or aluminum sulfate, zinc chloride, (Methods such as chlorides such as magnesium chloride, calcium chloride, nickel chloride and aluminum chloride, and acetates such as zinc acetate) in the presence of water to produce the compound (double decomposition method). A more preferred method is the following method.

The polyvalent metal salt of the salicylic acid derivative is generally used in an amount of about 0.8 to 1.5 equivalents, preferably 0.1 to 1 equivalent, per equivalent of the salicylic acid derivative or the salt of the salicylic acid derivative.
It can be produced by reacting about 9 to 1.2 equivalents of a polyvalent metal compound. The equivalent in this case refers to 0.5 mol of the polyvalent metal compound, for example, a divalent metal compound (for example, zinc sulfate) with respect to 1 mol of the salicylic acid derivative or the salt of the salicylic acid derivative. The bivalent metal compound corresponds to one equivalent. On this occasion,
If desired, heating may be performed, or an organic solvent may coexist. In some cases, the polyvalent metal salt of the salicylic acid derivative according to the present invention may form a hydrate. In the present invention, such a hydrate is also included in the polyvalent metal salt of the salicylic acid derivative. Is done.

The developer of the present invention contains the polyvalent metal salt of the above-mentioned salicylic acid derivatives (a) and (b),
If desired, various additives (eg, a sensitizer (color-forming accelerator), an ultraviolet absorber, an antioxidant, a light stabilizer, etc.) may be contained. As a sensitizer (color development accelerator),
For example, polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol,
Polyoxyalkylene glycol derivatives such as polyoxytetramethylene glycol, polyoxyethylene glycol oleate monoester, polyoxyethylene glycol laurate diester, polyoxypropylene glycol laurate diester, polyoxypropylene glycol oleate diester, Polyoxyalkylene fatty acid ester derivatives such as stearic acid diester of polyoxytetramethylene glycol; fatty acid amide derivatives such as stearic acid amide and oleic acid amide; dimers to styrene of styrene derivatives such as styrene chain oligomers and styrene cyclic oligomers Oligomeric derivatives and the like. The amount of the sensitizer contained in the color developer of the present invention is generally about 1 to 50 parts by weight, preferably 3 to 40 parts by weight, per 100 parts by weight of the polyvalent metal salt of the salicylic acid derivative. And more preferably 5 to 30 parts by weight.

As the ultraviolet absorber, for example, 2,4-
Benzophenone derivatives such as dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-dodecyloxybenzophenone;
-(2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di Tert-butylphenyl) benzotriazole derivatives such as benzotriazole, cyanoacrylate derivatives such as 2-ethylhexyl-2-cyano-3,3′-diphenylacrylate and ethyl-2-cyano-3,3′-diphenylacrylate. No. The amount of the ultraviolet absorber contained in the developer of the present invention,
Generally, the amount is about 0.1 to 30 parts by weight, preferably 100 parts by weight of the polyvalent metal salt of the salicylic acid derivative,
It is about 1 to 20 parts by weight.

Examples of the antioxidant include 2,6-di-tert-butylphenol and 2,6-diisopropyl-
4-methylphenol, 2,6-di-tert-butyl-4
-Methylphenol, 2-tert-butyl-4-methoxyphenol, 2,5-di-tert-octyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-octyl Hydroquinone, 1,
1,3-tris (2-methyl-4-hydroxy-5-te
rt-butylphenyl) butane, 1,1,3-tris (2
-Methyl-4-hydroxy-5-cyclohexylphenyl) butane, 1,1,3-tris (2-ethyl-4-hydroxy-5-tert-butylphenyl) butane, 1,
1,3-tris (3,5-di-tert-butyl-4-hydroxyphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) propane, 1, 1-bis (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, Screw (3-te
rt-butyl-5-methyl-2-hydroxyphenyl) methane, bis (3-tert-butyl-5-ethyl-2-hydroxyphenyl) methane, 1,3,5-trimethyl-
2,4,6-tris (3,5-di-tert-butyl-4-
Hydroxybenzyl) benzene, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid, 1,3,5-tris (4
-Tert-butyl-3-hydroxy-2-methyl-6-ethylbenzyl) isocyanuric acid, bis (2-methyl-4
-Hydroxy-5-tert-butylphenyl) sulfide and the like. The amount of the antioxidant contained in the color developer of the present invention is generally 0.1 to 30 parts by weight per 100 parts by weight of the polyvalent metal salt of the salicylic acid derivative.
It is about 1 part by weight, preferably about 1 to 20 parts by weight.

As the light stabilizer, for example, 2,2,4-
Trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, bis (2 , 2,6,6-tetramethylpiperidine) adipic acid ester and the like. The amount of the light stabilizer contained in the developer of the present invention is generally about 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of the polyvalent metal salt of the salicylic acid derivative. It is about parts by weight. These various additives include the salicylic acid derivatives (a) and (b) described above.
May be directly added to the color developer of the present invention containing the polyvalent metal salt of the present invention, or may be added to an aqueous dispersion of the color developer of the present invention described later. When added to the aqueous dispersion, after preparing the aqueous dispersion of the developer of the present invention, may be blended in the aqueous dispersion, or, when preparing the aqueous dispersion of the developer, the developer At the same time, they may be dispersed (emulsified and dispersed).

The color developer of the present invention is used in the form of an aqueous dispersion, a coating liquid obtained using the aqueous dispersion, and the like. Further, the aqueous dispersion of the color developer of the present invention is applied as it is to a support as a coating liquid to form a color developer layer, and is used as a recording sheet. As a method for preparing the aqueous dispersion of the developer of the present invention, for example, a developer containing a polyvalent metal salt of a salicylic acid derivative,
In an aqueous medium, for example, using a ball mill, an attritor, a sand grinder, a pebble mill, a cobol mill, a dyno mill, a high-speed impeller disperser, a high-speed stone mill, an annular mill, etc., pulverizing and dispersing to obtain an aqueous dispersion, a salicylic acid derivative A developer containing a polyvalent metal salt of
After dissolution in an organic solvent, for example, using an ultrasonic disperser, a homogenizer, a homomixer, a line homomixer, etc.
A method of emulsifying and dispersing and removing an organic solvent to obtain an aqueous dispersion. A more preferred method is a method of preparing an aqueous dispersion by emulsification and dispersion.

