JP2965604B2 - Developer composition, its production method and pressure-sensitive copying paper - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a developer composition, a method for producing the same, and a pressure-sensitive copying paper excellent in light resistance obtained by applying a coating solution containing the same.

[Background Art] A pressure-sensitive copying paper is provided with a color former capsule composition mainly composed of microcapsules containing an oily substance in which an electron-donating organic color former (hereinafter simply referred to as a color former) is dissolved. An upper paper coated on one side and a developer composition mainly composed of an electron-accepting color developer (hereinafter simply referred to as a color developer) that forms a color when contacted with the color former on one side of the support. There are various sheets such as middle paper coated with the color former capsule composition on the opposite side, and lower paper coated only with the developer composition on one side of the support. Generally, upper paper-lower paper, or upper paper It is practically used as a copy set by combining paper-medium paper-lower paper in this order. In addition, a self-coloring type pressure-sensitive copying paper in which a color developing agent and a color developing agent are applied on the same surface of a support to enable pressure-sensitive copying with one sheet is also known as one form thereof.

As the color developer, clays such as acid clay, activated clay, attapulgite, zeolite and bentonite, and phenol polymers such as phenol-aldehyde polymers and phenol-acetylene polymers are known. However, when the above-mentioned clays are used as a color developer, the clays adsorb substances in the air during the long-term storage, and the color-forming ability is significantly reduced. It has the disadvantage of discoloration or fading, and has the disadvantage that the print density is extremely reduced when it is exposed to water. On the other hand, the phenolic polymer has the drawbacks of poor light fastness of printing and yellowing of the color developer layer caused by exposure treatment. For this reason, substituted salicylates having excellent performances in various aspects have been attracting attention instead of the acidic substances as described above.

That is, the pressure-sensitive copying paper using the substituted salicylate hardly deteriorates in coloration ability even after long-term storage. Colored prints are relatively unlikely to be discolored or faded even after the date and time. When a substituted salicylate which is hardly soluble in water is used, the print density hardly decreases even if it is exposed to water. The developer layer has an advantage that yellowing hardly occurs even after exposure treatment. Further, the coloring ability is very high. It has excellent performance in various aspects, such as little change in print density and coloration ability even when treated for several hours at 100 ° C. or higher.

Thus, the performance of pressure-sensitive copying paper was greatly improved by using a substituted salicylate as a color developer instead of the color developer.

However, even pressure-sensitive copy paper using a substituted salicylate has a problem that, for example, a phenomenon in which a copied image is discolored when the copy paper after printing is exposed to direct sunlight is observed. What is desired is the current situation.

"Problems to be Solved by the Invention" It is an object of the present invention to solve the above problems and to provide a pressure-sensitive copying paper having excellent light fastness.

"Means for Solving the Problems" The present invention provides a compound represented by the general formula [I]: [In the formula [I], R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group, a phenyl group, It is a phenyl group, an aralkyl group or a aralkyl group with a nucleus, and _two adjacent groups out of R ₁ , R ₂ , R ₃ and R ₄ may combine to form a ring. n is an integer,
M represents a polyvalent metal atom. And a developer composition comprising a nucleus-substituted salicylate as a main component and 0.05 to 20 parts by weight of a compound represented by the general formula [II] per 100 parts by weight of the developer. .

(In the formula (II), R ₅ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, a phenyl group, a nucleus-substituted phenyl group, an aralkyl group, or a nucleus-substituted aralkyl group. .

A represents a monovalent metal atom or a polyvalent metal atom (excluding a nickel atom).

X is - (CH _{2) P} - or Wherein P is an integer of 0 or more, and R ₆ is a C ₁ -C ₃ alkyl group. m represents an integer. The present invention is also a pressure-sensitive copying paper obtained by applying a coating solution containing the above-described developer composition to a support.

