JP2003175670A - Developer composition for pressure-sensitive copying paper and pressure-sensitive copying paper using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color developer composition for a pressure-sensitive copying paper which manifests both of a high initial coloring speed and a high coloring density; and a pressure-sensitive copying paper. <P>SOLUTION: For this color developer composition, an alkylene oxide added compound of a specified styrene group substituted phenol is blended in a color developer of which the main component is a polyvalent metal salt of a specified salicylic acid derivative. Using such a color developer composition, a water-soluble dispersion is formed and is applied on a supporting body, and thus, this pressure-sensitive copying paper having a color developer layer is formed. Also, a favorable method regarding the manufacturing method for the water-soluble dispersion of the color developer is disclosed as well. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a color developer composition, a method for producing an aqueous dispersion thereof, and a pressure-sensitive composition which exhibits a high initial color development speed and a high color density obtained by applying a coating solution containing them. Regarding copy paper.

[0002]

2. Description of the Related Art Pressure-sensitive copying paper is generally called carbonless paper, and color is developed by writing pressure such as writing and impact pressure such as a typewriter, and a plurality of copies can be taken at the same time. It is a copy paper. Various types of pressure-sensitive copying paper have been proposed, but in principle, all of them are color-forming reactions between an electron-donating colorless dye (organic color-developing agent) and an electron-accepting color-developing agent. It is based on.

As the pressure-sensitive copying paper, what is called a transfer type is typical, and (a) an electron-donating organic color former (hereinafter simply referred to as "color former") is dissolved. An upper paper coated with an encapsulating colorant composition containing microcapsules encapsulating an oily substance as a main component on one side of a support, and (b) an electron acceptor that develops color when contacted with the color former on one side of the support. Medium paper coated with a color developer composition containing a sex developer (hereinafter, simply referred to as "color developer") as a main component, and the encapsulated color developer composition on the opposite surface,
(C) and various sheets such as lower paper having a developer composition applied on one surface of the support, and generally (a) upper paper-
(C) Lower paper or (a) Upper paper- (b) Middle paper-
(C) It is put into practical use as a copy set by combining the lower sheets in this order.

In addition, a self-coloring type pressure-sensitive type which is referred to as a single color-developing type, in which a color-developing composition and a color-developing composition are applied on the same surface of a support to enable pressure-sensitive copying with one sheet. Copy paper (so-called self-contained pressure-sensitive copy paper) is also known as one form thereof.

In recent years, as a developer for such pressure-sensitive copying paper,
Basically excellent advantage that the developed color image has higher color development ability than the inorganic type developer and the phenol type developer, and the resulting color image does not decrease in density due to moisture adhesion or normal file storage. Therefore, a polyvalent metal salt of a salicylic acid derivative has been increasingly used as the most preferable one.

However, the polyvalent metal salt of salicylic acid derivative has a basic problem that the coloring density is low immediately after printing and it takes time to reach the saturation density (so-called inferior initial coloring property). Can be a particular problem in cold regions and low room temperatures in winter. Various studies have been made to solve the problem, but it is not sufficient. Particularly, in recent years, with the increase in simultaneous copying of a large number of sheets, further improvement for expressing a faster color development speed and a higher color density with a small external force. Is much more desired.

That is, for example, in a handheld terminal for inputting orders at supermarket cash registers and family restaurants, receipts and order slips are printed on pressure-sensitive copying paper, but in order to process the input of orders and the like without error in a crowded store. It is imperative that a clearly printed receipt and order slip be printed in the shortest possible time.

Up to now, as a method for solving the problem relating to the initial color development, a method has been used in which the polyvalent metal salt of the salicylic acid derivative is mixed with the polyvalent metal salt of the rosin-modified phenol resin (Japanese Patent Laid-Open No. 2-255375). ), A mixture of the polyvalent metal salt of the salicylic acid derivative with a specific aryl ether (JP-A-4-43071), the salicylic acid derivative polyvalent metal salt of vegetable oil and an organic solvent having a boiling point of 200 ° C. or less. (JP-A-4-52184), the salicylic acid derivative polyvalent metal salt or the like having a boiling point of 150 to 33 of the biphenyl derivative or the like.
Dissolved in a high boiling organic solvent at 0 ° C. (JP-A-59)
No. 202889) is known. However, these methods have not been satisfactory for developing a high initial color development speed and a high color density at the same time.

The Applicants have been
Previously, a method of adding a specific amide compound (Japanese Patent Laid-Open No. 211987/1992) was proposed, and it was shown that a remarkable improvement in initial color developability was observed by using the amide compound together. It is strongly desired that a compound that can be produced at a lower cost can achieve at least the same or higher effects.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a color developer composition for pressure-sensitive copying paper and a pressure-sensitive copying paper which exhibit both initial color development speed and high color density.

[0011]

That is, according to the present invention, the following inventions are provided.

(1) A developer composition containing a developer containing a nucleus-substituted salicylate represented by the general formula (1) as a main component and a compound represented by the general formula (2). object.

