JPH11129614A - Developer composition and pressure sensitive recording material using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developer composition for improving a water resistance, yellowing resistance and heat resistance of a color developed image and having the other characteristics to be incorporated in a pressure sensitive copy material utilizing a color developing reaction of an electron donative colorless dye and an electron acceptive developer. SOLUTION: An electron donative colorless dye and an electron acceptive developer composition each contains as a main component a mixture of (A) a 3,5-bis(α-methylbenzyl)polyvalent metallic salt salicylate, (B) a nuclear substituted salicyl polyvalent metal salt represented by a general formula I, and (C) alkyl ester or polyvalent metal salt of (4-hydroxy-3,5-di-tert-butylphenyl) propionic acid represented by a general formula II. [In the formula I, R1 and R2 are each a hydrogen atom, a nonyl group or a dodecyl group, M is a polyvalent metal atom, and m is an atomic value of the M], and [in the formula II, R3 is 1-20C alkyl group or a polyvalent metal atom, n is an integer of 1 or 2 or more, and t-Bu is a tert-butyl group].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color developer composition for a pressure-sensitive copying material utilizing a color development reaction between an electron-donating colorless dye and an electron-accepting color developer, and the color developer composition. And a pressure-sensitive recording material having the support on the surface of a support.

[0002]

2. Description of the Related Art A pressure-sensitive copying paper mainly comprises a microcapsule or the like containing an oil-based substance in which an electron-donating colorless dye (hereinafter referred to as a color forming agent) is dissolved (eg, paper, plastic sheet, synthetic paper, etc.). (A composite sheet or the like) and a color developer composition mainly composed of an electron-accepting color developer (hereinafter referred to as a color developer) that forms a color by contacting the color former on one side of the support. There are various sheets such as a medium sheet coated with a color former capsule composition on the opposite side, and a lower sheet coated only with a developer composition on one side of a support.Generally, upper sheet-lower sheet, or The combination of the upper sheet, the middle sheet, and the lower sheet is used as a copy set. Also, it is used as a self-coloring type (so-called Cercon type) pressure-sensitive copying paper in which a color developing agent and a color developing agent are coated on the same surface of the support to enable pressure-sensitive copying with one sheet.

[0003] As a developer for such pressure-sensitive copying paper, for example, an inorganic developer such as acid clay, activated clay, attapulgite, zeolite, bentonite, silica, aluminum silicate, etc .; a phenol resin; Organic developers such as polyvalent metal salts are known.

[0004]

An organic developer has many advantages over an inorganic developer. In recent years, in particular, polyvalent metal salts of nucleus-substituted salicylic acid have been widely used. Proposals have been made (for example, Japanese Unexamined Patent Publication No.
JP-A-55410, JP-A-3-248883, JP-A-4-
No. 34515, JP-A-4-110186, JP-A-4-110186
211987, JP-A-4-224992, etc.). However, at present, a color developer which has both water resistance and light resistance of a color image and which does not impair the other recording characteristics to be provided has not yet been obtained with satisfactory quality. On the other hand, various quality improvement proposals have also been made for phenolic resins, but there is a large problem in light resistance, particularly in yellowing. The present inventors have conducted various studies to solve such problems, and as a result, have arrived at the present invention capable of exhibiting excellent performance in both water resistance and light resistance.

[0005]

According to the present invention, (A)
3,5-bis (α-methylbenzyl) salicylic acid polyvalent metal salt, and (B) a compound represented by the general formula (1)

[0006]

Embedded image [In the general formula (1), R ₁ and R ₂ represent a hydrogen atom, a nonyl group or a dodecyl group, M represents a polyvalent metal atom, and m represents a valence of M. And a polyvalent metal salt of salicylic acid represented by the general formula (C):

[0007]