Further, the present invention, a developer having a nucleus-substituted salicylate represented by the general formula [I] as a main component and a compound represented by the general formula [II] are dissolved in an organic solvent, and this solution is dissolved in an aqueous medium. This is a method for producing a developer composition dispersion obtained by emulsifying and dispersing under heating or without heating, and then heating the dispersion to distill and remove the organic solvent.

"Action" The substituted salicylates represented by the general formula [I] are all excellent in color developing ability, and typical examples thereof include 3-methyl-5-isononyl salicylic acid and 3-methyl-5-iso- Dodecyl salicylic acid, 3-methyl-5- (α-methylbenzyl) salicylic acid, 3-methyl-5- (α, α-dimethylbenzyl) salicylic acid, 3,5-disecondary butyl salicylic acid, 3,5-ditert-butyl- 6-methylsalicylic acid, 3-tert-butyl-5-phenylsalicylic acid, 3,5-ditertiaryamylsalicylic acid, 3-isononylsalicylic acid, 3-isononyl-5-methylsalicylic acid, 3-isononyl-6-methylsalicylic acid, 5 -Isononyl salicylic acid, 3,5-diisononyl salicylic acid, 3
-Isododecyl salicylic acid, 3-isododecyl-5-methyl salicylic acid, 3-isododecyl-6-methyl salicylic acid, 3-isopentadecyl salicylic acid, 5-isopentadecyl salicylic acid, 3,5-dicyclohexyl salicylic 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, 4-dimethyl) Benzyl) -5-methylsalicylic acid, 3,5-di (α, 4-dimethylbenzyl) 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- (4-
(Mesitylmethylbenzyl) salicylic acid, benzylated styrenated salicylic acid, pinenated salicylic acid, 2-hydroxy-3- (α, α-dimethylbenzyl) -1-naphthoic acid or 3-hydroxy-7- (α, α-dimethylbenzyl) ) -2-Naphthoic acid and the like.
Specific examples of polyvalent metals include magnesium, calcium,
Zinc, aluminum, iron, cobalt, nickel and the like can be mentioned, and zinc is most preferable. These may be used alone or as a mixture.

Here, the isononyl group, the isododecyl group, and the isopentadecyl group are each defined as a general term for the substituents formed by the addition of propylene trimer, propylene tetramer or 1-butene trimer and propylene pentamer.

Some of these substituted salicylates are crystalline by themselves, and their softening points also vary. In order to prepare a non-crystalline developer having a preferable softening point, the developer is appropriately mixed and adjusted to obtain desired physical properties.

If the softening point of the developer is too low, the developer applied to the paper surface and dried will penetrate and transfer between the paper fibers to lower the coloring density, and the aqueous dispersion of the developer is also likely to coagulate, Long-term storage stability may be lacking.

On the other hand, if the softening point of the color developer is extremely high, it hardly exhibits self-adhesion when coated and dried on the paper surface, so a large amount of adhesive must be used to fix it to the paper surface. However, the adhesive may form a film to prevent the transfer of the dye-dissolving oil present in the microcapsules, and the color developing ability may be slightly inferior.

For these reasons, the softening point range of the developer is preferably 20 ° C. or higher, more preferably about 30 ° C. to 85 ° C.

As a method of adjusting the softening point of the developer to a preferable temperature, first, a developer having a different softening point is mixed, and in order to lower the softening point of the developer, the softening point is adjusted. Adding a reducing substance, such as a metal salt of a fatty acid, a trialkylphenol, a trialkylalkylphenol or a styrene oligomer, and thirdly, a substance that increases the softening point of a developer having a softening point that is too low, such as polystyrene , Poly-α-methylstyrene or petroleum resin. The mixing ratio is not particularly limited.

In addition, the softening point in the present invention means a softening temperature in a state where a color developer contains equilibrium moisture in water. Usually, it is about 50 ° C. lower than the softening point in a dry state.

In the general formula [II], A is exemplified by a metal atom such as sodium, potassium, zinc, iron, magnesium, calcium, aluminum, cobalt, titanium, lead, manganese, and cadmium. Of these, zinc is particularly preferred.