[0013]

[Chemical 3] (In the formula, R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different and each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group,
A phenyl group, a nucleus-substituted phenyl group, an aralkyl group, or a nucleus-substituted aralkyl group, and
Two adjacent R ₁ , R ₂ , R ₃ and R ₄ may combine to form a ring. n is an integer of 1 to 3 and M is a polyvalent metal atom. )

[0014]

[Chemical 4] (In the formula, n ₁ is an integer of 1 to 7 and n ₂ is an integer of 1 to 5.)

(2) The developer composition according to (1), which is treated as an aqueous dispersion.

(3) A developer containing a nucleus-substituted salicylate represented by the general formula (1) as a main component and a compound represented by the general formula (2) are dissolved in an organic solvent, and this organic solution is dissolved. The method for producing an aqueous dispersion of a developer composition according to (2) above, which comprises emulsifying and dispersing in an aqueous medium, and further heating the emulsified dispersion to remove the organic solvent by distillation.

(4) An aqueous dispersion of the developer composition produced by the method described in (3) above.

(5) A color-developing layer obtained by coating a support with a coating solution containing the developer composition according to (1) or an aqueous dispersion of the color-developing composition according to (4). A pressure-sensitive copying paper characterized by having.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

As the main component of the developer composition of the present invention, a salt of the nucleus-substituted salicylic acid represented by the above formula (1) is used.

The substituted salicylate is not particularly limited, and conventionally known ones having excellent color developing ability are preferably used. For example, as typical examples thereof, 3-methyl-5-isononylsalicylic acid, 3-methyl-5-isododecylsalicylic acid, 3-methyl-5-isopentadecylsalicylic acid, 3-methyl-5- (α- Methylbenzyl) salicylic acid, 3-methyl- (α, α-dimethylbenzyl) salicylic acid, 3,5-di-secondarybutylsalicylic acid, 3,5-ditertiarybutyl-6-methylsalicylic acid, 3-tertiarybutyl-5-phenyl Salicylic acid, 3,5-diter-shalyamyl salicylic acid,
3-cyclohexyl-5-isononyl salicylic acid, 3-
Phenyl-5-isononylsalicylic acid, 3- (α-methylbenzyl) -5-isononylsalicylic acid, 3-isopropyl-5-isononylsalicylic acid, 3-isononylsalicylic acid, 3-isononyl-5-methylsalicylic acid, 3
-Isononyl-5-cyclohexylsalicylic acid, 3-isononyl-5-phenylsalicylic acid, 3-isononyl-
5- (α-methylbenzyl) salicylic acid, 3-isononyl-5- (4, α-dimethylbenzyl) salicylic acid, 3
-Isononyl-5- (α, α-dimethylbenzyl) salicylic acid, 3- (α, α-dimethylbenzyl) -5-isononylsalicylic acid, 3-isononyl-6-methylsalicylic acid, 5-isononylsalicylic acid, 3-tersia Ributyl-5-isononylsalicylic acid, 3,5-diisononylsalicylic acid, 3-isododecylsalicylic acid, 3-isododecyl-5-methylsalicylic acid, 3-isododecyl-6
-Methylsalicylic acid, 3-isopropyl-5-isododecylsalicylic acid, 3-isododecyl-5-ethylsalicylic acid, 5-isododecylsalicylic acid, 3-isopentadecylsalicylic acid, 3-isopentadecyl-5-methylsalicylic acid, 3-iso Pentadecyl-6-methylsalicylic acid, 5-isopentadecylsalicylic acid, 3,5-dicyclohexylsalicylic acid, 3-cyclohexyl-5- (α
-Methylbenzyl) salicylic acid, 3-phenyl-5-
(Α-Methylbenzyl) salicylic acid, 3-phenyl-5
-(Α, α-Dimethylbenzyl) salicylic acid, 3- (α
-Methylbenzyl) salicylic acid, 3- (α-methylbenzyl) -5-methylsalicylic acid, 3- (α-methylbenzyl) -6-methylsalicylic acid, 3- (α-methylbenzyl) -5-phenylsalicylic acid, 3, 5-di (α-methylbenzyl) salicylic acid, 3- (α-methylbenzyl) -5- (α, α-dimethylbenzyl) salicylic acid,
3- (α-methylbenzyl) -5-bromosalicylic acid,
3- (α-methyl-4′-methylbenzyl) -5-methylsalicylic acid, 3,5-di (α-methyl-4′-methylbenzyl) salicylic acid, 3- (α, α-dimethylbenzyl) -5- Methylsalicylic acid, 3- (α, α-dimethylbenzyl) -6-methylsalicylic acid, 3,5-di (α,
α-Dimethylbenzyl) salicylic acid, 5- [α-methyl-4 ′-(α-methylbenzyl) -benzyl] salicylic acid, 3- [α-methyl-4 ′-(α-methylbenzyl) -benzyl] salicylic acid, 3 -Α-methylbenzyl-5- [α-methyl-4 ′-(α-methylbenzyl)-
Benzyl] salicylic acid, 3- [α-methyl-4 ′-(α
-Methylbenzyl) -benzyl] -5-α-methylbenzylsalicylic acid, 3-α, α-dimethylbenzyl-5-
[Α-Methyl-4 ′-(α-methylbenzyl) -benzyl] salicylic acid, 3- [α-methyl-4 ′-(α-methylbenzyl) -benzyl] -5-α-methylbenzylsalicylic acid, benzylated styrene Salicylic acid, pinened salicylic acid, 2-hydroxy-3- (α, α-dimethylbenzyl) -1-naphthoic acid or 3-hydroxy-7-
Examples include polyvalent metal salts such as (α, α-dimethylbenzyl) -naphthoic acid.