The preparation of the aqueous dispersion of the color developer of the present invention is generally carried out in an aqueous medium in the presence of a dispersant. As the dispersant, ionic or nonionic surfactants are preferable, for example, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, cyanoethyl-modified polyvinyl alcohol, ether-modified polyvinyl alcohol, sulfonated-modified polyvinyl alcohol, polyacrylamide,
Polyacrylic acid, acrylamide / alkyl acrylate copolymer, alkali metal salt of polystyrenesulfonic acid, maleic anhydride / isobutylene copolymer, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, starch and derivatives thereof, casein, gum arabic, agar, Synthetic or natural polymer compounds such as gelatin, alkali metal salts of alkylbenzenesulfonic acid, alkali metal salts of alkylnaphthalenesulfonic acid, alkali metal salts of dialkylsulfosuccinic acid, alkali metal salts of alkylsulfonic acid, polyoxyethylene alkyl ether , Polyoxyethylene alkyl phenyl ether, polyhydric alcohol fatty acid esters, and the like.

Preferred are polyvinyl alcohol, alkyl-modified polyvinyl alcohol, cyanoethyl-modified polyvinyl alcohol, ether-modified polyvinyl alcohol, sulfonated-modified polyvinyl alcohol, alkali metal salts of polystyrenesulfonic acid, and alkali metal salts of alkylsulfonic acid. Is polyvinyl alcohol, and particularly preferably, has a saponification degree of 80.
~ 100% polyvinyl alcohol. These dispersants may be used alone or in combination of two or more. The amount of the dispersant is not particularly limited, but is generally, for example, about 1 to 30 parts by weight, based on 100 parts by weight of the developer containing the polyvalent metal salt of the salicylic acid derivative, preferably , About 1 to 20 parts by weight, more preferably about 1 to 15 parts by weight, particularly preferably about 1 to 10 parts by weight.

In the above method, the organic solvent to be used preferably has a low solubility in water, an excellent solubility of a color developer and a relatively low boiling point. Examples of the organic solvent include hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and 1-methylnaphthalene, dichloromethane, chloroform, tetrachloroethylene, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,1 2-trichloroethane, 1,1,
2,2-tetrachloroethane, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, o-chlorotoluene, m-chlorotoluene,
halogenated hydrocarbon solvents such as p-chlorotoluene,
Examples thereof include ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ester solvents such as ethyl acetate, butyl acetate and amyl acetate, and alcohol solvents such as butanol, pentanol, hexanol and cyclohexanol. These solvents may be used alone or in combination of two or more. The amount of the organic solvent used is not particularly limited, but is generally, for example, about 5 to 500 parts by weight, based on 100 parts by weight of a developer containing a polyvalent metal salt of a salicylic acid derivative, more preferably. About 20 to 300 parts by weight.

The emulsification and dispersion are carried out at a temperature not higher than the boiling point of the organic solvent, and are carried out under atmospheric pressure or under pressure. After the emulsification and dispersion, the organic solvent is distilled off to obtain an aqueous dispersion of the color developer. As a method for distilling off the organic solvent, the organic solvent can be distilled off by heating the organic solvent to a temperature higher than the boiling point of the organic solvent under atmospheric pressure or reduced pressure. The aqueous dispersion thus obtained can be further dispersed using a dispersing machine (for example, a sand grinder or an annular mill), if desired. The average particle diameter of the developer in the aqueous dispersion of the present invention is generally 10 μm or less, preferably 0.1 to 5 μm.
m, more preferably about 0.2 to 3 μm, and particularly preferably about 0.3 to 2 μm.

Specific examples of the method for preparing (preparing) the color developer and the aqueous dispersion of the color developer of the present invention will be briefly described below. Oxides of salicylic acids and polyvalent metals (for example,
Zinc oxide, magnesium oxide, etc.), and if necessary, a predetermined amount of an organic solvent or styrenes is added, and the mixture is heated to about 110 to 160 ° C. with stirring. At this temperature, styrenes (or the remaining amount of styrene) are added in about 0.5 to 5.0 hours, and at this temperature,
Hold for about 0.5 to 5 hours to produce the salicylic acid derivative. Next, an organic solvent, water and an alkali metal compound (for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc.) are added to prepare an alkali metal salt of a salicylic acid derivative. Then, a water-soluble polyvalent metal compound (eg, zinc sulfate, zinc chloride, etc.) is allowed to act on the alkali metal salt of the salicylic acid derivative to prepare a polyvalent metal salt of the salicylic acid derivative, and then separating the organic layer. By
An organic solvent solution containing a color developer containing the polyvalent metal salt of the salicylic acid derivative of the present invention is obtained. Sensitizer, ultraviolet absorber,
Additives such as antioxidants and light stabilizers are preferably added at this stage. Next, in an aqueous medium containing a dispersing agent, an organic solvent solution containing the color developer is added, and, for example, after emulsification using a homomixer or the like, the organic solvent is removed, whereby the developer according to the present invention is removed. An aqueous dispersion of the colorant can be produced.

The aqueous dispersion of the color developer of the present invention may contain a binder (binder), a pigment and the like in addition to the color developer, and can be used as a coating liquid. Further, various additives such as, for example, an antifoaming agent, a pH adjuster, and a viscosity adjuster may be added to the coating liquid as desired. When the aqueous dispersion of the developer of the present invention is used as a coating solution, the coating solution has a solid content of about 10 to 50% by weight, preferably 20 to 40% by weight.
% By weight.

The binder is not particularly restricted but includes, for example, polyvinyl alcohol, casein,
Synthetic or natural high molecular compounds such as starch and its derivatives, gum arabic, methylcellulose, carboxymethylcellulose, polyacrylic acid, styrene / butadiene copolymer latex, latex such as acrylic acid latex, and the like. The binder may be used alone or in combination of two or more. The amount of the binder used is not particularly limited, but is generally adjusted to be about 5 to 40% by weight, preferably about 10 to 30% by weight of the total solids in the coating solution.

