JPH09202038A - Developing sheet for pressure sensitive copying paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developing sheet for pressure sensitive copying paper which provides an image having high resolution at the time of ink jet recording, has excellent waterproof property, does not generate bleeding and feathering, and has excellent coloring property and storage stability as a pressure sensitive copying paper. SOLUTION: In this developing sheet, a developer layer which contains a multivalent metallic salt of a nucleus substituted aromatic carboxylic acid derivative and a pigment is provided on a support body. In the developer layer, 3-20wt.% of diallyl amine-(meta)acrylamide copolymer or its salt based on the whole solid quantity of the multivalent metallic salt of the nucleus substituted aromatic carboxylic acid derivative and the pigment is added.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color-developing sheet for pressure-sensitive copying paper, which is suitable for ink jet recording, and in particular, an image at the time of ink jet recording has a high resolution and is excellent in water resistance and pressure-sensitive copying. The present invention relates to a color-developing sheet for pressure-sensitive copying paper which is excellent in color developability and storability as paper.

[0002]

2. Description of the Related Art A pressure-sensitive copying paper is prepared by applying a microcapsule composition containing microcapsules containing a hydrophobic core substance in which an electron-donating color former (leuco dye) is dissolved as a main component to one side of a support. The paper and the one side of the support were coated with a developer main component containing an electron-accepting developer as a main component, which was colored when contacted with the color former, and the other side was coated with a microcapsule composition. There are middle paper and lower paper in which the developer composition is applied on one side of the support, and these three types of sheets are combined as upper paper, lower paper or upper paper, middle paper, lower paper in this order as a copy set. It has been put to practical use. Also known as a form of pressure-sensitive copying paper is a self-coloring 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 recording with one sheet. Has been.

Conventionally, pressure-sensitive copying paper has been mainly used as slip (form) paper, and the slip format is often printed by letterpress printing or offset printing by a professional printer. However, in recent years, the demand for pressure-sensitive copying paper has been diversified, mainly for general slips, delivery slips, contract documents, etc., as the usage thereof has expanded. Recently, with the streamlining of paperwork, demand for computer output is increasing due to numbering of slips and printing of individual information.
There is an increasing number of use cases where an inkjet recording head connected to a computer is provided and recording is performed simultaneously with printing. Inkjet recording system uses high-speed printing, low noise,
It has features such as flexibility of recording patterns and easy multicolor printing.

However, when ink jet recording is performed using conventional pressure-sensitive copying paper, the resolution of the recorded image is low, causing bleeding and feathering. Further, the water resistance is not sufficient, and there is a problem that the image density is remarkably reduced due to water smearing and the recorded image is bleeded. In order to solve these problems, JP-A-3-236986 discloses that a developer-containing layer containing a developer and a pigment contains a cationic substance having a quaternary ammonium group or a tertiary amino group. However, these cationic substances decrease the color development of pressure-sensitive copying paper, and when stored under high humidity for a long time, the recorded image disappears or the white paper turns yellow. However, the current situation is that satisfactory results have not always been obtained.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems and relates to a color-developing sheet for pressure-sensitive copying paper having ink jet recording suitability, and in particular, an image at the time of ink jet recording has a high resolution, An object of the present invention is to provide a color-developing sheet for pressure-sensitive copying paper which is excellent in water resistance, has no bleeding and feathering, and is excellent in color development and storability as pressure-sensitive copying paper.

[0006]

The present invention provides a color-developing sheet for pressure-sensitive copying paper, which comprises applying a coating liquid containing a polyvalent metal salt of a nuclear-substituted aromatic carboxylic acid derivative and a pigment as main components. The coated layer contains the diallylamine- (meth) acrylamide copolymer or a salt thereof in an amount of 3 to 10% by weight based on the total weight of the polyvalent metal salt of the nuclear-substituted aromatic carboxylic acid derivative and the pigment. It is a color developing sheet for pressure copying paper.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, the present invention provides a developer layer containing a polyvalent metal salt of such a nuclear-substituted aromatic carboxylic acid derivative, which contains a specific copolymer or a specific amount of the salt. is there. In the present invention, by using a polyvalent metal salt of a nuclear-substituted aromatic carboxylic acid derivative as a color developer, a color-developing sheet for pressure-sensitive copying paper excellent in color developability can be obtained, and a nuclear-substituted aromatic group in the color-developing layer. Incorporation of 3 to 10% by weight of diallylamine- (meth) acrylamide copolymer or a salt thereof with respect to the total weight of the polyvalent metal salt of the carboxylic acid derivative and the pigment improves ink jet recording suitability. By the way,
If the amount added is less than 3% by weight, the desired effect of improving the ink jet recording suitability cannot be obtained. If the amount added exceeds 10% by weight, the viscosity of the coating solution is drastically increased and the preservability of the pressure-sensitive copy recorded image is deteriorated. Therefore, the addition amount of the diallylamine- (meth) acrylamide copolymer or its salt is adjusted within the above range.