Specific examples of the polyvalent metal M in the formula (1) include magnesium, calcium, zinc, aluminum, iron, cobalt and nickel, but zinc is most preferable. These may be used alone or as a mixture.

Some of these substituted salicylates are crystalline alone, and their softening points are also variable. In order to prepare a non-crystalline developer having a preferable softening point, these are appropriately mixed and prepared as follows so as to have desired physical properties.

That is, if the softening point of the developer is too low,
The developer, which is applied and dried on the surface of a support such as paper, permeates and migrates between the paper fibers, reducing the color density, and the aqueous dispersion of the developer easily solidifies, resulting in long-term storage stability. Will lack. On the other hand, if the softening point of the color developer is too high,
When it is applied to the surface of the paper, which is a support, and dried, it hardly exhibits a binding action, so that a large amount of an adhesive or a binder must be used in order to firmly fix it on the paper surface. In that case, this adhesive or the like acts as a barrier film to prevent smooth transfer of the color former existing in the microcapsules, and the color developing ability may be lowered. For these reasons, the softening point range of the developer is preferably 20 ° C. or higher, more preferably about 30 to 85 ° C.

The first method of adjusting the softening point of the developer to the above-mentioned preferable temperature is to mix the developers having different softening points. Secondly, a substance that can raise or lower the softening point of the color developer is mixed. For example, as the substance for lowering the softening point, for example, a metal salt of fatty acid, trialkylphenol, triaralkylphenol or styrene oligomer can be added, and conversely, for increasing the softening point, for example, polystyrene, poly- α-Methylstyrene, petroleum resin or the like can be added.

The softening point in the present invention means the softening temperature in the state where the developer contains equilibrium water in water.
Such softening temperature is usually 50 from the softening point in the dry state.
It is about ℃ lower.

In the present invention, a specific styrene-substituted phenol alkylene oxide adduct represented by the formula (2) is used in combination with the above-mentioned developer containing a nucleus-substituted salicylate as a main component.

Specific examples of the styrene-substituted phenol include mono-, di-, and tri-styrene-substituted phenols. For example, the mono-styrene-substituted phenols include 2-α-methylbenzylphenol and 4-α-. Methylbenzylphenol, 2- (α, α-dimethylbenzyl) phenol, 4- (α, α-dimethylbenzyl)
Phenol may be mentioned, and examples of the di-styrene-substituted phenol include 2,4-di (α-methylbenzyl) phenol, 2,6-di (α-methylbenzyl) phenol,
2,4-di (α, α-dimethylbenzyl) phenol may be mentioned, and further tri-styrene-substituted phenols include 2,4,6-tri (α-methylbenzyl) phenol and 2-α-. Methylbenzyl-4- [α-methyl-
4 ′-(α-methylbenzyl) benzyl] phenol,
Examples thereof include styrene phenol compounds such as 2- [α-methyl-4 ′-(α-methylbenzyl) benzyl] -4- [α-methyl-4 ′-(α-methylbenzyl) benzyl] phenol. These are used alone or as a mixture of two or more thereof.

These styrene-substituted phenols are used as an alkylene oxide addition compound, and examples of the alkylene oxide include ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), etc., and ethylene oxide is particularly preferable.

The alkylene oxide addition compound of styrene-substituted phenol can be produced by addition reaction of these singly or in combination of two or more kinds.

The alkylene oxide may be added to the styrene-substituted phenol by a conventional method, and the number of added moles (n ₁ in the general formula (2)) is usually 1 to 7, preferably 1 to 3. When the number of added moles exceeds 7, foaming or the like occurs and the performance deteriorates, which is not preferable.

The addition ratio of the alkylene oxide adduct of styrene-substituted phenol represented by the general formula (2) to the nucleus-substituted salicylate represented by the general formula (1) is 100% by weight of the nucleus-substituted salicylate. The amount is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, per part by mass.

If the compound represented by the general formula (2) is blended in a much larger amount than that, the color-forming performance of the resulting pressure-sensitive copying paper is deteriorated, and the surface of the color developer layer exhibits tackiness, which causes a problem during printing. It may cause troubles. On the other hand, if the amount is less than the above range, the effect of the present invention is not achieved.