The pigment is not particularly limited. Examples thereof include zinc oxide, zinc carbonate, calcium carbonate, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, titanium oxide, talc, kaolin, activated clay, and diatomaceous earth. , Zinc hydroxide, aluminum hydroxide, magnesium hydroxide, alumina, inorganic pigments such as silica,
Organic pigments such as styrene microballs, nylon particles, urea-formalin fillers, polyethylene particles, cellulose fillers, starch particles and the like can be mentioned. The pigments may be used alone or in combination. The amount of the pigment used is not particularly limited, but is generally adjusted to be about 5 to 90% by weight, preferably about 10 to 80% by weight of the total solids in the coating solution.

The coating solution obtained by using the aqueous dispersion of the color developer of the present invention thus prepared is prepared by a known method.
For example, using a coating apparatus such as an air knife coater, a blade coater, a roll coater, a size press coater, a curtain coater, a short dwell coater, and the like, a support (for example, paper, a plastic sheet, a synthetic paper, or a composite sheet combining these) The recording sheet of the present invention can be prepared by forming a layer containing a polyvalent metal salt of a salicylic acid derivative of the present invention (hereinafter, also referred to as a color developer layer) by coating and drying the same. In the recording sheet of the present invention, the weight of the developer layer on the support (that is, the coating amount) is not particularly limited, and is generally 0.5 g / m ² or more, preferably, in dry weight,
It is about 0.5 to 10 g / m ² .

The form of the recording sheet of the present invention is not particularly limited, and examples thereof include a pressure-sensitive recording sheet, a heat-sensitive recording sheet, and a heat-sensitive multi-copy sheet described in JP-A-10-166723. Is mentioned. A more preferred recording sheet is a pressure-sensitive recording sheet. Examples of the pressure-sensitive recording sheet include, for example, a lower sheet provided with a color developer layer, in which microcapsules containing an electron-donating color-forming compound and capsule oil are used in combination with an upper sheet coated on one side of the sheet. (FIG. 1), in which a color developer layer is provided on one side of the sheet and a microcapsule layer is provided on the opposite side of the sheet, which is inserted between the upper sheet and the lower sheet to make a plurality of copies. Sheet (FIG. 2), and a single copy sheet (FIG. 3) in which microcapsules and a developer are applied to the same surface of the sheet.

The microcapsules are prepared by dissolving a solution of an electron-donating color-forming compound in capsule oil, for example,
It can be produced by various known microencapsulation methods such as a coacervation method, an interfacial polymerization method, an internal polymerization method, a phase separation method, and an external polymerization method. Examples of the wall film material of the microcapsules include polyurethane, epoxy resin, polyurea, urea-formimaldehyde resin, melamine-formimaldehyde resin, and the like. Examples of the electron-donating color-forming compound include a triarylmethane compound, a diarylmethane compound, a rhodamine-lactam compound, a fluoran compound, an indolylphthalide compound, a pyridine compound, a spiro compound, and a fluorene compound. And various known compounds such as phenothiazine compounds. These electron-donating color-forming compounds may be used alone or in combination of two or more. Examples of capsule oils include cottonseed oil, castor oil, kerosene, paraffin, chlorinated paraffin,
Naphthenic oil, alkylated biphenyl, alkylated terphenyl, alkylated naphthalene, diarylalkane,
Various oils such as hydrogenated terphenyl and dialkyl phthalate can be mentioned. These capsule oils may be used alone or in combination.

The color-developing ink of the present invention contains the color-developing agent of the present invention containing a polyvalent metal salt of a salicylic acid derivative (a) or (b), a photocurable compound, a photopolymerizing agent and a pigment. It is. In the color developing ink of the present invention, the content of the color developing agent of the present invention is not particularly limited,
Generally, 10-60% by weight, more preferably 20-5%
0% by weight.

Examples of the photocurable compound used in the color developing ink of the present invention include epoxy acrylate, rosin-modified epoxy acrylate, polyester acrylate, polyurethane acrylate, polyether acrylate, alkyd acrylate, lauryl acrylate, 2-ethylhexyl acrylate, and the like. Acrylate prepolymers such as 2-hydroxyethyl acrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, ethylene oxide-modified bisphenol F diacrylate, trimethylolpropane triacrylate, and trimethylolethane trimethacrylate; Monomers. The content of the photocurable compound in the color developing ink is not particularly limited, and is generally 20 to 90% by weight, more preferably,
30 to 80% by weight.

Examples of the photopolymerizing agent include acetophenone derivatives, benzyl derivatives, benzoin derivatives, anthraquinone derivatives, oxime derivatives, xanthone derivatives,
Thioxanthone derivatives and the like can be mentioned. The content of the photopolymerizing agent in the color developing ink is not particularly limited, and is generally 0.5 to 40% by weight, more preferably,
1 to 20% by weight. Further, as the pigment, for example,
Titanium oxide, zinc oxide, calcium carbonate, aluminum hydroxide, barium sulfate, alumina white, kaolin,
Activated clay and the like can be mentioned. The content of the pigment in the developed ink is not particularly limited.
-50% by weight, more preferably 3-30% by weight. In the developed ink of the present invention, if desired, for example,
It may contain a polymerization inhibitor, a dispersant, and further, the above-described sensitizer (color-forming accelerator), an ultraviolet absorber, an antioxidant, a light stabilizer, and the like.

The color ink of the present invention can be prepared by mixing a color developer, a photocurable compound, a photopolymerizing agent, a pigment and the like. Upon mixing, if desired, for example,
A mixer such as an attritor or a three-roll mill can be used. The color developing ink of the present invention can be used as a recording sheet by forming a layer containing the polyvalent metal salt of the salicylic acid derivative of the present invention on a support. For example, using the color developing ink of the present invention, a support (for example,
After printing on paper, plastic sheet, synthetic paper, or composite sheet combining them) or on the other side of the support on which microcapsules containing the electron-donating chromogenic compound and capsule oil are applied on one side ,
By irradiating light to cure the printing surface, a recording sheet can be produced.

Examples of the printing method include offset printing and relief printing. More preferably, the offset printing method is used. As the light irradiation source, for example, a mercury lamp or a metal halide lamp can be used. When the developed color ink of the present invention is used, generally, the amount of the developed color ink applied on the support by printing is not particularly limited, but is generally 0.5 g / m ² or more as the ink. Is 0.5 to 5 g /
m ² , and more preferably about 1 to 3 g / m ² .

[0046]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.
In the following,% represents% by weight.

