JP2825942B2 - Manufacturing method of pressure-sensitive copying paper - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for producing pressure-sensitive copying paper using microcapsule ink, and particularly to a method for drying a pressure-sensitive copying paper having good performance into a relatively small drying apparatus. The present invention relates to a method of easily manufacturing using the method.

(Prior Art) A combination of an electron-donating color developing agent such as crystal violet lactone and benzoyl leucomethylene blue and an electron-accepting developer such as activated clay, phenol-formaldehyde condensate, and a polyvalent metal salt of an aromatic carboxylic acid. Various chromogens, such as a combination or a combination of a metal salt such as a nickel carboxylate and N, N-di-benzyl-di-thio-oxamide, an organic iron phosphate and lauryl gallate, and a ligand compound. 2. Description of the Related Art Pressure-sensitive copying paper utilizing the principle of developing color by the reaction of a substance is well known.

In general, such a pressure-sensitive copying paper is prepared by coating a microcapsule containing a chromogenic substance prepared by a method such as a phase separation method, an interfacial polymerization method or an in-situ method on a support, and forming an upper paper (CB); Lower paper (CF) coated with another chromogenic substance that reacts with the body substance to form a color, and medium paper (CFB) coated with the microcapsules and the chromogenic substance on separate surfaces of the support Are appropriately combined for practical use.

In addition, there is also a so-called simple pressure-sensitive copying paper in which the microcapsules and the chromogenic substance are coated on the same surface of the support as a laminated or mixed layer, and a capsule layer is further provided on the back surface of the single pressure-sensitive copying paper. And a single pressure-sensitive copying paper set in which the lower paper and the middle paper are appropriately combined.

Usually, these pressure-sensitive copying papers are produced by applying a water-based paint to a support with a large coating machine.
As a special manufacturing method, there is a method in which capsules are made into ink and spot printed by a printing machine.

In the case of spot printing of capsule ink, expensive capsule paint can be printed only on the required portion of the support, so that, for example, the color tone is partially compared with the method of applying the water-based paint to the entire support with a large coating machine. This makes it easy to obtain copy paper of different types, and exhibits extremely economical characteristics depending on the target variety. However, although the printing method has a great merit as compared with the method using a coating machine, there is a point that it is still not enough depending on the method.

For example, in order to obtain a pressure-sensitive copying paper having good coloring by applying the capsule ink to the support, it is necessary to increase the coating amount as much as possible. Then, a large-sized drying apparatus for evaporating a large amount of solvent is required. Further, when the solvent used is particularly alcohol, there is a disadvantage that paper is easily wrinkled. On the other hand, when using the ultraviolet curing type capsule ink, it can be manufactured with a small drying device as compared with the case of using the evaporation drying type ink, but the resin ratio is lower than that of the evaporation drying type ink. Because of this, the printed portion is likely to be transparent, and the capsule is less likely to be pressure-ruptured due to the effect of the resin, so that the color development tends to be inferior.

In addition, the inventors of the present invention use a microcapsule containing a chromogenic substance, an alcohol-based volatile organic solvent, an ultraviolet curable compound, and a capsule ink containing a photopolymerization initiator as a basic component, thereby improving color development. It has been found that pressure-sensitive copying paper having good opacity of a printed portion and having no wrinkles can be obtained by using a relatively small drying device (Japanese Patent Application No. 1-279301). However, this method cannot be said to be sufficient depending on the conditions.For example, when printing at high speed, the polymerization of the ultraviolet curable substance is likely to be insufficient, and the strength of the formed film is reduced. The fixing to the support becomes insufficient, and the obtained pressure-sensitive copying paper has a disadvantage that it is easily stained by friction.

(Problems to be Solved by the Invention) An object of the present invention is to solve the above-mentioned drawbacks when producing pressure-sensitive copying paper using capsule ink, and to provide a more practical pressure-sensitive copying paper. To provide a method of manufacturing.

(Means for Solving the Problems) The present invention provides (a) a microcapsule containing a chromogenic substance, (b) a volatile organic solvent, (c) an adhesive, (d) an ultraviolet curable compound, and e) A method for producing pressure-sensitive copying paper, characterized by printing a capsule ink containing a photopolymerization initiator as a basic component on a support and curing the ink.

(Action) The present inventors compensated for the decrease in film strength caused by insufficient polymerization of the ultraviolet-curable compound in the ink in high-speed printing by adding an adhesive to the ink, whereby The inventors have found that the friction resistance of pressure-sensitive copying paper is improved, and have completed the present invention.

Examples of the chromogenic substance used in the present invention include a combination of an electron-donating color former and an electron-accepting developer or a combination of a metal salt and a ligand compound.

Examples of the electron-donating color former include the following substances which are known in the field of pressure-sensitive copying paper.

3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethylindol-3-yl)
Phthalide, 3,3-bis (1,2-dimethylindole-3-
Yl) -5-dimethylaminophthalide, 3,3-bis (9
-Ethylcarbazol-3-yl) -6-dimethylaminophthalide and other triallylmethane dyes, 4,4'-bis-dimethylaminobenzhydryl benzyl ether, N
Diphenylmethane dyes such as -halophenyl-leuco auramine, N-2,4,5-trichlorophenyl leuco auramine, thiazine dyes such as benzoyl leucomethylene blue and p-nitrobenzoyl leucomethylene blue;
3-methyl-spiro-dinaphthopyran, 3-phenyl-
Spiro dyes such as spiro-dinaphthopyran and 3-propyl-spiro-dibenzopyran; lactam dyes such as rhodamine-B-anilinolactam, rhodamine (o-chloroanilino) lactam and rhodamine (o-chloroanilyl) lactam; 3-dimethyl Amino-7-methoxyfluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3- (N-ethyl-p-toluidino) -7
-Methylfluoran, 3-diethylamino-7-N-methylaminofluoran, 3-diethylamino-7-dibenzylaminofluoran, 3- (N-ethyl-p-toluidino) -6-methyl-7-phenylamino Fluoran, 3-diethylamino-6-methyl-7-phenylaminofluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-phenylaminofluoran, 3-piperidino-methyl-7- Fluoran dyes such as phenylaminofluoran and 3-diethylamino-6-methyl-7-xylidinofluoran; 3,3-bis [2
-(P-dimethylaminophenyl) -2- (p-methoxyphenyl) ethylene-2-yl] -4,5,6,7-tetrachlorophthalide and the like, and a mixture thereof.