To prepare the aqueous dispersion of the developer, for example, the developer represented by the general formula (1) is dissolved in an organic solvent and emulsified and dispersed in an aqueous medium. The organic solvent has various properties such as relatively low solubility in water, good solubility of the color developer, low boiling point, and resistance to chemical changes during preparation of the dispersion. Those having are preferred.

Specific examples of the organic solvent include, but are not limited to, benzene, toluene, xylene, chloroform, carbon tetrachloride, trichloroethane, and the like.
Examples include chlorobenzene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, butanol, amyl alcohol, and methyl tertiary butyl ether. These may be used alone or in combination of two or more.

The amount of the organic solvent used is appropriately selected according to the size of the target dispersed particles and the like, and it is desirable to use it in the range of about 500 parts by mass or less relative to 100 parts by mass of the color developer.

In the method for producing the aqueous dispersion of the developer composition of the present invention, the specific developer represented by the general formula (1) and the compound represented by the general formula (2) are added as described above. It is dissolved in an organic solvent, and then this organic solvent solution is emulsified and dispersed in an aqueous medium, preferably in the presence of a dispersant. At this time, if the compound represented by the general formula (2) is also dissolved in an organic solvent, there is an advantage that the preparation work becomes easy.

As the dispersant used when emulsifying and dispersing in an aqueous medium, those which are commonly used for preparing an aqueous dispersion are used, and examples thereof include alkali salts of alkyl sulfates and alkali salts of alkylbenzenesulfonic acid, Anionic surfactants such as alkali salts of alkylnaphthalene sulfonic acid, alkali salts of oleic acid amide sulfonic acid, alkali salts of dialkyl sulfosuccinic acid; nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester; Gum arabic,
Natural polymer substances such as sodium alginate, agar and gelatin; semi-compatible polymer substances such as carboxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl starch, phosphorylated starch, sodium lignin sulfonate; methyl vinyl ether / maleic anhydride copolymer Alkali salts of polymers and copolymers such as, styrene / maleic anhydride copolymer, acrylic acid polymer, acrylic acid / methyl methacrylate copolymer, acrylic acid / acrylamide copolymer, vinylbenzene sulfonic acid polymer, etc. And synthetic polymer substances such as polyvinyl alcohol, polyacrylamide, vinylcarboxylic acid ester / acrylamide copolymer, and the like. These dispersants may be used alone or in combination of two or more.

In the method of the present invention, vinylcarboxylic acid ester / acrylamide copolymers are particularly preferable among them, and the degree of polymerization is 100 or more.
Alkyl or alkoxyalkyl ester 4 having at least 70 to 96 mol% of acrylamide and 4 or less carbon atoms of acrylic acid, methacrylic acid, itaconic acid or maleic acid
An acrylamide copolymer having a copolymerization ratio of ˜30 mol% is particularly preferable because it has a large protective colloid property and a small foaming property.

The amount of these dispersants used is appropriately adjusted according to the size of the target dispersed particles and the like, but is preferably about 1 to 30 parts by mass with respect to 100 parts by mass of the color developer. Adjusted.

The prepared aqueous dispersion of the developer is subjected to heat treatment to remove the organic solvent by distillation to obtain an aqueous dispersion of the developer composition consisting of spherical particles.

The aqueous dispersion of the color developer composition thus obtained may be further pulverized and / or dispersed, if desired.

As such a crushing / dispersing machine, for example, various sand mill type crushers using crushing media such as ball mill, pepper mill, sand grinder (vertical type, horizontal type), cobol mill, attritor, dyno mill; 3
Examples include high-speed grinding machines such as the present roll mill, high-speed impeller disperser, high-speed stone mill, and high-speed impact mill, but are not limited to these specific devices.
A sand mill type pulverizer (vertical type, horizontal type) and a high-speed impeller disperser are preferable, and a sand mill type pulverizer (vertical type, horizontal type) is more preferable, considering the ease of setting treatment conditions, pulverization efficiency, and the like.

Generally, the concentration of the color developer in the aqueous dispersion is preferably as high as it is allowed, and a high concentration of 10% or more is possible, and the preferable upper limit is about 55%. With such a high concentration, not only the transportation cost can be reduced, but also a high-concentration coating liquid can be prepared, the drying efficiency in the coating process can be improved, and the quality improving effect of the obtained color paper for pressure-sensitive copying paper can be improved. Can be expected.

In the present invention, a color developing paper for pressure-sensitive copying paper is obtained by applying a coating liquid containing an aqueous dispersion of the color developing agent composition to a support such as paper to form a color developing agent layer. By combining this with a color-developing agent layer, a pressure-sensitive copying paper having the color-developing agent layer can be obtained.

