JPS6139915B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a pressure-sensitive recording paper and a method for manufacturing the same. In more detail, colorless dye precursor and its solvent, oil absorption 50 according to JIS K-5101 method.
ml/100g or more of organic or/and inorganic powder and higher fatty acid amide or a combination of higher fatty acid amide and other waxes applied to a support and pressure-sensitive recording paper, and its manufacturing method. It is.

The pressure-sensitive recording paper of the present invention is a sheet coated with an electron-accepting substance (such as clays, phenols, organic carboxylic acids, etc.) that undergoes a color reaction with a colorless dye precursor (electron-donating substance). They are used in combination.

Conventionally, as an example of using a colorless dye precursor, the colorless dye precursor is used as an electron donating substance, and the electron accepting substance is combined with a color developer such as clay, phenols, or organic carboxylic acids. A colorless dye precursor is dissolved in a solvent, microencapsulated, and coated on a support, and the other color developer is coated on another support or the same support in two layers, and both are used in isolation. There is pressure-sensitive recording paper. However, microencapsulating a solvent in which a colorless dye precursor is dissolved as an internal phase oil requires a complicated microencapsulation process using many types of materials, and is also expensive. There are always many points that are unsatisfactory from an economic standpoint. Furthermore, many applications have been filed and used for transfer type recording papers that do not undergo the microencapsulation process. For example, JP-A-54-74111 discloses a pressure-sensitive copying material coated with a coating substance consisting of a wax or wax mixture that dissolves a colorless dye precursor and an oily and/or fatty substance as a fluidizing agent. The manufacturing method is described. However, this method has the disadvantage that the fluidizing agent oozes out over time because the fluidizing agent is in a liquid state and is mixed in the coating material in a free liquid state. Furthermore, JP-A-51-77410 relates to a master sheet used as a dry multi-sheet copying material, and is composed of a porous filler and a binder. There is a description of a copying material impregnated with a filler and provided as an intermediate layer between a flexible base material and a protective overcoat layer. However, in this case, the porous filler is coated between the flexible base material and the top coat layer, and the top coat layer protects the liquid medium from seeping out from the intermediate layer. Since synthetic wax is used, the manufacturing process is complicated as it involves a double coating process.

As a result of intensive research into the above-mentioned drawbacks, the present inventors have completed a pressure-sensitive recording paper manufactured without the conventional microencapsulation process.

The above object of the present invention is to produce a colorless dye precursor, a non-volatile solvent, and an oil absorption amount of 50ml/100 according to JIS K-5101 method.
The present invention provides a pressure-sensitive recording paper in which a support is coated with an organic or/or inorganic powder having a weight of at least 100 g, and a higher fatty acid amide or a combination of the higher fatty acid amide and another wax.

Furthermore, the above object of the present invention is to dissolve a colorless dye precursor in a non-volatile solvent and absorb it into an organic or/and inorganic powder having an oil absorption of 50 ml/100 g or more according to the JIS K-5101 method. A product achieved by mixing and dispersing amides or higher fatty acid amides in combination with other waxes and coating the mixture on a support as an aqueous coating liquid or a solution by melting with heat. It is.

The feature of the present invention is that a solution of a colorless dye precursor dissolved in a nonvolatile solvent (hereinafter abbreviated as dye solution)
It has the effect of desensitizing the color development that occurs when organic and/or inorganic powder is oil-absorbed and impregnated with higher fatty acid amides, and in addition, it has the same peeling or transfer effect as other waxes. It is to hold it.

Further, the present invention is characterized in that the combination of higher fatty acid amides or higher fatty acid amides and other waxes is transferred to the corresponding electron-accepting coated paper together with the oil-absorbing powder impregnated with the dye solution, and the paint solution is simultaneously applied. It has the effect of exuding water.

Furthermore, another feature of the present invention is that the oil-absorbing powder impregnated with the dye solution is used in combination with higher fatty acid amides or higher fatty acid amides and other waxes to form an aqueous dispersion coating liquid or by thermally melting the oil-absorbing powder. It is an object of the present invention to provide a pressure-sensitive recording paper that can be produced by any method of preparing a molten ink composition.

Next, the components used in the present invention will be specifically listed, but the components are not limited thereto.