The diallylamine- (meth) acrylamide copolymers or salts thereof used in the present invention are disclosed in JP-A-6-61.
No. 4-77572, a copolymer of diallylamine with (meth) acrylamide and another vinyl-based monomer copolymerizable with them, which does not substantially contain a carboxyl group, or a copolymer thereof. It is salt. It should be noted that a pigment is usually added to the color developing layer in an amount of 50 to 95% by weight of the total solid content of the color developing layer, 1 to 20% by weight of an organic color developer, and 1 to 40% by weight of a binder.

Examples of the color developer used in the present invention include salicylic acid, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid, and 3-tert-butyl-5-.
Methylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3-methyl-5-benzylsalicylic acid, 3-phenyl-5- (α, α-dimethylbenzyl) salicylic acid, 3-cyclohexyl-5- (α, α- Dimethylbenzyl) salicylic acid, 3- (α, α-dimethylbenzyl)
-5-methylsalicylic acid, 3,5-di-cyclohexylsalicylic acid, 3,5-di- (α-methylbenzyl) salicylic acid, 3,5-di- (α, α-dimethylbenzyl) salicylic acid, 3- (α- Methylbenzyl) -5- (α, α
-Dimethylbenzyl) salicylic acid, 4-methyl-5-cyclohexylsalicylic acid, 2-hydroxy-1-benzyl-3-naphthoic acid, 1-benzoyl-2-hydroxy-3-naphthoic acid, 3-hydroxy-5-cyclohexyl-2 -Naphthoic acid, 2-hydroxy-4-[(4-carboxy-5-hydroxy) phenyl] -1-naphthoic acid, 3-methyl-5- (iso) nonylsalicylic acid, 3-
Methyl-5- (iso) dodecylsalicylic acid, 3-methyl-5- (iso) pentadecylsalicylic acid, 3-methyl-
5- (α-methylbenzyl) salicylic acid, 3-methyl-
5- (α, α-dimethylbenzyl) salicylic acid, 3,5
-Di-sec-butylsalicylic acid, 3,5-di-ter
t-Butyl-6-methylsalicylic acid, 3-tert-butyl-5-phenylsalicylic acid, 3,5-di-tert.
-Amylsalicylic acid, 3-cyclotoxyl-5- (iso) nonylsalicylic acid, 3-phenyl-5- (iso) nonylsalicylic acid, 3- (α-methylbenzyl) -5-
(Iso) nonylsalicylic acid, 3-isopropyl-5
(Iso) nonylsalicylic acid, 3- (iso) nonylsalicylic acid, 3- (iso) nonyl-5-methylsalicylic acid, 3
-(Iso) nonyl-5-cyclohexyl salicylic acid, 3
-(Iso) nonyl-5-phenylsalicylic acid, 3- (iso) nonyl-5- (α-methylbenzyl) salicylic acid,
3- (iso) nonyl-5- (4, α-dimethylbenzyl) salicylic acid, 3- (iso) nonyl-5- (α, α-
Dimethyldonzyl) salicylic acid, 3- (α, α-dimethylbenzyl) -5- (iso) nonylsalicylic acid, 5-
(Iso) nonylsalicylic acid, 3- (iso) nonyl-6-
Methylsalicylic acid, 3-tert-butyl-5- (iso) nonylsalicylic acid, 3,5-di (iso) nonylsalicylic acid, 3- (iso) dodecylsalicylic acid, 3- (iso) dodecyl-5-methylsalicylic acid, 3- (Iso) dodecyl-6-methylsalicylic acid, 3-isopropyl-5
-(Iso) dodecylsalicylic acid, 3- (iso) dodecyl-5-ethylsalicylic acid, 5- (iso) dodecylsalicylic acid, 3- (iso) pentadecylsalicylic acid, 3- (iso) pentadecyl-5-methylsalicylic acid, 3- (Iso) pentadecyl-6-methylsalicylic acid, 5- (iso) pentadecylsalicylic acid, 3-cyclohexyl-5
-(Α-methylbenzyl) salicylic acid, 3-phenyl-
5- (α-methylbenzyl) 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- (α-methylbenzyl) -5-bromosalicylic acid, 3- (α, 4-dimethylbenzyl) -5-methylsalicylic acid, 3,5-di (α, 4-dimethylbenzyl) salicylic 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, 2-hydroxy-3- (α,
Examples thereof include aromatic carboxylic acids such as α-dimethylbenzyl) -1-naphthoic acid or 3-hydroxy-7- (α, α-dimethylbenzyl) -2-naphthoic acid and polyvalent metal salts thereof. Specific examples of polyvalent metals include magnesium, calcium, zinc, aluminum, iron, cobalt,
Nickel etc. are mentioned. These may be used alone or as a mixture.