As the coating liquid for forming the developer layer, an aqueous dispersion of the developer composition obtained as described above is usually used, and further as an adhesive or a binder, for example, starch, casein or arabic gum. , Carboxymethyl cellulose, polyvinyl alcohol, styrene / butadiene copolymer latex, vinyl acetate latex and the like are blended. Furthermore, inorganic raw materials such as zinc oxide, magnesium oxide, titanium oxide, aluminum hydroxide, calcium carbonate, magnesium sulfate, calcium sulfate and various auxiliaries known in the field of pressure-sensitive copying paper production can be added as appropriate.

The total mass ratio of the developer containing a salicylate of the general formula (1) as a main component and the alkylene oxide addition compound represented by the general formula (2) in all solid components in the coating liquid ( It may be referred to as a developer component ratio.) Is about 10 to 80%. 10 color developer components
If it is less than 80%, sufficient color developability cannot be obtained, and if it exceeds 80%, the surface properties of the color developing paper deteriorate, which is not preferable.

The thus-prepared coating liquid for forming the developer layer in the present invention is a high-quality paper by a usual coating device such as an air knife coater, a blade coater, a roll coater, a size press coater, a curtain coater and a short dwell coater. It is coated on a support such as coated paper, synthetic paper or film, and finally finished as pressure-sensitive copying paper. The coating amount of the coating liquid on the support is not particularly limited, but is a dry mass of 0.5 to 10 g / m ^2, preferably,
It is about ² to 8 g / m ² .

That is, the pressure-sensitive copying paper of the present invention is constructed by combining the color-developing paper having the color-developing layer obtained as described above and the color-developing paper coated with the encapsulated color-developing composition. . The color forming agent of the color forming paper combined with the color developing paper is not particularly limited, and those conventionally used can be used, for example, fluoran compounds,
Phenothiazine compounds, Rhodamine lactam compounds, Triphenylmethanephthalide compounds, Indolylphthalide compounds, Triazine compounds, Triphenylmethane compounds, Spiropyran compounds, Leukoauramine compounds, Indolylazaphthalide compounds And the like are preferred.

The above coating liquid has a developer layer and a color developer layer on the same surface of a support, or a mixed coating layer of a developer liquid and a coating liquid containing an encapsulated color developer. Of course, it can also be applied to a self-coloring type pressure-sensitive copying paper having.
The color developer layer in the present invention includes such a mixed coating layer.

[0051]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In addition, "parts" and "%" in the examples represent "parts by mass" and "% by mass", respectively, unless otherwise specified.

[Production Example 1] In a flask with an internal volume of 1 L equipped with a stirrer and a thermometer, 73% of mono-α-methylbenzylphenol, 25% of di-α-methylbenzylphenol and tri-α-methyl were prepared according to a conventional method. Benzylphenol 2%
Mixture (average molecular weight 228, hereinafter referred to as SP)
After 228 g was charged and EO was added thereto using potassium hydroxide as a catalyst, the catalyst was treated to add 2 moles of EO to SP (viscosity 450 mPa · s / 25 ° C., hydroxyl value 17
8) 316 g was obtained (hereinafter, this 2 mol adduct of SP is referred to as SP-2EO).

In the same manner, EO5 mol adduct of SP (viscosity 305 mPa · s / 25 ° C., hydroxyl value 125) and EO15 mol adduct of SP (softening point 20-27 ° C. hydroxyl value 73) were synthesized. Similarly, hereinafter, the EO5 mol adduct of SP and the EO15 mol adduct of SP are referred to as SP-5EO and SP-15EO, respectively.

Production Example 2 In a 1 L flask similar to Production Example 1, a mixture of di-α-methylbenzylphenol 95% and tri-α-methylbenzylphenol 5% (average molecular weight 307, hereinafter DSP 307)
After adding g, EO was added to this using potassium hydroxide as a catalyst, and the catalyst was treated to add 2 mol of EO to DSP (viscosity 4,100 mPa · s / 25 ° C., hydroxyl value 14
2) 395 g was obtained (hereinafter, 2 mol addition product of DSP is
Notated as SP-2EO. ).

In the same manner, 5 mol of EO adduct of DSP (viscosity 950 mPa · s / 25 ° C., hydroxyl value 106),
And a 15 mol adduct of DSP (softening point 22 to 30 ° C., hydroxyl value 58) were synthesized. Hereinafter, the EO5 mol adduct of DSP and the EO15 mol adduct of DSP are referred to as DSP-5EO and DSP-15EO, respectively.

[Production Example 3] In a 1 L flask similar to Production Example 1, 13% of di-α-methylbenzylphenol and 75% of tri-α-methylbenzylphenol were prepared by a conventional method.
405 g of a mixture of 12% tetra-α-methylbenzylphenol (average molecular weight 405, hereinafter referred to as TSP) was charged, and EO was added thereto using potassium hydroxide as a catalyst, and then the catalyst was treated to add 5 mol of EO to TSP. Material (viscosity 10,500 mPa · s / 25 ° C, hydroxyl value 90) 6
25 g was obtained. Hereinafter, this EO5 mol addition product of TSP is described as TSP-5EO.