Embedded image [In the general formula (2), R ₃ represents an alkyl group having 1 to 20 carbon atoms or a polyvalent metal atom, n represents an integer of 1 or 2 or more, and t-Bu represents a tert-butyl group. And a polyvalent metal salt of (4-hydroxy-3,5-di-tert-butylphenyl) propionic acid represented by the following formula: , Water resistance of recorded images and uncolored areas,
It is possible to obtain a pressure-sensitive recording material which is excellent in light resistance and satisfies other characteristics to be provided. Here, the nonyl group or dodecyl group means a propylene trimer or propylene tetramer added to a benzene ring.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Components (A) of the developer composition according to the present invention include magnesium, calcium, zinc and aluminum as polyvalent metals constituting 3,5-bis (α-methylbenzyl) salicylate. , Iron, cobalt, nickel, but preferably calcium, zinc, aluminum, most preferably zinc. Examples of the nucleus-substituted salicylic acid polyvalent metal salt represented by the general formula (2) of the component (B) include 3- and / or 5-nonylsalicylic acid, 3,5-di-nonylsalicylic acid, 3- and / or 5-dodecyl Salicylic acid, 3-nonyl-5-dodecylsalicylic acid, 3-dodecyl-5-nonylsalicylic acid, magnesium, calcium, zinc, aluminum, iron, cobalt, nickel salts of 3,5-di-dodecylsalicylic acid, preferably nickel salts. Calcium, zinc and aluminum salts, most preferably zinc salts. As the alkyl ester of (4-hydroxy-3,5-di-tert-butylphenyl) propionic acid represented by the general formula (2) of the component (C),
Methyl, ethyl, propyl (linear or branched), butyl, pentyl, hexyl, octyl, nonyl, decyl,
Esters such as dodecyl and octadecyl are exemplified, and the polyvalent metal salts include magnesium, calcium, zinc, aluminum, iron, cobalt and nickel salts, preferably calcium, zinc and aluminum salts, most preferably zinc salts. It is.

The mixing ratio (weight) of the components (A), (B) and (C) is as follows: A: B: C = 15-83: 15
83: 2 to 30, preferably 40 to 70:25 to 55:
5-10. If the component (A) is smaller than this range [the component (B) is larger than this range], the heat resistance tends to be unsatisfactory, and the component (B) is smaller than this range [the component (A) is larger than this range]. ], The water resistance tends to be unsatisfactory. If the component (C) is smaller than this range, the light resistance tends to be unsatisfactory, and if the component (C) is larger than this range, no particular effect can be expected to increase, and a negative effect is exerted on the coloring speed and the coloring density. Causes fear.

[0010] Each of these components is mixed with a solid powder at a predetermined mixing ratio and is mechanically pulverized and atomized in water containing a dispersant, or the solid powder of each component is individually mixed with a dispersant. It is also possible to mechanically pulverize and atomize in water, mix each dispersion at a predetermined ratio, and obtain an aqueous fine dispersion of the developer composition. It is most preferable to prepare a fine water dispersion and apply it to the surface of the support.

In order to prepare an aqueous dispersion of a homogeneous mixture of the developer composition, (1) a mixture in which each component is blended at a predetermined ratio is prepared by mixing the components in a water-soluble manner because the mixture has a good solubility. After being dissolved and inert in an organic solvent having a relatively low boiling point and emulsified and dispersed in water containing a dispersant, the organic solvent is distilled off. (2) A mixture obtained by mixing and grinding each component at a predetermined ratio is melt-emulsified and dispersed in water containing a dispersant heated to a temperature higher than its softening point (preferably 30 ° C. or higher) and then cooled (for example, JP-A-1-34782). (3) The respective components are mixed at a predetermined ratio, then melted, uniformly kneaded, and cooled and pulverized. The composition is subjected to a mechanical pulverization method as usual, such as a ball mill, a pebble mill, a sand grinder, a co-ball mill, and a high-speed impact error. Obtained by the atomization method.

The concentration of the aqueous dispersion of the thus obtained developer composition is usually adjusted to a concentration of about 10% to 55% by weight, and further, an adhesive, an inorganic or organic pigment, a benzophenone, or a benzotriazole-based ultraviolet absorber is used. Colorants, zinc laurate, dialkyl lauramide, stearoyl amide, etc., as appropriate, and as a developer solution coating solution, on a suitable support surface such as high quality paper, coated paper, synthetic paper, film, etc. Coated and dried to finish as pressure-sensitive copying paper. Of course, the present invention is also applicable to so-called self-coloring type pressure-sensitive copying paper.

[0013]

Next, examples of the present invention will be described together with comparative examples. Here, “%” is shown on a weight basis unless otherwise specified.