Example 1 138.1 g (1 mol) of salicylic acid and zinc oxide 6 were placed in a 2000 ml glass reactor equipped with a stirrer.
9 g (5% based on salicylic acid), styrene 52.1
g (0.5 mol), and stir and mix.
Keeping the temperature at 45 ° C, 156.2 g (1.5 mol) of styrene
Was continuously fed at 1 g / min. After supply, one more
The mixture was stirred at 45 ° C for 1 hour to obtain a light brown transparent viscous substance. When the obtained viscous substance (reaction mixture, the same applies hereinafter) was analyzed by high performance liquid chromatography, the salicylic acid derivative (a) in which 1 mol of salicylic acid was substituted with 1 to 3 mol of styrene.
And the salicylic acid derivative (b) obtained by substituting 4 to 10 mol of styrene for 1 mol of salicylic acid was 80:20. The reaction mixture was cooled to 50 ° C., 350 g of 1,2-dichloroethane, 350 g of water and 135 g of a 30% aqueous sodium hydroxide solution were added, and the mixture was stirred and mixed at 30 ° C. for 1 hour. Next, 643.8 g of an aqueous solution containing 143.8 g (0.5 mol) of zinc sulfate heptahydrate was continuously supplied at a rate of 10 g / min. After the addition, the mixture was further stirred at 30 ° C. for 1 hour,
Zincing was performed. The lower layer (organic layer) was separated to obtain 760 g of a 1,2-dichloroethane solution containing a zinc salt of a salicylic acid derivative of the present invention. 1,2-Dichloroethane was further added to this solution to adjust the concentration to 50%. Next, 100 g of water was added to polyvinyl alcohol (Kurarepovar PV).
A205) An aqueous solution in which 2.0 g was dissolved was mixed with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 10,000 rpm.
While stirring at pm, 80 g of the 1,2-dichloroethane solution was added, and emulsification and dispersion were performed. 1,2-Dichloroethane was distilled off while heating the obtained emulsion with stirring, and 92 g (average particle diameter 0.8 μm) of a 45% concentration aqueous zinc salt of a salicylic acid derivative of the present invention was obtained. Obtained.

Example 2 138.1 g (1 mol) of salicylic acid and zinc oxide 1 were placed in a 2000 ml glass reactor equipped with a stirrer.
0.4 g (7.5% based on salicylic acid) and 52.1 g (0.5 mol) of styrene were added, and the reactor was kept at 145 ° C. while stirring and mixing, and 208.3 g of styrene (2.
0 mol) was continuously fed at 1 g / min. After the supply, the mixture was further stirred at 145 ° C. for 2 hours to obtain a light brown transparent viscous substance. When the reaction mixture was analyzed by high performance liquid chromatography, 1 mol of salicylic acid contained 1 to 3 styrene.
The weight ratio of the mole-substituted salicylic acid derivative (a) to the salicylic acid derivative (b) obtained by substituting 4 mols of styrene with 1 mol of salicylic acid was 65:35. The reaction mixture was
After cooling to 0 ° C, 350 g of 1,2-dichloroethane,
50 g and 135 g of a 30% aqueous sodium hydroxide solution were added, and the mixture was stirred and mixed at 30 ° C. for 1 hour. Next, zinc sulfate
Aqueous solution 64 containing 143.8 g (0.5 mol) of heptahydrate
3.8 g was continuously fed at 10 g / min. After dripping,
Further, the mixture was stirred at 30 ° C. for 1 hour to perform zincation. The lower layer (organic layer) was separated to obtain 810 g of a 1,2-dichloroethane solution containing a zinc salt of a salicylic acid derivative of the present invention.
To this solution was further added 1,2-dichloroethane,
The concentration was adjusted to 50%. Next, 2.0 g of polyvinyl alcohol (Kuraray Povar PVA205) was added to 100 g of water.
Homomixer [Special Kika Kogyo Co., Ltd.]
While stirring at 10,000 rpm.
80 g of the 1,2-dichloroethane solution described above was added, and emulsification and dispersion were performed. While heating the obtained emulsion under stirring, 1,2-dichloroethane was distilled off to obtain a concentration of 45%.
92 g of an aqueous dispersion of a zinc salt of a salicylic acid derivative of the present invention
(Average particle diameter 0.8 μm) was obtained.

Example 3 138.1 g (1 mol) of salicylic acid and zinc oxide 1 were placed in a 2000 ml glass reactor equipped with a stirrer.
3.8 g (10% based on salicylic acid), styrene 5
2.1 g (0.5 mol) was added, and the reactor was kept warm at 145 ° C. while stirring and mixing, and 312.5 g of styrene (3.0 mol) was added.
Mol) was continuously fed at 1 g / min. After the supply, the mixture was further stirred at 155 ° C for 2 hours to obtain a pale brown transparent viscous substance. When the reaction mixture was analyzed by high performance liquid chromatography, the weight ratio of the salicylic acid derivative (a) in which 1 mol of salicylic acid was substituted with 1 to 3 mol of styrene and the salicylic acid derivative (b) in which 1 mol of salicylic acid was substituted with 4 to 10 mol of styrene was as follows. 45:55. The reaction mixture was
After cooling to 0 ° C, 350 g of 1,2-dichloroethane,
50 g and 135 g of a 30% aqueous sodium hydroxide solution were added, and the mixture was stirred and mixed at 30 ° C. for 1 hour. Next, zinc sulfate
Aqueous solution 64 containing 143.8 g (0.5 mol) of heptahydrate
3.8 g was continuously fed at 10 g / min. After dripping,
Further, the mixture was stirred at 30 ° C. for 1 hour to perform zincation. The lower layer (organic layer) was separated to obtain 910 g of a 1,2-dichloroethane solution containing a zinc salt of a salicylic acid derivative of the present invention.
To this solution was further added 1,2-dichloroethane,
The concentration was adjusted to 50%. Next, 2.0 g of polyvinyl alcohol (Kuraray Povar PVA205) was added to 100 g of water.
Homomixer [Special Kika Kogyo Co., Ltd.]
While stirring at 10,000 rpm.
80 g of the 1,2-dichloroethane solution described above was added, and emulsification and dispersion were performed. While heating the obtained emulsion under stirring, 1,2-dichloroethane was distilled off to obtain a concentration of 45%.
92 g of an aqueous dispersion of a zinc salt of a salicylic acid derivative of the present invention
(Average particle diameter 0.8 μm) was obtained.