M and A may be a common metal atom or may be different.

In addition, p is an integer of 0 or more and is not particularly limited, but usually an integer of about 0 to 15 is more preferable. m is an integer and represents the valence of A.

Specific examples of the compound represented by the general formula [II] include 3-tert-butyl-4-hydroxy-5- (2-benzotriazolyl) phenylpropionic acid and 3- (2-benzotriazolyl)- 4-hydroxy-5- (α, α-dimethylbenzyl) phenylpropionic acid, 3-tert-butyl-4-hydroxy-5- (2-benzotriazolyl) phenylisobutyric acid, 3- (2-benzotriazolyl) ) -4-Hydroxy-phenylacetic acid, 3-tert-butyl-4-hydroxy-5- (2-benzotriazolyl) benzoic acid, 3-tert-butyl-4-hydroxy-5- (2-benzotriazoly) L) phenylpropionic acid, 3- (2-benzotriazolyl) -4-hydroxy-5- (α, α-dimethylbenzyl) phenylbutyric acid, 3
-Octyl-4-hydroxy-5- (2-benzotriazolyl) phenyltridecanoic acid, 3-tert-amyl-4-hydroxy-5- (2-benzotriazolyl) phenyldecanoic acid, 3-phenyl- 4-hydroxy-5
(2-benzotriazolyl) phenylpropionic acid, 3
Metal salts such as -allyl-4-hydroxy-5- (2-benzotriazolyl) phenylpropionic acid.
Examples of the metal include sodium, magnesium, aluminum, potassium, calcium, cobalt, zinc and the like.

The compound represented by the general formula [II] is used alone or in combination. The compounding ratio is variously selected depending on the purpose of use of the color developer, and is not particularly limited. When a large amount is blended, the resulting coloring paper for pressure-sensitive copying paper may cause a decrease in the color-forming performance and a yellowing of the color developer-containing layer. 0.05 to 20 parts by weight per 100 parts by weight of salicylate,
More preferably, about 0.1 to 10 parts by weight of the compound represented by the general formula [II] is contained in the coating liquid for coloring paper.

To prepare a developer dispersion, for example, the general formula [I]
Is preferably dissolved in an organic solvent and emulsified and dispersed in an aqueous medium. The organic solvent is required to have various properties such as relatively low solubility in water, good solubility of the developer, low boiling point, and low resistance to chemical change during the preparation of the dispersion. You. At this time, when the compound represented by the general formula [II] is also dissolved in an organic solvent, there is an advantage that the preparation operation becomes easy.

Specific examples of the organic solvent include benzene, toluene, xylene, chloroform, carbon tetrachloride, trichloroethane, chlorobenzene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, butanol, amyl alcohol or methyl tert-butyl ether. No.

The amount of the organic solvent used is appropriately adjusted depending on the size of the intended developer-dispersed particles and the like, but is preferably adjusted within a range of about 500 parts by weight or less based on 100 parts by weight of the developer. .

When the organic solvent solution thus obtained is emulsified and dispersed in an aqueous medium with or without heating, the aqueous medium preferably contains an emulsifier. Examples of emulsifiers include low molecular weight anionic surfactants such as polyvinyl alcohol and alkali salts of alkyl sulfates and alkali salts of alkylbenzene sulfonic acids; anionic natural polymers such as gum arabic; acrylic acid polymers; vinylbenzene sulfonic acid polymers , Acrylic acid / acrylamide copolymer,
Examples thereof include alkali salts of an anionic polymer such as an ethylene / maleic anhydride copolymer. These may be used in combination of two or more.

The aqueous dispersion of the color developer thus prepared is subjected to heat treatment to remove the organic solvent by distillation to prepare a color developer aqueous dispersion composed of spherical particles.