The term "(iso) alkyl" means isoalkyl or normal alkyl. Further, the isononyl group, the isododecyl group and the isopentadecyl group are defined as substituents formed by addition of propylene trimer, propylene tetramer or 1-butene trimer and propylene pentamer, respectively.

In addition to calcium carbonate, examples of the pigment include zinc oxide, magnesium oxide, titanium dioxide, aluminum hydroxide, kaolin, clay, calcined kaolin, delaminated kaolin, structured kaolin, magnesium sulfate, calcium sulfate and the like. Inorganic pigments and organic pigments (plastic pigments) such as polystyrene resin fine particles, urea formalin resin fine particles, and minute hollow particles are appropriately used within a range that does not impair the effects of the present invention.

As the binder, for example, starch, casein, gum arabic, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, styrene / butadiene copolymer latex, vinyl acetate latex and the like are blended.

The method for preparing the coating liquid for forming the color developing sheet is not particularly limited and may be appropriately prepared. For example, a method of coating a support with a coating liquid obtained by mechanically dispersing an organic developer together with an inorganic pigment, a binder, a dispersant and other additives in water. Further, the developer is dissolved in an organic solvent and emulsified in water, the organic solvent is distilled off by a method such as steam distillation, and then an inorganic pigment, a binder, and a coating liquid obtained by adding other additives to the support. How to apply. Alternatively, a method of applying a coating liquid obtained by mixing the both to a support is used.

As the organic solvent used for emulsifying and dispersing the developer, halogenated hydrocarbons having a boiling point of 200 ° C. or less, aromatic hydrocarbons, esters, ketones, ethers, amides and nitriles are preferable. Among these, those having a solubility in water at room temperature of 5 or less are more preferable. Specific examples of the organic solvent include chloroform, methylchloroform, benzene, toluene, xylene, chlorobenzene,
Examples thereof include ethyl acetate, butyl acetate, isopropyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and dimethylacetamide.

The water-soluble polymer used for emulsification includes polyvinyl alcohol, maleic anhydride-isobutylene copolymer, carboxymethyl cellulose, hydroxyethyl cellulose, polyacrylamide, polyacrylic acid, acrylamide-alkyl acrylate copolymer, ether. Examples thereof include synthetic or natural polymers such as modified polyvinyl alcohol, polyvinylpyrrolidone, starch, casein, gum arabic and gelatin.

In the present invention, the method for preparing the coating liquid for the color developing layer is not particularly limited. Furthermore, various auxiliary agents such as a water-proofing agent, a curing agent, a cross-linking agent, an antifoaming agent, a coloring agent, a wetting agent, a flow modifier and an antiseptic agent are appropriately added to the coating liquid for the color developing layer. It

The developer for the color developing sheet thus prepared is
Usual coating of air knife coater, blade coater, rod blade coater, roll coater, bar coater, size press coater, bill blade coater, curtain coater, short dwell coater, bar coater, etc. on a support such as paper, synthetic paper, film, etc. It is applied by the device and finished as a color-developing sheet for pressure-sensitive copying paper.

The coating amount on the support is not particularly limited, but it is 3 to 10 g / m ^{2 on} a dry basis, preferably 4 to 7 g / m ² .
m ² . The color-developing sheet for pressure-sensitive copying paper thus obtained can be passed through an on or off super calender, a soft nip calender or the like for pressure smoothing finish.