Example 4 138.1 g (1 mol) of salicylic acid and zinc oxide 2 were placed in a 3000 ml glass reactor equipped with a stirrer.
7.6 g (20% based on salicylic acid), styrene 5
2.1 g (0.5 mol) was added, and the reactor was kept warm at 145 ° C. while stirring and mixing, and 416.8 g (4.0) of styrene was added.
Mol) was continuously fed at 2 g / min. After the supply, the mixture was further stirred at 160 ° C for 1.5 hours to obtain a light brown transparent viscous substance. When the reaction mixture was analyzed by high performance liquid chromatography, 1 mol of salicylic acid contained 1 to 1 styrene.
Salicylic acid derivative (a) substituted with 3 moles and salicylic acid 1
The weight ratio of the salicylic acid derivative (b) obtained by substituting 4 to 10 mol of styrene for mol was 35:65. The reaction mixture was cooled to 50 ° C., 350 g of 1,2-dichloroethane, 350 g of water, and 135 g of a 30% aqueous sodium hydroxide solution were added, and the mixture was stirred and mixed at 30 ° C. for 1 hour. Next, zinc sulfate
Aqueous solution 64 containing 143.8 g (0.5 mol) of heptahydrate
3.8 g was continuously fed at 10 g / min. After dripping,
Further, the mixture was stirred at 30 ° C. for 1 hour to perform zincation. The lower layer (organic layer) was separated to obtain 820 g of a 1,2-dichloroethane solution containing a zinc salt of a salicylic acid derivative of the present invention.
To this solution was further added 1,2-dichloroethane,
The concentration was adjusted to 50%. Next, 2.0 g of polyvinyl alcohol (Kuraray Povar PVA205) was added to 100 g of water.
Homomixer [Special Kika Kogyo Co., Ltd.]
While stirring at 10,000 rpm.
80 g of the above-mentioned 1,2-dichloroethane solution was added and emulsified. While heating the obtained emulsion under stirring,
The 1,2-dichloroethane was distilled off to obtain 92 g of an aqueous dispersion of a zinc salt of a salicylic acid derivative of the present invention having a concentration of 45% (average particle diameter 0.8 μm).

Example 5 138.1 g (1 mol) of salicylic acid and zinc oxide 6. were placed in a 2000 ml glass reactor equipped with a stirrer.
9 g (5% based on salicylic acid), styrene 52.1
g (0.5 mol), and stir and mix.
Keeping the temperature at 45 ° C, 156.2 g (1.5 mol) of styrene
Was continuously fed at 1 g / min. After supply, one more
The mixture was stirred at 45 ° C. for 1 hour to obtain a light brown transparent viscous substance. When the reaction mixture was analyzed by high performance liquid chromatography, the weight of a salicylic acid derivative (a) in which 1 mol of salicylic acid was substituted with 1 to 3 mol of styrene and a salicylic acid derivative (b) in which 4 to 10 mol of styrene reacted with 1 mol of salicylic acid were used. The ratio was 80:20. The reaction mixture was
After cooling to 0 ° C, 350 g of 1,2-dichloroethane,
50 g and 135 g of a 30% aqueous sodium hydroxide solution were added thereto, followed by stirring and mixing at 30 ° C. for 1 hour. Next, zinc sulfate
Aqueous solution 64 containing 143.8 g (0.5 mol) of heptahydrate
3.8 g was continuously fed at 10 g / min. After dripping,
Further, the mixture was stirred at 30 ° C. for 1 hour to perform zincation. The lower layer (organic layer) was separated to obtain 760 g of a 1,2-dichloroethane solution containing a zinc salt of a salicylic acid derivative of the present invention. 1,2-Dichloroethane was further added to this solution to adjust the concentration to 50%. To 80 g of this 1,2-dichloroethane solution, as a sensitizer, an average molecular weight of about 100
0 g of polyoxytetramethylene glycol (manufactured by Merck, polytetrahydrofuran 1000) was added,
Dissolved. Next, an aqueous solution obtained by dissolving 2.0 g of polyvinyl alcohol (Kuraray Poval PVA205) in 100 g of water was stirred using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at a rotation speed of 10,000 rpm while the above 1, 2 was stirred. -Dichloroethane solution (84 g) was added to perform emulsification and dispersion. While heating the obtained emulsion under stirring,
The 1,2-dichloroethane was distilled off to obtain 98 g of an aqueous dispersion of a zinc salt of a salicylic acid derivative of the present invention containing a sensitizer having a concentration of 45% (average particle diameter: 0.7 μm).

Comparative Example 1 To 40 g of zinc salt of 3,5-di (α-methylbenzyl) salicylic acid was added 40 g of 1,2-dichloroethane to prepare 80 g of a 50% 1,2-dichloroethane solution. Next, an aqueous solution obtained by dissolving 2.0 g of polyvinyl alcohol (Kuraray Povar PVA205) in 100 g of water was subjected to a rotation speed of 1 using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.).
While stirring at 0000 rpm, 80 g of the 1,2-dichloroethane solution was added, and emulsification and dispersion were performed. 1,2-Dichloroethane was distilled off while heating the obtained emulsion while stirring, and 92 g of a 45% aqueous dispersion of zinc salt of 3,5-di (α-methylbenzyl) salicylic acid having a concentration of 45% was obtained.
(Average particle diameter 0.8 μm) was obtained.

Comparative Example 2 Zinc salt of 3,5-di (α-methylbenzyl) salicylic acid, zinc salt of 3- (α-methylbenzyl) -5- (1 ′, 3′-diphenylbutyl) salicylic acid and 3- (1 ', 3'
Mixture 4 of -diphenylbutyl) -5- (α-methylbenzyl) salicylic acid zinc salt in a weight ratio of 72:14:14
0 g, 40 g of 1,2-dichloroethane was added, and the concentration was 5
80 g of a 0% 1,2-dichloroethane solution was prepared.
Next, an aqueous solution obtained by dissolving 2.0 g of polyvinyl alcohol (Kuraray Povar PVA205) in 100 g of water was subjected to a rotation speed of 100 using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.).
While stirring at 00 rpm, 80 g of the 1,2-dichloroethane solution was added, and emulsification and dispersion were performed. While heating the obtained emulsion under stirring, 1,2-dichloroethane was distilled off to obtain 92 g of an aqueous dispersion of zinc salt of a salicylic acid derivative having a concentration of 45% (average particle diameter: 0.8 μm). .