The obtained aqueous developer dispersion may be subjected to a wet pulverization treatment, if necessary. Examples of the fine pulverizer include various types of sand mills using a pulverizing medium such as a ball mill, a pebble mill, a sand grinder (vertical type, horizontal type), a cobol mill, an attritor, a dyno mill, and the like.
High-speed grinders such as this roll mill, high-speed impeller disperser, high-speed stone mill, and high-speed impact mill, etc. can be mentioned, but in consideration of easy setting of processing conditions, crushing efficiency, etc., a sand mill type crusher (vertical type, horizontal type) A high-speed impeller disperser is preferable, and among them, a sand mill type pulverizer (vertical type, horizontal type) is more preferable.

In general, the concentration of the developer in the aqueous dispersion is usually as high as 10% or more, and a preferable upper limit is about 55%. Such a high concentration not only reduces the transportation cost, but also makes it possible to prepare a high-concentration coating liquid, thereby increasing the drying efficiency in the coating process and improving the quality of the obtained color paper for pressure-sensitive copying paper. Can also be expected.

The coating solution for forming the developer layer, the developer-containing composition dispersion thus obtained, usually further as an adhesive,
For example, starch, casein, gum arabic, carboxymethylcellulose, polyvinyl alcohol, styrene / butadiene copolymer latex, vinyl acetate latex, etc. are blended, and further, zinc oxide, magnesium oxide, titanium oxide, aluminum hydroxide, calcium carbonate And inorganic pigments such as magnesium sulfate and calcium sulfate, and various auxiliaries known in the field of pressure-sensitive copying paper can be appropriately added.

The amount of the developer layer coating solution applied to the support is not particularly limited, but is about ² to 8 g / m ² in terms of dry weight. The thus-prepared coating solution for the developer layer is applied to a high quality paper, a coated paper, a synthetic paper, a film by a usual 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. Etc., and finished as pressure-sensitive copying paper.

In addition, the method of the present invention is a self-coloring method having a developer layer and a color former layer on the same surface of a support, or having a mixed coating layer of a developer coating liquid and a coating liquid containing an encapsulated color former. Of course, the present invention can also be applied to a type pressure-sensitive copying paper (so-called self-contained type).

"Examples" Examples will be described below in order to further clarify the effects of the present invention, but the present invention is not limited only to these. In the examples, "parts" and "%" represent "parts by weight" and "% by weight", respectively, unless otherwise specified.

Example 1 2000 g of water and 400 g of zinc sulfate (heptahydrate) are placed in a 20,000 ml stainless steel cylindrical container equipped with a stirrer and a thermometer and dissolved therein. 8500 g of a 10% aqueous solution of sodium 3,5-di (α-methylbenzyl) salicylate
Is added with vigorous stirring of the contents. By the double decomposition, the inside of the container immediately becomes a thixotropic liquid. Here, 150 g of a copolymer of α-methylstyrene and styrene (copolymerization ratio; 40 to 60 mole percent, average molecular weight; about 1500) and 3- (2-benzotriazolyl)-
900 g of methyl isobutyl ketone solution containing 20 g of zinc 4-hydroxyphenylacetate are added in a short time. Since the fluidity of the thixotropic-dropped contents gradually improves, when the contents easily flow, the container is heated to a temperature of 75 ° C. and allowed to stand. The aqueous phase is separated into the upper layer and the oil phase is separated into the lower layer.
Transfer to 5000ml hard glass beaker. This further
600 g of water, 2.5 g of sodium carbonate, 500 g of a 5% aqueous solution of polyvinyl alcohol (ketonization degree: 98%, polymerization degree: about 1700) and a copolymer of ethyl acrylate and acrylamide (copolymerization ratio: 13 to 87 mol%, polymerization degree About 400) Add 25 g of a 25% aqueous solution, and add a homomixer (model M, manufactured by Tokushu Kika Kogyo Co., Ltd.)
An oil-in-water emulsion is obtained by performing the emulsification operation at 9000 rotations for 20 minutes. This is transferred to a 10,000 ml hard glass three-necked flask equipped with a stirrer, a thermometer and a distillation port, and 2,000 g of water is further added thereto. About 640 g of methyl isobutyl ketone and about water from the distillation port
Upon removal of 640 g, the contents are an emulsion of 39% total solids containing little methyl isobutyl ketone. The average particle diameter of the obtained developer-dispersed particles was 2.4 μm. The softening point of the dispersed phase is 78 ° C.