Example 1 (Preparation of Aqueous Dispersion Liquid of Developer Composition) 2000 g of water and zinc sulfate (7 water) were placed in a cylindrical stainless steel container having an internal volume of 20 L equipped with a stirrer and a thermometer. 400 g of salt) was added and dissolved. 8500 g of a 10% aqueous solution of sodium 3,5-di (α-methylbenzyl) salicylate
Was added while stirring the contents vigorously. The metathesis immediately produced zinc 3,5-di (α-methylbenzyl) salicylate and sodium sulfate, and the inside of the container became a thixotropic liquid.

In the container, a copolymer of α-methylstyrene and styrene (copolymerization ratio: 40:60 mol%,
Average molecular weight: about 1500) 150 g and SP-2EO
900 g of methyl isobutyl ketone solution containing 20 g was added in a short time. With the lapse of time, the fluidity of the thixotropic contents gradually improved, and when the contents became flowable to some extent, the container was heated to bring the temperature of the contents to 75 ° C. and allowed to stand.

After standing, the aqueous phase separates into the upper layer and the oil phase into the lower layer.
Transferred to a 00 mL beaker made of hard glass. Furthermore, 600 g of water, 2.5 g of sodium carbonate, polyvinyl alcohol (saponification degree: 98%, polymerization degree: about 1700)
Add 500 g of a 5% aqueous solution and 60 g of a 25% aqueous solution of a copolymer of ethyl acrylate and acrylamide (copolymerization ratio: 13:87 mol%, degree of polymerization: about 400) at a temperature of 35-35.
20 at 8800 to 9000 rpm with a homomixer (Model M, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 40 ° C.
The emulsification operation was performed for a minute. Thus, an oil-in-water type emulsion was obtained.

The emulsion was transferred to a hard glass three-necked flask with an internal volume of 10 L equipped with a stirrer, a thermometer and a distillation port, and 2000 g of water was further added, and the flask was heated while gently stirring the contents. And boiled. When methyl isobutyl ketone and a part of water are taken out from the distillation port, the content is 38% of total solid content containing no methyl isobutyl ketone.
Became an emulsion. The emulsion is an aqueous dispersion of the developer composition, and the average particle size of the dispersed particles is 1.5 μm.
It was m. The softening point of the dispersed phase was 77 ° C.

(Preparation of developer coating solution) 18 parts of an aqueous dispersion of the 38% developer composition obtained by the above treatment, 94 parts of calcium carbonate and 100 parts of water are mixed and dispersed, and a binder is further added. As a 10% aqueous solution of polyvinyl alcohol 50
Part, 50% carboxy-modified SBR latex (SN
-307, manufactured by Sumitomo Nogatac Co., Ltd.) was mixed and dispersed to prepare a developer coating solution.

(Production of color developing paper for pressure-sensitive copying paper) The above-mentioned color developer coating solution was applied to one side of a base paper of 40 g / m ² as a support so that the dry mass was 5 g / m ² . After drying, a color developing paper for pressure-sensitive copying paper was obtained.

[Second Embodiment] In the first embodiment, SP-2
An aqueous dispersion of the developer composition was prepared in the same manner as in Example 1 except that 20 g of SP-5EO was used instead of 20 g of EO. The average particle size of the resulting developer-dispersed particles was 1.5 μm (total solid content: 38%). Hereinafter, a color-developing paper for pressure-sensitive copying paper was obtained in the same manner as in Example 1.

Comparative Example 1 SP-2 in Example 1
An aqueous dispersion of the developer composition was prepared in the same manner as in Example 1 except that 20 g of SP-15EO was used instead of 20 g of EO. The average particle size of the obtained developer dispersed particles was 1.5 μm (total solid content: 38%).

Example 3 The aqueous dispersion of the color developer composition obtained in Example 1 was pulverized with a horizontal sand mill (Grain Mill GMH-S20M, manufactured by Asada Iron Works Co., Ltd.) under the condition of 3 kg / min. A more finely divided aqueous developer dispersion was prepared. The average particle size of the obtained developer-dispersed particles is 1.
3 μm (total solid content 38%). Hereinafter, a color-developing paper for pressure-sensitive copying paper was obtained in the same manner as in Example 1.

Example 4 1000 g of zinc 3-isododecylsalicylate and 700 g of toluene were mixed and dissolved at 50 ° C. to prepare a toluene solution. 20 g of the above DSP-2EO was added to and dissolved in this toluene solution. The toluene solution was transferred to a stainless steel beaker with an internal volume of 5 L, water 600 g, sodium carbonate 2.5
g, copolymer of ethyl acrylate and acrylamide (copolymerization ratio: 13 to 87 mol%, degree of polymerization: about 400) 25%
100 g of an aqueous solution was added, and a homomixer (Model M, manufactured by Tokushu Kika Kogyo Co., Ltd.) was used at a temperature of 35 to 40 ° C. for 8800 min.
The emulsification operation was performed for 20 minutes at a rotation speed of ˜9000 times to obtain an oil-in-water emulsion.