[0019]

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

The diallylamine- (meth) acrylamide copolymer hydrochloride used in the examples is described in JP-A-64-7.
What was synthesize | combined according to the reference example-2 of the Example of 7572 gazette was used. Example 1 [Preparation of liquid for developing layer development] 10 parts of zinc salt of 3,5-di (α-methylbenzyl) salicylic acid was added to 10 parts of toluene to give 70 parts.
The toluene solution was dissolved at 0 ° C and emulsified in 30 parts of water containing 0.6 parts of polyvinyl alcohol having a degree of polymerization of 1700 and a saponification degree of 98% using a homomixer, and then toluene was distilled by steam to distill off and reveal. An aqueous dispersion of colorant particles was obtained. Add light calcium carbonate (Tamapearl TP-1
21; Okutama Kogyo Co., Ltd.) 90 parts, 20 parts of 25% aqueous solution of oxidatively modified starch, 16 parts of styrene-butadiene copolymer latex in solid form, and 5 parts of diallylamine-acrylamide copolymer hydrochloride in solid form. After that, the solid content concentration was adjusted to 30% to prepare a coating liquid for the color developing layer.

[Production of color developing sheet for pressure-sensitive copying paper] Basis weight 4
On the surface of the base paper of 0 g / m ^2, the coating solution for the color developing layer was applied by an air knife coater so that the dry coating amount was 6 g / m ² , and dried to obtain a color developing sheet for pressure-sensitive copying paper.

Example 2 A color developing sheet for pressure-sensitive copying paper was obtained in the same manner as in Example 1 except that 3 parts of solid diallylamine-acrylamide copolymer hydrochloride was added.

Example 3 A color developing sheet for pressure-sensitive copying paper was obtained in the same manner as in Example 1 except that 10 parts of solid diallylamine-acrylamide copolymer hydrochloride was added.

Comparative Example 1 A color developing sheet for pressure-sensitive copying paper was obtained in the same manner as in Example 1 without adding the diallylamine-acrylamide copolymer hydrochloride.

Comparative Example 2 A color developing sheet for pressure-sensitive copying paper was obtained in the same manner as in Example 1 except that 1 part of solid diallylamine-acrylamide copolymer hydrochloride was added.

Comparative Example 3 A color developing sheet for pressure-sensitive copying paper was obtained in the same manner as in Example 1 except that 15 parts of solid diallylamine-acrylamide copolymer hydrochloride was added.

[Performance Comparison Test] Six types of color developing sheets for pressure-sensitive copying paper obtained as described above were subjected to an evaluation test by the following method, and the results are shown in Table 1.

(1) Color development by pressure-sensitive copying A color development sheet and a commercially available top paper (KS copy bright / blue color development, N-40 / Shin-Oji Paper Co., Ltd.) are overlapped so that the coated surfaces face each other, and a line is formed. The paper was passed through a super calendar set to a pressure of 10 kg / cm for color development, and after 1 hour, the color density was measured with a Macbeth densitometer RD-941.

(2) Preservability A color developing sheet and a commercially available top paper (KS copy bright / blue coloring, N-40 / Shin Oji Paper Co., Ltd.) are laminated so that the coated surfaces face each other, and the linear pressure is 10 kg. Paper is passed through a super calendar set to / cm to develop color, 40 ° C, 90%
The color density was measured by a Macbeth densitometer RD-941 after being stored in a thermo-hygrostat of RH for 72 hours.

(3) Inkjet recording suitability: Inkjet recording was performed with an inkjet printer, and the degree of sharpness (feathering) of the image was sensory evaluated according to the following evaluation criteria. “Evaluation criteria” ○: Feathering is almost nonexistent. B: Feathering is recognized and there is a practical problem. X: Feathering is remarkable.

(4) Evaluation of Water Resistance of Inkjet Recorded Image Inkjet recording was carried out with an inkjet printer, the recorded image was immersed in water for 10 minutes, and the degree of bleeding of the recorded image was evaluated organoleptically based on the following evaluation criteria. “Evaluation criteria” ○: Almost no bleeding. B: Bleeding is recognized and there is a practical problem. X: Remarkably blurred.

[0032]

[Table 1]

[0033]

As is apparent from Table 1, the color-developing sheets for pressure-sensitive copying paper obtained in the examples of the present invention have a high resolution image at the time of ink jet recording, excellent water resistance, and It was a color-developing sheet for pressure-sensitive copying paper which was excellent in color development and storability as pressure-sensitive copying paper.

Claims (1)

[Claims] 1. A color-developing sheet for pressure-sensitive copying paper in which a color-developing layer containing a polyvalent metal salt of a nuclear-substituted aromatic carboxylic acid derivative and a pigment is provided on a support, wherein the color-developing layer contains diallylamine-.
A pressure-sensitive copying paper, characterized in that a (meth) acrylamide copolymer or a salt thereof is contained in an amount of 3 to 10% by weight based on the total solid amount of the polyvalent metal salt of the nuclear-substituted aromatic carboxylic acid derivative and the pigment. Developer sheet.