(Preparation of developer coating solution)

18 parts of the 39% developer dispersion obtained by the above treatment, 93 parts of calcium carbonate and 100 parts of water were mixed and dispersed, and 50 parts of a 10% aqueous solution of polyvinyl alcohol as a binder were further added.
% Of carboxy-modified SBR latex (SN-307, manufactured by Sumitomo Nogatack Co., Ltd.) was mixed and dispersed to prepare a developer coating solution.

[Manufacture of color-developed paper for pressure-sensitive copying paper]

5 g of dry weight of the above developer coating solution on one side of 40 g / m ² base paper
/ m ² and dried to obtain a color-developed paper for pressure-sensitive copying paper.

Example 2 In Example 1, 3- (2-benzotriazolyl)
Developer water was used in the same manner as in Example 1 except that zinc 3-tert-butyl-4-hydroxy-5- (2-benzotriazolyl) benzoate was used instead of zinc 4-hydroxyphenylacetate. A dispersion was prepared.

The average particle diameter of the obtained developer-dispersed particles was 3.0 μm.

Next, the aqueous dispersion was treated with a sand grinder (Igarashi Kikai Co., Ltd., MODEL NO, OSG-8G) under the condition of 2 kg per minute to prepare a developer dispersion having an average particle size of 2.7 μm. Thereafter, a color-developed paper for pressure-sensitive copying paper was obtained in the same manner as in Example 1.

Example 3 In Example 1, 3- (2-benzotriazolyl)
Developer as in Example 1 except that sodium 3-tert-butyl-4-hydroxy-5- (2-benzotriazolyl) phenylpropionate was used instead of zinc-4-hydroxyphenylacetate. An aqueous dispersion was prepared. The average particle diameter of the obtained developer-dispersed particles was 2.0 μm.

 Thereafter, in the same manner as in Example 1, a color-developed paper for pressure-sensitive copying paper was obtained.

Example 4 In Example 1, 3- (2-benzotriazolyl)
Instead of zinc 4-hydroxyphenylacetate,
(2-benzotriazolyl) -4-hydroxy-5-
A developer aqueous dispersion was prepared in the same manner as in Example 1 except that sodium (α, α-dimethylbenzyl) phenylbutyrate was used. The average particle diameter of the obtained developer dispersed particles is 2.
2μ.

 Thereafter, in the same manner as in Example 1, a color-developed paper for pressure-sensitive copying paper was obtained.

Example 5 In Example 2, instead of zinc 3-tert-butyl-4-hydroxy-5- (2-benzotriazolyl) benzoate, 3-tert-butyl-4-hydroxy-
A developer aqueous dispersion was prepared in the same manner as in Example 2 except that zinc 5- (2-benzotriazolyl) phenylpropionate was used. The average particle diameter of the obtained developer-dispersed particles was 2.0 μm.

 Thereafter, in the same manner as in Example 2, a color developing paper for pressure-sensitive copying paper was obtained.

Example 6 500 g of zinc 3-isododecylsalicylate was added to 400 g of toluene.
At 50 ° C. to prepare a toluene solution. To this toluene solution was added 3-octyl-4-hydroxy-5-
Zinc (2-benzotriazolyl) phenyl tridecanoate
Add 5 g and dissolve.