The emulsion was transferred to a hard glass three-necked flask with an internal volume of 10 L equipped with a stirrer, a thermometer and a distillation port, and 2000 g of water was added, and the flask was heated while stirring the contents slowly. And boiled. When about 700 g of toluene and 650 g of water were taken out from the distillation port, the content became an emulsion containing no toluene and having a total solid content of 38%. The average particle size of the obtained developer-dispersed particles is 1.5 μm.
It was m. The softening point of the dispersed phase was 64 ° C.

Next, this dispersion was pulverized with a sand grinder (MODEL No. OSG-8G, manufactured by Igarashi Kikai Co., Ltd.) under the condition of 2 kg / min to obtain an aqueous dispersion of a developer having an average particle diameter of 1.3 μm. Prepared. Thereafter, in the same manner as in Example 1, a color developing paper for pressure-sensitive copying paper was obtained.

[Fifth Embodiment] In the fourth embodiment, the DSP-
An aqueous dispersion of the developer composition was prepared in the same manner as in Example 4 except that 20 g of DSP-5EO was used instead of 20 g of 2EO. The average particle size of the obtained developer dispersed particles was 1.3 μm (total solid content: 38%). Hereinafter, a color-developing paper for pressure-sensitive copying paper was obtained in the same manner as in Example 1.

[Comparative Example 2] In Example 4, the DSP-
An aqueous dispersion of the developer composition was prepared in the same manner as in Example 4 except that 20 g of DSP-15EO was used instead of 20 g of 2EO. The average particle size of the obtained developer dispersed particles was 1.3 μm (total solid content: 38%). Less than,
A color developing paper for pressure sensitive copying paper was obtained in the same manner as in Example 1.

Example 6 Copolymer of 500 g of zinc 3,5-di (α-methylbenzyl) salicylate, α-methylstyrene and styrene (copolymerization ratio: 40:60 mol%, average molecular weight: about 1500) 150 g, 350 g of zinc 3-isododecylsalicylate, and 700 g of toluene were mixed and dissolved at 50 ° C. to prepare a toluene solution.

TSP-5EO 20 was added to this toluene solution.
g was added and dissolved. Separately, in a stainless steel beaker with an internal volume of 5 L, water 600 g, sodium carbonate 25
g, copolymer of ethyl acrylate and acrylamide (copolymerization ratio: 13 to 87 mol%, degree of polymerization: about 400) 25%
100 g of the aqueous solution was added, and a homomixer (Model M, manufactured by Tokushu Kika Kogyo Co., Ltd.) was run at 880 to 380 min.
An emulsification operation was performed for 20 minutes at a rotation speed of 0 to 9000 times to obtain an oil-in-water emulsion.

This was transferred to a hard glass three-necked flask with an internal volume of 10 L equipped with a stirrer, a thermometer and a distillation port, and 2000 g of water was further added, and then the flask was heated and boiled while gently stirring the contents. Let About 700 g of toluene and about 650 g of water were taken out from the distillation port to obtain an emulsion containing toluene as a content and having a total solid content of 38%. The average particle size of the dispersed particles of the resulting developer composition is 1.5.
was μm. The softening point of the dispersed phase was 75 ° C.
Hereinafter, a color-developing paper for pressure-sensitive copying paper was obtained in the same manner as in Example 1.

Example 7 The aqueous dispersion of the developer composition obtained in Example 6 was applied to a horizontal sand mill (Grain Mill G MI-S20M, manufactured by Asada Iron Works Co., Ltd.) at 4 min.
The dispersion was pulverized under the conditions of kg to prepare an aqueous dispersion of the developer composition. The average particle size of the obtained aqueous dispersion particles of the color developer was 1.3 μm (total solid content: 38%). Thereafter, in the same manner as in Example 1, a color-developing paper for pressure-sensitive copying paper was obtained.

[Comparative Example 3] In Example 1, SP-2
An aqueous dispersion of the developer composition was prepared in the same manner except that 20 g of EO was not used. The average particle size of the resulting aqueous dispersion particles of the color developer was 1.5 μm (total solid content: 38
%)Met. Thereafter, in the same manner as in Example 1, a color-developing paper for pressure-sensitive copying paper was obtained.

[Comparative Example 4] In Example 4, the DSP-
An aqueous dispersion of the developer composition was prepared without using 20 g of 2EO. The average particle size of the resulting aqueous dispersion particles of the color developer was 1.3 μm (total solid content: 38%). In the same manner, a color developing paper for pressure sensitive copying paper was obtained.

[Comparative Example 5] In Example 6, the TSP-
An aqueous dispersion of the developer composition was prepared without using 20 g of 5EO. The average particle size of the resulting aqueous dispersion particles of the color developer was 1.5 μm (total solid content: 38%). In the same manner, a color developing paper for pressure sensitive copying paper was obtained.