Example 1 (Preparation of a developer composition dispersion) 55 gr of zinc 3,5-bis (α-methylbenzyl) salicylate, 37 gr of zinc 5-dodecylsalicylate and (4-hydroxy-3,5)
-Di-tert-butylphenyl) propionic acid methyl ester (8 gr) was dissolved in toluene (90 gr), and sodium carbonate (0.2 gr) and polyvinyl alcohol (degree of saponification:
2.5 gr, ethyl acrylate-acrylamide copolymer (copolymerization ratio 13:87)
Mol%, degree of polymerization about 400) water 10 containing 1.5 gr
0gr and 2 to 8800 to 9000 times / min with a homomixer (Specialty Chemical Industry: Model M) at 35 to 40 ° C.
It was emulsified and dispersed for 0 minutes. The emulsified dispersion is then added to water 20
After adding 0 gr, toluene was distilled out with water under gentle stirring. After the outflow of toluene was stopped, cooling was performed to obtain an aqueous dispersion containing about 38% of the developer composition. The average particle size of the dispersed fine particles was 1.0 μm. (Preparation of coating liquid) 27 gr of the 38% color developer composition dispersion obtained above, 1 gr of 10% sodium polyacrylate,
A coating solution is prepared by adding 75 gr of calcium carbonate, 5 gr of 16% polyvinyl alcohol, 5 gr of 48% carboxy-modified SBR latex (Sumitomo Nogatack Co., Ltd .: SN-307) and water to adjust the concentration of the developer composition to 10%. I got (Preparation of a color-developed sheet for pressure-sensitive copying) The coating solution thus obtained was applied to a surface of a PPC paper (manufactured by Ricoh Co., Ltd.) at 5 gr / m ² using a rod blade and dried at about 105 ° C. To form a color developing sheet.

Example 2 The procedure of Example 1 was repeated except that 46 gr of zinc 3,5-bis (α-methylbenzyl) salicylate and 46 gr of zinc 5-dodecylsalicylate were used. By operating in the same manner as in Example 1, a color-developed sheet was obtained.

Example 3 In the preparation of the developer composition dispersion liquid in Example 1, 55 gr of zinc 3,5-bis (α-methylbenzyl) salicylate and 37 gr of zinc 3,5-di-nonylsalicylate were used. A color-developed sheet was obtained in the same manner as in Example 1 except for using it. Example 4 In the preparation of the developer composition dispersion liquid in Example 1, instead of (4-hydroxy-3,5-di-tert-butylphenyl) propionic acid methyl ester,
A developer sheet was obtained in the same manner as in Example 1 except that 8 gr of lauryl ester was used.

Example 5 55 g of zinc 3,5-bis (α-methylbenzyl) salicylate, 37 gr of zinc 5-dodecylsalicylate and zinc (4-hydroxy-3,5-di-tert-butylphenyl) propionate 8g salt
The mixture was melted, kneaded uniformly, cooled and pulverized to obtain 0.2 g of sodium carbonate, 2.5 g of polyvinyl alcohol (degree of saponification: 98%, degree of polymerization: about 1700), and ethyl acrylate-acrylamide copolymer (Copolymerization ratio: 13:87 mol%, degree of polymerization: about 400) Added to 300 gr of water containing 1.5 gr, and the content was heated to 25 ° C. or more under a rotation of about 8,000 times / minute with a sand grinder. The mixture was pulverized for 3 hours while cooling externally so as not to disturb. Thereafter, the content was taken out from the sand grinder to obtain a dispersion containing about 25% of the developer composition. The average particle size of the dispersed color developer composition was 1.0 μm. Using this developer composition dispersion, in the same manner as in Example 1,
Preparation of a coating solution and preparation of a color developing sheet for pressure-sensitive copying were performed.

Comparative Example 1 A developing sheet for pressure-sensitive copying was prepared in the same manner as in Example 1 except that only 100 gr of zinc 3,5-di (α-methylbenzyl) salicylate was used. Obtained.

Comparative Example 2 The procedure of Example 1 was repeated, except that only 100 g of 5-dodecylsalicylic acid was used, to obtain a color developing sheet for pressure-sensitive copying.

Comparative Example 3 In Example 1, 60 gr of zinc 3,5-bis (α-methylbenzyl) salicylate was used.
And a color developing sheet for pressure-sensitive copying was obtained in the same manner as in Example 1, except that zinc chloride 5-dodecylsalicylate was used.

Comparative Example 4 92 gr of zinc 3,5-bis (α-methylbenzyl) salicylate in Example 1
And a color developing sheet for pressure-sensitive copying was obtained in the same manner as in Example 1, except that methyl (4-hydroxy-3,5-di-tert-butylphenyl) propionate was used in an amount of 8 gr.