Separately, in a stainless steel beaker with an internal volume of 3,000 ml, water 600 g, sodium carbonate 2.5 g, a 25% aqueous solution of a copolymer of ethyl acrylate and alkylamide (copolymerization ratio: 13 to 87 mole percent, degree of polymerization: about 400) Add 100g, 35 ℃
Homomixer (Model M, manufactured by Tokushu Kika Kogyo Co., Ltd.) at a speed of 8800 to 9000 rpm
By performing the emulsification operation for 20 minutes, an oil-in-water emulsion is obtained. The mixture is transferred to a 10,000 ml hard glass three-necked flask equipped with a stirrer, a thermometer, and a distillation port. Further, 1000 g of water is added, and the flask is heated and boiled while slowly stirring the contents. When about 320 g of toluene and about 340 g of water are taken out from the distillation port, the content becomes an emulsion having a total solid content of 39% containing little toluene. The average particle diameter of the obtained developer-dispersed particles was 2.4 μm. The softening point of the dispersed phase was 63 ° C. Thereafter, a color-developed paper for pressure-sensitive copying paper was obtained in the same manner as in Example 1.

Comparative Example 1 In Example 1, 3- (2-benzotriazolyl)
Instead of zinc 4-hydroxyphenylacetate, an ultraviolet absorber, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole (trade name TINUVIN 32)
0, manufactured by CIBA-GEIGY), except that 20 g of a developer was prepared in the same manner as in Example 1.

The average particle size of the obtained developer-dispersed particles was 2.8 μm.

 Thereafter, in the same manner as in Example 1, a color-developed paper for pressure-sensitive copying paper was obtained.

Comparative Example 2 In Example 1, 3- (2-benzotriazolyl)
Instead of zinc 4-hydroxyphenylacetate, an ultraviolet absorber 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotrial (trade name TINUVI
Example 1 except that 20 g of N327, CIBA-GEIGY) was used.
A developer aqueous dispersion was prepared in the same manner as described above.

The average particle size of the obtained developer-dispersed particles was 2.5 μm.

 Thereafter, in the same manner as in Example 1, a color-developed paper for pressure-sensitive copying paper was obtained.

Comparative Example 3 In Example 1, 3- (2-benzotriazolyl)-
A developer aqueous dispersion was prepared in the same manner as in Example 1 except that zinc 4-hydroxyphenylacetate was not used.

The average particle diameter of the obtained developer-dispersed particles was 2.2 μm.

Thereafter, a color-developed paper for pressure-sensitive copying paper was obtained in the same manner as in Example 1.

Comparative Example 4 A developer aqueous dispersion was prepared in the same manner as in Example 2 except that zinc 3-tert-butyl-4-hydroxy-5- (2-benzotriazolyl) benzoate was not used. .

The average particle size of the obtained developer-dispersed particles was 2.5 μm.

Thereafter, a color-developed paper for pressure-sensitive copying paper was obtained in the same manner as in Example 2.

Comparative Example 5 In Example 1, 3- (2-benzotriazolyl)-
A color developing paper for pressure-sensitive copying paper was obtained in the same manner except that 2,2'-methylenebis (4-methyl-6-tert-butylphenol) was used in place of zinc 4-hydroxyphenylacetate.

The following quality evaluation tests were performed on the thus obtained color-developed paper for pressure-sensitive copying paper, and the results are shown in Table 1.

[Preparation of upper paper]

Crystal violet lactone is dissolved in alkylated naphthalene, and a capsule coating solution prepared by microencapsulating this oily liquid is coated on one side of high-quality paper with a dry weight of 4 g / m ^2.
And dried to obtain upper paper.

[Creating medium paper]

The same capsule coating liquid as that of the upper paper was applied to the base paper surface of the color-developed paper for pressure-sensitive copying paper so as to have a dry weight of 4 g / m ² and dried to obtain a middle paper.

Low-Temperature Color Development Test The developed paper and the upper paper were left in an atmosphere of 0 ° C. for 10 hours.
Next, the coated surfaces of the colored paper and the upper paper are opposed to each other, and the color is developed by a dropping type color tester (weight: 100 g, height: 10 cm) in an atmosphere of 0 ° C. Seconds later,
One day later, the color density was measured.