[Comparative Example 6] In Example 1, SP-2
Instead of EO, the two described in JP-A-4-43071
A color developing paper for pressure-sensitive copying paper was obtained in the same manner as in Example 1 except that 20 g of (2,4 bis-α-methylbenzylphenoxy) ethanol was used.

Comparative Example 7 SP-2 in Example 1
Instead of EO, N, N described in JP-A-4-211987
A developer for pressure-sensitive copying paper was obtained in the same manner as in Example 1 except that 20 g of dicyclohexylamide was used.

The following 14 types of color-developing paper for pressure-sensitive copying paper thus obtained were subjected to the following quality evaluation tests, and the results are shown in Table 1.

[Quality Evaluation Test] (Preparation of Upper Paper) A capsule coating liquid prepared by dissolving crystal violet lactone as a color former in alkylated naphthalene and microcapsulating the oily liquid was prepared.
The fine paper was coated on one surface so that the dry mass was 4 g / m ^2, and dried to obtain a fine paper (color paper) having a color layer.

(Color development performance test) In order to see the color development effect at low temperature, the color developing paper and the upper paper were left in an atmosphere of 1 ° C. for 10 hours. Next, the coated surfaces of the color paper and the top paper are made to face each other, and in a 1 ° C atmosphere, a drop-type color tester (weight: 15
0 g, height: 10 cm) to develop color, and as a parameter of the initial color development rate, 1 from the pressing pressure with a Macbeth reflection densitometer.
The color density after 0 seconds was used as the final density, and the color density one day after the pressing was measured with a Macbeth reflection densitometer.

[0083]

[Table 1]

[0084]

The effects of the present invention are confirmed as follows with reference to Table 1 which summarizes the above examples and comparative examples.

(A) First, Example 1 [using SP-2EO as a compound of formula (2)], Example 2 [using SP-5EO as a compound of formula (2)], and Comparative Example 3 [general formula (2)] No compound], Comparative Example 6 [instead of the compound of formula (2), 2
-(2,4 bis-α-methylbenzylphenoxy) ethanol], Comparative Example 7 [instead of the compound of formula (2),
The use of the N, N-dicyclohexylamide] shows that the use of the developer composition of the present invention has a remarkable effect on the initial color density and the final color density as compared with the comparative example. I understand. In Example 3 [using SP-2EO as the compound of formula (2)], the particle diameter of dispersed particles was further reduced by a sand mill treatment.
It can be seen that the color development characteristics are further improved.

(B) In Comparative Example 1 [using SP-15EO as the compound of the formula (2)], when the number of moles of EO added (n ₁ in the formula (2)) is 15, which is too large,
It can be seen that due to foaming or the like, the color development characteristic rather deteriorates.

(C) Similarly to the fourth and fifth embodiments,
The effects of the present invention can be confirmed by comparing the results of Comparative Example 2 and Comparative Example 4 or by comparing the results of Example 6 and Example 7 with Comparative Example 5.

As described above, according to the present invention, a high color density and a remarkable effect of improving the initial color developability can be produced much easier and cheaper than the compounds used in the conventional color developers. It can be realized by using a possible compound.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shigeo Sakaguchi             Sanko Stock, 708 Shimonogo Town, Moriyama City, Shiga Prefecture             Company Shiga factory (72) Inventor Takashi Ishibashi             Osaka Prefecture Ibaraki City Itokaichi 1-chome 10-24 Sanko Stock             Inside the company (72) Inventor Ryo Miyake             Osaka Prefecture Ibaraki City Itokaichi 1-chome 10-24 Sanko Stock             Inside the company F term (reference) 2H085 AA07 BB37 BB39 DD02 DD45                       FE03

Claims (5)

[Claims] 1. A developer composition comprising a developer containing a nucleus-substituted salicylate represented by the general formula (1) as a main component, and a compound represented by the general formula (2). . [Chemical 1] (In the formula, R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different and each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group,
A phenyl group, a nucleus-substituted phenyl group, an aralkyl group, or a nucleus-substituted aralkyl group, and
Two adjacent R ₁ , R ₂ , R ₃ and R ₄ may combine to form a ring. n is an integer of 1 to 3 and M is a polyvalent metal atom. ) [Chemical 2] (In the formula, n ₁ is an integer of 1 to 7 and n ₂ is an integer of 1 to 5.) 2. The developer composition according to claim 1, which is treated as an aqueous dispersion. 3. A developer containing a nucleus-substituted salicylate represented by general formula (1) as a main component and a compound represented by general formula (2) are dissolved in an organic solvent, and the organic solution is aqueous. The method for producing an aqueous dispersion of a developer composition according to claim 2, wherein the dispersion is emulsified and dispersed in a medium, and the emulsion is heated to distill off the organic solvent. 4. An aqueous dispersion of a developer composition produced by the method of claim 3. 5. A developer layer formed by applying a coating liquid containing the developer composition according to claim 1 or an aqueous dispersion of the developer composition according to claim 4 to a support. A pressure-sensitive copying paper characterized by having.