Comparative Example 3 3- (α-methylbenzyl) salicylic acid, 5- (α-methylbenzyl) salicylic acid, 3,5-di (α-methylbenzyl) salicylic acid, 3- (α-methylbenzyl) -5
-(1 ', 3'-diphenylbutyl) salicylic acid, 3-
(1 ′, 3′-diphenylbutyl) -5- (α-methylbenzyl) salicylic acid, 3- [4 ′-(α′-methylbenzyl) -α-methylbenzyl] -5- (α-methylbenzyl) salicylic acid And 3- (α-methylbenzyl) -5
A mixture of-[4 '-(α'-methylbenzyl) -α-methylbenzyl] salicylic acid, that is, a salicylic acid derivative (a-1) in which 1 mole of styrene reacted with 1 mole of salicylic acid, 1 mole of salicylic acid A mixture of a salicylic acid derivative (a-2) reacted with 2 mol of styrenes and 3 mol of a salicylic acid derivative (a-3) reacted with 1 mol of styrene per 1 mol of salicylic acid in a weight ratio of 38:40:22. 40 g of 1,2-dichloroethane in 40 g of zinc salt
And a 50% strength 1,2-dichloroethane solution 80
g was prepared. Next, an aqueous solution obtained by dissolving 2.0 g of polyvinyl alcohol (Kuraray Poval PVA205) in 100 g of water was stirred using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 10,000 rpm while the above 1,2- Emulsion and dispersion were performed by adding 80 g of a dichloroethane solution. While heating the obtained emulsion under stirring,
The 1,2-dichloroethane was distilled off to obtain 92 g of an aqueous dispersion of a zinc salt of a salicylic acid derivative having a concentration of 45% (average particle diameter: 0.8 μm).

Synthesis Example 1 In a 2000 ml glass reactor equipped with a stirrer, 152.2 g (1.0 mol) of methyl salicylate, 9
38.1 g of 8% sulfuric acid (25% based on methyl salicylate)
%) And 500 g of 1,2-dichloroethane, and the reactor was kept at 0 to 2 ° C. while stirring and mixing.
6.8 g (4.0 mol) were continuously fed at 1.0 g / min. After the supply, the mixture was further stirred at 0 to 2 ° C for 2 hours.
63.4 g of a 49% aqueous sodium hydroxide solution was added to the reaction mixture.
After heating, the mixture was heated to distill off 1,2-dichloroethane. Further, 133 g of a 30% aqueous sodium hydroxide solution
In addition, the mixture was heated to perform hydrolysis. Next, zinc sulfate
Aqueous solution 64 containing 143.8 g (0.5 mol) of heptahydrate
3.8 g was continuously fed at 10 g / min. After dripping,
Further, the mixture was stirred at 30 ° C. for 1 hour to perform zincation. The produced zinc salt was separated by filtration and dried to obtain a salicylic acid derivative zinc salt (600 g). The zinc salt of the salicylic acid derivative was separated by silica gel column chromatography to obtain 50 g of a zinc salt of the salicylic acid derivative in which 1 mol of salicylic acid was substituted with 4 to 10 mol of styrene.

Comparative Example 4 One mole of the salicylic acid produced in Synthesis Example 1 contained 4 to 4 parts of styrene.
35.6 g of zinc salt of salicylic acid derivative substituted by 10 mol
To 40 g of a mixture of 4.4 g of zinc salt of 3,5-di (α-methylbenzyl) salicylic acid and 40 g of 1,2-dichloroethane, 80 g of a 50% 1,2-dichloroethane solution was prepared. Next, an aqueous solution obtained by dissolving 2.0 g of polyvinyl alcohol (Kuraray Povar PVA205) in 100 g of water was mixed with a homomixer [Tokusai Kika Kogyo Co., Ltd.]
While stirring at 10,000 rpm.
80 g of the 1,2-dichloroethane solution described above was added, and emulsification and dispersion were performed. While heating the obtained emulsion under stirring, 1,2-dichloroethane was distilled off to obtain a concentration of 45%.
92 g of an aqueous dispersion of a zinc salt of a salicylic acid derivative (average particle diameter 0.8 μm) was obtained.

Comparative Example 5 One mole of the salicylic acid produced in Synthesis Example 1 contained 4 to 4 parts of styrene.
2 g of a zinc salt of a 10 mol substituted salicylic acid derivative and 3,
Zinc salt of 5-di (α-methylbenzyl) salicylic acid 38
40 g of 1,2-dichloroethane was added to 40 g of the resulting mixture, and 80 g of a 50% strength 1,2-dichloroethane solution was added.
Was prepared. Next, an aqueous solution obtained by dissolving 2.0 g of polyvinyl alcohol (Kuraray Poval PVA205) in 100 g of water was stirred with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 10,000 rpm while the above 1, 2 was stirred. -Dichloroethane solution (80 g) was added to perform emulsification and dispersion. While heating the obtained emulsion under stirring,
The 1,2-dichloroethane was distilled off to obtain 92 g of an aqueous dispersion of a zinc salt of a salicylic acid derivative having a concentration of 45% (average particle diameter: 0.8 μm).

The composition ratio (weight ratio) of the zinc salt of the salicylic acid derivative prepared in Examples 1 to 4 and Comparative Examples 1 to 5, and
Table 1 (Table 1) shows the dispersion stability evaluation measured by the following method.
Indicated according to Evaluation of dispersion stability of aqueous dispersion of zinc salt of salicylic acid derivative (dispersion stability test) 40 g of aqueous dispersion of zinc salt of each salicylic acid derivative produced in Examples 1 to 4 and Comparative Examples 1 to 5 (solids concentration 45%) were placed in glass sample bottles of 50 ml each, stored at 40 ° C. for 30 days, and the sedimentation rate of each aqueous dispersion was measured. The sedimentation rate was calculated by multiplying the value obtained by dividing the height of the sediment in the sample bottle by the height of the liquid surface by 100. The smaller the numerical value of the sedimentation rate, the better the dispersion stability.