Urea-formaldehyde resin can be cited as an organic powder having an oil absorption of 50 ml/100 g or more. This corresponds to an oil absorption amount of 370 ml/100 g according to the JIS K-5101 method, such as PERGOPAK-M sold by Ciba Geigy in Switzerland.

Inorganic powders with oil absorption of 50ml/100g or more include active clays such as montmorillonite, bentonite, and kaolin, various calcined kaolins made from calcined kaolin minerals, silicic acids with a weight ratio of SiO ₂ of 80% or more,
Examples include aluminum oxides containing 80% or more of A ₂ O ₃ by weight, and light calcium carbonate.

Higher fatty acid amides include behenic acid amide, oxystearic acid amide, stearic acid amide, palmitic acid amide, oleic acid amide, ricinoleic acid amide, erucic acid amide, lauric acid amide, methylolated fatty acid amide, ethylene bisstearic acid amide, ethylene Examples include bisoleic acid amide.

Examples of waxes include animal waxes such as beeswax and serrata wax, vegetable waxes such as carnauba wax, petroleum waxes such as paraffin wax and microcrystalline wax, and synthetic waxes such as higher alcohols, synthetic paraffin, and chlorinated paraffin. .

As colorless dye precursors, crystal violet lactone, malachide green lactone,
3.3-bis(paradimethylaminophenyl)-6
-Aminophthalide, 3.3-bis(paradimethylaminophenyl)-6-paratoluenesulfonamide, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-7-(N-
methylanilino)fluorane, 3-diethylamino-7(N-methylparatoluidino)fluorane, 3-dimethylamino-6-methoxyfluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-6-methyl-7 -phenylaminofluorane, 3-diethylamino-7
-Phenylfluorane, 3-morpholino-5.6
-Benzofluorane, 6'-chloro-8'-methoxy-indolino-benzospiropyran, benzo-β
-naphthospiropyran, 3-methyl-di-β-naphthospiropyran, etc.

Nonvolatile solvents include alkylnaphthalenes, diallylalkanes, alkylbiphenyls, hydrogenated terphenyls, phenylene oxides, triallyl-dimethanes, phenylene oxides, alkylbenzenes, benzylnaphthalenes, diallylalkylenes, and allyl indans. Examples include synthetic oils, mineral oils, fish oils, vegetable oils, and whale oils.

Next, the blending ratio of the components of the coating liquid of the present invention will be mentioned. The colorless dye precursor depends on the coloring density, and the lower limit of the allowable range is a problem, but it is preferably 1 to 5% by weight. The amount of nonvolatile solvent is sufficient to dissolve the colorless dye precursor, and if the amount is large, it will ooze from the coating layer of the support to the corresponding electron-accepting coated sheet, causing contamination. 10-30% by weight is preferred. Organic powders with an oil absorption of 50 ml/100 g or more have the ability to absorb and impregnate the dye solution mentioned above, but organic powders with an oil absorption of 370 ml/100 g or more, such as urea-formaldehyde resin (Pergo Pack M), have an oil absorption of more than three times as much. The tolerance range of this organic powder is 3~
20% by weight is preferred. Furthermore, inorganic powders with oil absorption of 50ml/100g or more can be used in combination with organic powders or alone, and the permissible range is 10 to 40% by weight.
is preferred.

The higher fatty acid amide is preferably used in an amount of 10 to 50% by weight, since it desensitizes the coloring of organic and inorganic powder impregnated with a dye solution and sufficiently satisfies peeling after coating. In addition, other waxes can sufficiently exhibit exfoliating effects and are used in combination with the above-mentioned higher fatty acid amides, with a blending ratio of 10 to 25%.
Weight percent is preferred.

The support may be paper, synthetic paper, or paper pre-coated with a protective agent such as starch particles or fine cellulose powder.

In addition, fillers, film forming agents, emulsifiers, lubricants,
By appropriately mixing melting point depressants, antioxidants, ultraviolet absorbers, image stabilizers, etc., various manufacturing characteristics can be improved.

Regarding the case of coating the support, it is possible to coat the entire surface of the support by various coating methods such as air knife coating, blade coating, and gravure coating, or it is possible to coat only the necessary parts of the support. A so-called spot printing method may also be used.

Hereinafter, the present invention will be described in detail according to examples, but the examples are given merely to explain the present invention, and the present invention is not limited to these examples.