Comparative Example 5 The procedure of Example 1 was repeated except that zinc 5-dodecylsalicylate and 8 gr of (4-hydroxy-3,5-di-tert-butylphenyl) propionic acid methyl ester were used. In the same manner as in the above, a color-developed sheet for pressure-sensitive copying was obtained. [Evaluation test method and results] The pressure-sensitive copying developer sheet obtained in each of the examples and comparative examples and the upper paper (blue type, manufactured by Oji Paper Co., Ltd.) were superposed on each other so that the coating surfaces faced each other, and the motor was electrically operated. After coloring depending on the type, the following performance tests were respectively performed. Table 1 shows the results.

Water resistance test : Immediately after the color-developing sheet was colored by an electric type, it was immersed in running water at 25 to 30 ° C. and left for 20 minutes, and the degree of fading of the color-developed image was visually judged.

Judgment Rank A: Almost no fading B: Substantial fading C: Substantial fading Lightfastness test : Immediately after coloring, the colored sheet was left under sunlight irradiation for about 10 hours (cumulative), and the degree of fading of the colored image was visually observed. It was determined by

Judgment Rank A: Almost no fading B: Slight fading C: Corresponding fading Yellowing resistance test : In the light resistance test, the yellowing degree of the uncolored white paper part was compared with the white paper part not irradiated with sunlight. The comparison was visually determined.

A: almost yellowing B: considerably yellowing (between A and C) C: considerable yellowing Heat resistance test : Put the coloring sheet in an oven at 105 ° C.
After allowing to stand for 16 hours, the color was developed, and the degree of color development of the developed image was visually determined.

A: Strong color development B: Slight color development C: Weak color development Example Comparative example {} Test number 1 2 3 4 5 1 2 3 4 5 5} ───────── 水性 Water resistance A A A A A A A CA A CA A Light resistance B B B B B B B B B B B Yellow resistance A A A A ACBBAA Heat resistance AAAAAAACAAC──────────────────────────── Table 1 As described above, the color image obtained by the color-developing sheet for pressure-sensitive copying according to the present invention is excellent in water resistance, yellowing resistance and heat resistance, and has a well-balanced performance as other pressure-sensitive copying materials.

[0028]

The color image obtained from the pressure-sensitive copying paper using the developer composition according to the present invention is excellent in water resistance and light resistance, and has a good balance of other properties.
It is extremely useful as a pressure-sensitive recording material.

Claims (5)

[Claims] 1. A pressure-sensitive recording material utilizing a color reaction between an electron-donating colorless dye and an electron-accepting developer, comprising: (A) 3,5-bis (α-methylbenzyl) salicylic acid polyvalent metal salt And (B) a general formula (1) [In the general formula (1), R ₁ and R ₂ represent a hydrogen atom, a nonyl group or a dodecyl group, M represents a polyvalent metal atom, and m represents a valence of M. And a nucleus-substituted salicylic acid polyvalent metal salt represented by the general formula (2): [In the general formula (2), R ₃ represents an alkyl group having 1 to 20 carbon atoms or a polyvalent metal atom, n represents an integer of 1 or 2 or more, and t-Bu represents a tert-butyl group. A color developer composition comprising, as a main component, a mixture consisting of an alkyl ester of (4-hydroxy-3,5-di-tert-butylphenyl) propionic acid or a polyvalent metal salt represented by the formula: 2. The mixing ratio (weight) of the components (A), (B) and (C) is A: B: C = 15-83:
The developer composition according to claim 1, wherein the ratio is 15 to 83: 2 to 30. 3. The developer composition according to claim 1, wherein the component (B) is a polyvalent metal salt of 3-dodecylsalicylic acid and / or 5-dodecylsalicylic acid. 4. The developer composition according to claim 1, wherein the component (B) is a 3,5-di-nonylsalicylic acid polyvalent metal salt. 5. A pressure-sensitive recording material utilizing a color reaction between an electron-donating colorless dye and an electron-accepting developer, wherein (A) 3,5-bis (α-methylbenzyl) salicylic acid polyvalent metal salt And (B) a general formula (1) [In the general formula (1), R ₁ and R ₂ represent a hydrogen atom, a nonyl group or a dodecyl group, M represents a polyvalent metal atom, and m represents a valence of M. A polyvalent metal salt of salicylic acid represented by the general formula (C): [In the general formula (2), R ₃ represents an alkyl group having 1 to 20 carbon atoms or a polyvalent metal atom, n represents an integer of 1 or 2 or more, and t-Bu represents a tert-butyl group. And a polyvalent metal salt of (4-hydroxy-3,5-di-tert-butylphenyl) propionic acid represented by the following formula: A pressure-sensitive recording material characterized by being contained in a layer.