[0059]

[Table 1] From these results, it was found that the aqueous dispersion obtained by dispersing the zinc salt of the salicylic acid derivative of the present invention hardly sedimented under standing and had excellent aqueous dispersion stability.

Examples 6 to 9 and Comparative Examples 6 to 10 The aqueous dispersions of the zinc salt of the salicylic acid derivative prepared in Examples 1 to 4 and Comparative Examples 1 to 5 were mixed with various materials having the following composition to form a 20% A coating solution was prepared.

Aqueous dispersion of zinc salt of 45% salicylic acid derivative 10 g Aqueous dispersion of 69% light calcium carbonate 50 g Aqueous suspension of 20% starch 9 g Aqueous dispersion of 50% carboxy-modified SBR latex 5 g Water 142.5 g 20 % Coating solution 216.5 g This coating solution was applied to a high-quality paper (50 g / m ² ) so that the coating amount (weight of the color developer layer) at the time of drying was 3.0 g / m ² , dried, and dried. A pressure recording sheet (lower sheet) was prepared.

Evaluation of pressure-sensitive recording sheet The prepared pressure-sensitive recording sheet (lower sheet) was evaluated by the following method. (Coloring test) Each pressure-sensitive recording sheet (lower sheet) thus prepared, and a micro containing 3-N, N-diethylamino-6-methyl-7-anilinofluoran as a main electron-donating color-forming compound. A commercially available upper sheet for black coloring coated with capsules [N-4 manufactured by Mitsubishi Paper Mills, Ltd.]
0] was stored in a constant temperature and humidity room at 23 ° C. and 60% (relative humidity) for 24 hours. Next, in the constant temperature and humidity chamber, the upper sheet and the lower sheet were superposed on each other with their application surfaces facing each other, and a load pressure of 300 kg / cm ² was applied for 1 second to develop color. After the pressurization, the color density of the recorded image after 24 hours was reduced to $ 8.
0 was measured using a color difference meter [manufactured by Nippon Denshoku Industries Co., Ltd.].
Indicated by value. The results are shown in Table 3 (Table 3). The color density of the recorded image indicates that the smaller the Y value, the deeper the color. (Light resistance test of blank paper) The direction of the coated surface was adjusted every two hours so that the coated surface of each of the prepared pressure-sensitive recording sheets (lower sheet) was almost perpendicular to the sun, and was exposed to sunlight for 10 hours. did. Each pressure-sensitive recording sheet (lower sheet) exposed to sunlight and microcapsules containing 3-N, N-diethylamino-6-methyl-7-anilinofluoran as a main electron-donating color-forming compound Is coated on a commercially available black color upper sheet [N-4 manufactured by Mitsubishi Paper Mills, Ltd.]
0] was stored in a constant temperature and humidity room at 23 ° C. and 60% (relative humidity) for 24 hours. Next, in the constant temperature and humidity chamber, the upper sheet and the lower sheet were superposed on each other with their application surfaces facing each other, and a load pressure of 300 kg / cm ² was applied for 1 second to develop color. After pressurization, the color density of the recorded image after 24 hours was measured using a # 80 color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd.), and indicated by a Y value. The results are shown in Table 3 (Table 3).
The color density (Y value) of the recorded image after the light fastness test of the white paper;
The smaller the difference in the coloring density (Y value) in the coloring test, the better the light resistance of the white paper. (Water Resistance Test of Recorded Image) Each lower sheet colored in the color development test was immersed in water at 23 ° C. for 4 hours, and the residual density of the recorded image was measured with a # 80 color difference meter [manufactured by Nippon Denshoku Industries Co., Ltd.] And measured using a Y value. The results are shown in Table 2 (Table 2). The smaller the difference between the residual density (Y value) after the water resistance test and the color density (Y value) of the color development test, the better the water resistance of the recorded image.

[0063]

[Table 2] From the results in Table 2, the recording sheet obtained by applying the aqueous dispersion containing the zinc salt of the salicylic acid derivative of the present invention has a good color density even when the coated surface is exposed to sunlight, and
It was found that a good residual density was maintained even after the recorded image was immersed in water.

Examples 10 to 11 The aqueous dispersions of the zinc salt of the salicylic acid derivative prepared in Examples 1 and 5 were mixed with various materials having the following compositions to prepare 20% coating solutions.

Aqueous dispersion of zinc salt of 45% salicylic acid derivative 10 g Aqueous dispersion of 69% light calcium carbonate 50 g 20% aqueous suspension of starch 9 g 50% Aqueous dispersion of carboxy-modified SBR latex 5 g Water 142.5 g 20 % Coating solution 216.5 g This coating solution was applied to a high-quality paper (50 g / m ² ) so that the coating amount (weight of the color developer layer) at the time of drying was 3.0 g / m ² , followed by drying and drying. A pressure recording sheet (lower sheet) was prepared.

Evaluation of pressure-sensitive recording sheet The prepared pressure-sensitive recording sheet (lower sheet) was evaluated by the following method. (Low-Temperature Coloring Test) Each of the prepared pressure-sensitive recording sheets (lower sheet) and 3-N, N-diethylamino-6-methyl-7-anilinofluoran are contained as main electron-donating color-forming compounds. A commercially available black coloring upper sheet coated with microcapsules [N-4 manufactured by Mitsubishi Paper Mills, Ltd.
0] in a constant temperature and humidity room at 5 ° C. and 30% (relative humidity).
Stored for 4 hours. Next, in this constant temperature and humidity chamber, both application surfaces of the upper sheet and the lower sheet face each other and are superimposed,
A color was applied for 1 second under a load pressure of 300 kg / cm ² . After pressurization, the color density of the recorded image after 10 seconds and 24 hours was measured using a # 80 color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd.) and indicated by the Y value. The results are shown in Table 3 (Table 3). The color density of the recorded image indicates that the smaller the Y value, the deeper the color.

[0067]

[Table 3] From the results shown in Table 3, the recording sheet obtained by applying an aqueous dispersion containing a developer obtained by further adding a sensitizer (polyoxytetramethylene glycol) to the zinc salt of the salicylic acid derivative of the present invention is as follows. It has been found that the color develops in a short time under a low temperature environment.