Example 1 A dye solution prepared by dissolving 10 parts of crystal violet lactone in 90 parts of diallylethane oil (trade name: Hysol SAS manufactured by Nisseki Chemical Co., Ltd.) at 70°C was mixed with urea-formaldehyde resin (trade name: Pergopack M manufactured by Ciba-Geigy). ) and stirred well until uniformly impregnated with the dye solution. continue
50 parts of light calcium carbonate (trade name: Softon)
2200 (manufactured by Shiraishi Calcium)) to completely absorb the free dye solution. At this time, it took on a pale blue color. 100 milled separately in a ball mill for 72 hours
30% stearamide with a melting point of ~105℃ (trade name Stearamide S, manufactured by Kao Soap)
270 parts were mixed into the urea-formaldehyde resin and light calcium carbonate previously impregnated with the dye solution. The mixed powder, which had a pale blue color, disappeared by mixing with stearamide and became a pure white aqueous dispersion. Here, 15 parts of wheat starch was mixed as a filler to prevent contamination, and 60 parts of 25% styrene-maleic anhydride copolymer (trade name: Maron MS-25, manufactured by Daido Kogyo) were mixed as a binder.
445 parts of water was added to form a 30% aqueous coating solution. This coating liquid was applied to a 40 g/m ² base paper using a Mayer bar in a coating amount of 6 g/m ² . When the resulting coated paper was overlaid with a coated sheet for existing pressure-sensitive recording paper containing p-phenylphenol resin as a color developer and printed under pressure, a clear blue colored image was formed.

Example 2 25 parts of urea-formaldehyde resin (trade name: Pergopack M, manufactured by Ciba Geigy) was mixed with 90 parts of diisopropylnaphthalene (trade name: KMC Oil, manufactured by Kureha Chemical) and 3-diethylamino-6-methyl.
10 parts of 7-phenylaminofluorane was mixed into the dye solution dissolved at 70°C and stirred thoroughly until the dye solution was uniformly impregnated. Subsequently, 65 parts of light calcium carbonate (trade name: Softon 2200, manufactured by Shiraishi Calcium) was mixed, and the free dye solution was completely absorbed by the light calcium carbonate. At this point, it had a pale reddish black color.

100-105 that has been pre-pulverized in a ball mill for 72 hours
300 parts of an aqueous dispersion of 30% stearamide (trade name: Stearamide S, manufactured by Kao Soap) having a melting point of .degree. C. was added to the above mixture and stirred well. The mixture, which had a pale black color, turned into a pure white aqueous dispersion by mixing stearamide. Here, 10 parts of kaolin and 25% styrene-maleic anhydride copolymer (trade name: Maron MS) are used as fillers.
-25, manufactured by Daido Kogyo) 80 parts of binder are mixed,
453 parts of water was added to make a 30% aqueous coating solution. This coating liquid was coated on a 50 g/m ² base paper using a Meyer bar in a coating amount of 7 g/m ² . When the prepared coated paper was overlaid with a coated sheet that acts as a color developer for 3.5 tert butylsalicylate zinc for existing pressure-sensitive recording paper and printed under pressure, a clear black colored image was obtained. .

Example 3 40 parts of urea-formaldehyde resin is mixed into a dye solution prepared by dissolving 10 parts of crystal violet lactone in 90 parts of diallylethane oil at 70°C and thoroughly stirred to uniformly impregnate the dye solution. It continued until. Subsequently, 30 parts of calcined kaolin (trade name: Ancilex, manufactured by ENGELHARD) was mixed, and the free dye solution was completely absorbed by the calcined kaolin.
At this time, the mixture took on a pale blue color. 30% with a melting point of 80°C, previously milled in a ball mill for 50 hours
250 parts of an aqueous dispersion of lauric acid amide (trade name: Diamond Y, manufactured by Nippon Kasei) was added to the above mixture and stirred well. The mixture, which had a pale blue color, turned into a white aqueous dispersion by mixing lauric acid amide. Furthermore, 60 parts of 25% styrene-maleic anhydride copolymer was added as a binder, and 650 parts of water was added.
30% aqueous coating solution was prepared. This was coated on a 50 g/m ² base paper using a Mayer bar to give a coating weight of 7 g/m ² . When the prepared coated paper was layered with a p-phenyl-phenol resin developer sheet and type-pressed, a clear blue colored image was obtained.