Light resistance test (color generation) microscopic colored paper and upper paper superposed so coated surfaces face each other, the color image is formed by applying a load of 100 kg / cm ^2, measured color density by a Macbeth color densitometer that the value was defined as D _0. Next, the the value of the color density was measured after addressed 6Hrs sunlight was D _1.

The light fastness (coloring part) is defined by the following formula, but the value is 100
The closer to, the better the light resistance.

Light Resistance Test superposed so that later on the paper addressed 6Hrs sunlight into (blank portion) developing colored paper is coated faces facing, to form a colored image under a load of 100 kg / cm ^2, Macbeth color densitometer in the value measured color density was D _3. Also, without applying the sunlight, the upper papers are overlapped so that the coated surfaces face each other, a color image is formed by applying a load of 100 kg / cm ² , the color density is measured with a Macbeth color densitometer, and the value is expressed as D. _{And 2} .

The light fastness (blank area) is defined by the following formula, but the value is 100
The closer to, the better the light resistance.

"Effects" As is clear from the results in Table 1, the pressure-sensitive copying paper of the present invention had excellent characteristics in both low-temperature coloring and light fastness.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toranosuke Saito, 1-10-24, Itokaichi, Ibaraki City, Osaka Prefecture Inside Sanko Development Research Institute Inc. (72) Inventor, Shigeru Oda 1-10-24, Itokaichi, Ibaraki City, Osaka Prefecture (In Japanese) JP-A-3-202384 (JP, A) JP-A-3-57690 (JP, A) JP-A-3-175083 (JP, A) JP 3-57687 (JP, A) JP-A-57-191087 (JP, A) JP-A-62-1216786 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) B41M 5/124 -5/165 B41M 5/28-5/34

Claims (3)

(57) [Claims] 1. A compound of the formula [I] [In the formula (I), R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group, a phenyl group, It is a phenyl group, an aralkyl group or a aralkyl group with a nucleus, and _two adjacent groups out of R ₁ , R ₂ , R ₃ and R ₄ may combine to form a ring. n is an integer,
M represents a polyvalent metal atom. And a developer having 0.05 to 20 parts by weight of the compound represented by the general formula [II] per 100 parts by weight of the developer. (In the formula (II), R ₅ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, a phenyl group, a nucleus-substituted phenyl group, an aralkyl group, or a nucleus-substituted aralkyl group. . A represents a monovalent metal atom or a polyvalent metal atom. However, nickel atoms are excluded. X is - (CH _{2) P} - or Wherein P is an integer of 0 or more, and R ₆ is a C ₁ -C ₃ alkyl group. m represents an integer. ] 2. A pressure-sensitive copying paper obtained by applying a coating solution containing the developer composition according to claim 1 to a support. 3. A compound of the general formula [I] [In the formula (I), R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group, a phenyl group, It is a phenyl group, an aralkyl group or a aralkyl group with a nucleus, and _two adjacent groups out of R ₁ , R ₂ , R ₃ and R ₄ may combine to form a ring. n is an integer,
M represents a polyvalent metal atom. And a developer having a core substituted salicylic acid salt as a main component, and dissolving 0.05 to 20 parts by weight of a compound represented by the general formula (II) per 100 parts by weight of the developer in an organic solvent. Of a developer composition dispersion obtained by emulsifying and dispersing the organic solvent in an aqueous medium with or without heating, and then heating the dispersion to remove the organic solvent by distillation. (In the formula (II), R ₅ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, a phenyl group, a nucleus-substituted phenyl group, an aralkyl group, or a nucleus-substituted aralkyl group. . A represents a monovalent metal atom or a polyvalent metal atom. However, nickel atoms are excluded. X is - (CH _{2) P} - or Wherein P is an integer of 0 or more, and R ₆ is a C ₁ -C ₃ alkyl group. m represents an integer. ]