Example 12 138.1 g (1 mol) of salicylic acid and zinc oxide 1 were placed in a 2000 ml glass reactor equipped with a stirrer.
0.4 g (7.5% based on salicylic acid) and 52.1 g (0.5 mol) of styrene were added, and the reactor was kept at 145 ° C. while stirring and mixing, and 208.3 g of styrene (2.
0 mol) was continuously fed at 1 g / min. After the addition, the mixture was further stirred at 145 ° C. for 2 hours to obtain a pale brown transparent viscous substance. When the reaction mixture was analyzed by high performance liquid chromatography, 1 mol of salicylic acid contained 1 to 3 styrene.
A molar substituted salicylic acid derivative (a) and salicylic acid 1
The weight ratio of the salicylic acid derivative (b) in which styrene was substituted by 4 to 10 mol per mol was 65:35. The reaction mixture was cooled to 50 ° C., 350 g of 1,2-dichloroethane, 350 g of water, and 135 g of a 30% aqueous sodium hydroxide solution were added, and the mixture was stirred and mixed at 30 ° C. for 1 hour. Next, zinc sulfate
Aqueous solution 64 containing 143.8 g (0.5 mol) of heptahydrate
3.8 g was continuously fed at 10 g / min. After dripping,
Further, the mixture was stirred at 30 ° C. for 1 hour to perform zincation. The lower layer (organic layer) was separated to obtain 810 g of a 1,2-dichloroethane solution containing a zinc salt of a salicylic acid derivative of the present invention.
1,2-Dichloroethane was distilled off while heating the solution with stirring to obtain 410 g of a zinc salt of a salicylic acid derivative of the present invention. Various materials having the following composition are mixed with the zinc salt of the salicylic acid derivative of the present invention, and 100 to 1
After homogenization at 50 ° C., a developed ink of the present invention was prepared. 28 g of zinc salt of the salicylic acid derivative of the present invention; rosin-modified epoxy acrylate [trade name: Banbeam UV-22C, manufactured by Harima Chemicals, Inc.] 17 g; tricyclodecane dimethanol diacrylate [trade name: Iupimer UV SA-1002; Made by Mitsubishi Yuka Co., Ltd.] 44 g ・ 2,2-dimethoxy-2-phenylacetophenone [trade name: Irgacure 651, manufactured by Ciba-Geigy] 4 g ・ Titanium oxide [trade name: Taipaque CR93, manufactured by Ishihara Sangyo Co., Ltd.] 7 g Developed ink 100g

Comparative Example 11 Example 12 was repeated, except that the zinc salt of 3,5-di (α-methylbenzyl) salicylic acid was used in place of the zinc salt of the salicylic acid derivative of the present invention.
A color developing ink was prepared by the method described in (1).

Evaluation of Developed Ink The developed inks prepared in Example 12 and Comparative Example 11 were evaluated by the following methods. (Offset printing suitability test) The developed color ink was printed on a form paper (Mitsubishi Diamond Foam) at a filling amount of ² g / m ² using an offset printing machine, processed with an ultraviolet irradiation device (high-pressure mercury lamp), and then developed. The color ink was dried.
The dampening solution uses a 15% aqueous solution of isopropyl alcohol,
Water was supplied by Dahlgren method. After printing at 5,000 m, the water roller was observed for dirt. When there was no dirt, it was represented by ○, and when there was dirt, it was represented by x. The results are shown in Table 4 (Table 4).

[0071]

[Table 4] From the results shown in Table 4, it was found that the developed ink prepared using the zinc salt of the salicylic acid derivative of the present invention did not stain the water roller at the time of offset printing and had excellent suitability for offset printing.

[0072]

According to the present invention, there is provided a color developer having good dispersion stability, excellent light fastness of white paper, and excellent water resistance of a recorded image, an aqueous dispersion thereof, a recording sheet and a color developing ink. It became possible.

[Brief description of the drawings]

FIG. 1 is a schematic structural diagram of an example of a pressure-sensitive recording sheet.

FIG. 2 is a schematic structural diagram of an example of a pressure-sensitive recording sheet.

FIG. 3 is a schematic structural diagram of an example of a pressure-sensitive recording sheet.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Masakatsu Nakatsuka 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture F-term (reference) 2H085 AA07 BB26 DD14 DD15 DD32 DD43 DD45 DD46 DD48 FE03 HH03 4J039 AD09 AD21 AE04 AE06 BA13 BA14 BA16 BA18 BA23 BA30 BA31 BA32 BA35 BC03 BC16 BC17 BC20 BC31 BC48 BC54 BE01 BE27 CA06 EA35 EA38 EA44 GA01 GA02

Claims (11)

[Claims] 1. A developer containing a polyvalent metal salt of a salicylic acid derivative, wherein the salicylic acid derivative comprises (a) at least one salicylic acid derivative obtained by substituting 1 mol of salicylic acid with 1 to 3 mol of styrene. ~ 85% by weight,
(B) at least one salicylic acid derivative obtained by substituting 4 mols or more of styrenes for 1 mol of salicylic acids;
A color developer characterized by containing 0% by weight. 2. The color developer according to claim 1, wherein the polyvalent metal salt of the salicylic acid derivative is a zinc salt of a salicylic acid derivative. 3. The color developer according to claim 1, wherein the salicylic acid derivative is obtained by reacting salicylic acids and styrenes in the presence of a polyvalent metal oxide. 4. The developer according to claim 3, wherein the salicylic acids and styrenes are reacted at a molar ratio of 1: 1.5 to 1: 5.0. 5. The developer according to claim 3, wherein the oxide of the polyvalent metal is zinc oxide. 6. A polyvalent metal salt of a salicylic acid derivative is obtained by subsequently reacting a salicylic acid derivative obtained by reacting a salicylic acid with a styrene in the presence of a polyvalent metal oxide to obtain a polyvalent metal salt. 2. The developer according to claim 1, wherein 7. An aqueous dispersion of a color developer obtained by dispersing the color developer according to claim 1 in water. 8. A recording sheet having a layer containing a polyvalent metal salt of a salicylic acid derivative according to claim 1 on a support. 9. A recording sheet obtained by applying a coating solution obtained by using the aqueous dispersion of the color developer according to claim 7 onto a support. 10. A color developing ink comprising a color developing agent, a photocurable compound, a photopolymerizing agent and a pigment, wherein the color developing agent is the color developing agent according to claim 1. 11. A recording sheet obtained by printing on a support using the developed color ink according to claim 10.