Example 4 30 parts of urea-formaldehyde resin was mixed into a dye solution prepared by dissolving 10 parts of crystal violet lactone in 90 parts of diallylethane oil at 70°C, and stirred thoroughly until the dye solution was evenly impregnated. continued. Subsequently, 50 parts of light calcium carbonate (trade name: Softon 2200, manufactured by Shiraishi Calcium) was mixed to completely absorb the free dye solution. At this time, the mixture took on a pale blue color. Next, use a ball mill in advance
180 parts of an aqueous dispersion of 30% lauric acid amide (product name: Diamond Y, manufactured by Nippon Kasei) having a melting point of 80°C and pulverized for 50 hours and 100 parts of 30% chlorinated paraffin (product name: Empara 70, manufactured by Ajinomoto Co., Ltd.) Mixed. The mixture turned from pale blue to white. Furthermore, 60 parts of 25% styrene-maleic anhydride copolymer was added as a binder, and 545 parts of water was added to prepare a 30% aqueous coating solution. Apply this to 40g/ ^m2 base paper with a coating amount of 7
It was coated using a Mayer bar so that it had a coating weight of g/m ² . When the prepared coated paper was layered with a developer sheet of p-phenyl-phenol resin and type-pressed, a clear colored image was obtained.

Example 5 Urea-formaldehyde resin was mixed with crystal violet in 95 parts of diisopropylnaphthalene.
10 parts of lactone was mixed into the dye solution dissolved at 70° C. and stirred thoroughly until uniformly impregnated with the dye solution. Next, use oleic acid amide (trade name Fatty Acid Amide 0, manufactured by Kao Soap), which has a melting point of 85°C.
70 parts of beeswax and 30 parts of beeswax were melted at 90°C, and the above mixture was added thereto and homogenized. The prepared coating melt was coated on base paper of 40 g/m ² in an amount of 6 g/m ² by the hot melt coating method. When this coated paper was layered with a color developer sheet of p-phenylphenol resin and pressure was applied from above, the coated layer was peeled off and transferred to obtain a blue colored image.

Claims (1)

[Claims] 1. Colorless dye precursor, non-volatile solvent, JISK
- Pressure-sensitive recording paper made by coating a support with an organic or/and inorganic powder with an oil absorption of 50 ml/100 g or more according to the 5101 method, and a combination of higher fatty acid amides or higher fatty acid amides and other waxes. . 2. The pressure-sensitive recording paper according to claim 1, wherein the organic powder having an oil absorption of 50 ml/100 g or more is a urea-formaldehyde resin. 3. The pressure-sensitive recording paper according to claim 1, wherein the inorganic powder having an oil absorption of 50 ml/100 g or more is selected from the group of activated clays, calcined kaolins, silicic acids, aluminum oxides, and calcium carbonate. . 4. The higher fatty acid amide is selected from the group of behenic acid amide, oxystearic acid amide, palmitic acid amide, oleic acid amide, stearic acid amide, methylolated fatty acid amide, ethylene bis fatty acid amide, methylene bis fatty acid amide, and lauric acid amide. A pressure-sensitive recording paper according to claim 1. 5. The pressure-sensitive recording paper according to claim 1, wherein the wax is selected from the group of animal waxes, vegetable waxes, petroleum waxes, and synthetic waxes. 6. The colorless dye precursor is selected from the group of triphenylmethane phthalide series, fluorane series, phenothiazine series, indolylphthalide series, ryukoauramine series, spiropyran series, triphenylmethane series and rhodamine lactam series. A pressure-sensitive recording paper according to claim 1. 7. The pressure-sensitive recording paper according to claim 1, wherein the nonvolatile solvent is selected from vegetable oils, animal oils, mineral oils, and synthetic oils such as alkylnaphthalene-based and diallylalkane-based oils. 8 Dissolve the colorless dye precursor in a non-volatile solvent and adjust the oil absorption amount to 50ml/100 according to the JIS K-5101 method.
The oil is absorbed into an organic or/and inorganic powder having a weight of more than A method for producing pressure-sensitive recording paper that is coated on a support as a liquid.