Examples of the electron-accepting developer include the following substances which are known in the field of pressure-sensitive copying paper.

Acid clay, activated clay, attapulgite, zeolite, clays such as bentonite, phenolic resins, polyvalent metal salts of various aromatic carboxylic acids as described in JP-B-51-25174, and JP-A-54-106316. Zinc salts of 2,2'-bisphenolsulfone compounds and mixtures thereof.

Examples of the combination of a metal salt and a ligand compound include the following combinations which are known in the field of pressure-sensitive copying paper.

Nickel stearate and N, N'-di-benzyl-di-
Thio-oxamide, nickel laurate and α-benzylglyoxime, tricaprylmethylammonium vanadate and dodecylamine 8-hydroxyquinoline sulfonate, benzyllauryldimethylammonium molybdate and lauryl protocatechuate, titanium stearate and lauryl gallate, Iron naphthenate and benzyl gallate, polyferrophenylmethylsiloxane and methylenebis (8-oxyquinoline), copper palmitate and N, N'-
Bis-2-octanoyloxyethyldiethyldithiooxamide, cobalt laurate and di-o-tolylguanidine, hinokitiol and polyvanadophenylmethylsiloxane, organic iron phosphate and gallic acid described in JP-A-58-38191 Combinations of lauryl and the like and mixtures thereof.

When the chromogenic substance is microencapsulated as described above, the chromogenic substance is usually encapsulated in a state of being dissolved in oil. Examples of such oil include the following substances.

Vegetable oils such as cottonseed oil, mineral oils such as kerosene, paraffin, naphthenic oil, chlorinated paraffin, aromatics such as alkylated biphenyl, alkylated terphenyl, alkylated naphthalene, diarylethane, triarylmethane, diphenylalkane Hydrocarbons, oleyl alcohol, tridecyl alcohol, benzyl alcohol,
-Phenylethyl alcohol, alcohols such as glycerin, organic acids such as oleic acid, dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate,
Esters such as dioctyl phthalate, diethyl adipate, propyl adipate, di-n-butyl adipate, and dioctyl adipate; and organic phosphoric acid compounds such as tricresyl phosphate, tributyl phosphate, tributyl phosphite, and tributyl phosphoxamide. Phenylcellosolve, benzyl carbitol, polypropylene glycol, ethers such as propylene glycol monophenyl ether, amides such as N, N-dimethyllauramide, N, N-dimethylstearamide, N, N'-dihexyloctylamide, Diisobutyl ketone,
Ketones such as methylhexyl ketone; alkylene carbonates such as ethylene carbonate and propylene carbonate; and mixtures thereof.

The amount of the chromogenic substance is usually adjusted in the range of about 1 to 80 parts by weight with respect to 100 parts by weight of the oil.

As the encapsulation method, a conventionally known coacervation method, interfacial polymerization method, in-situ method and the like can be appropriately selected and used, but it is preferable to use a synthetic resin as a wall film material, among which a melamine formaldehyde resin is used. A capsule having a coating of is particularly preferable because a pressure-sensitive copying paper having more excellent quality such as color clarity can be obtained. In addition, these microcapsules can contain an antioxidant, an ultraviolet absorber, and the like, if necessary.

As the volatile organic solvent used in the present invention,
For example, benzene, toluene, xylene, cyclohexane, hexane, trichloroethylene, ligroin, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, methanol, Ethanol, n-
Propyl alcohol, isopropyl alcohol, n-butanol, n-hexanol, cyclohexanol,
-Ethylhexyl alcohol and the like. Among them, alcohols having 3 or less carbon atoms are particularly preferable in terms of drying properties under high-speed printing.

As the ultraviolet curable compound, for example, a compound having one or more vinyl or vinylidene groups, preferably a plurality of compounds, and specifically having an acryloyl group, a methacryloyl group, an allyl group, an unsaturated polyester, a vinyloxyacrylamide group, etc. Compounds. The most typical ones are the reactants of polyols, polyamines or amino alcohols with unsaturated carboxylic acids and the reactants of acrylates or methacrylates having hydroxyl groups with polyisocyanates. Representative compounds include, for example, polyethylene glycol diacrylate, propylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate hexanediol diacrylate, 1,2-butanediol diacrylate, epoxy resin and Reactant with acrylic acid,
Examples include a reaction product of methacrylic acid, pentaerythritol, and acrylic acid, a condensate of maleic acid, diethylene glycol, and acrylic acid, methyl methacrylate, styrene, and a mixture thereof.

In addition, the compounding ratio of the volatile organic solvent and the ultraviolet curable compound is usually in the range of 95: 5 to 10:90 (parts by weight),
It is more preferably in the range of 80:20 to 20:80 (parts by weight).
Above all, when curing the smear ink only with an ultraviolet irradiation device, the range of 65:35 to 20:80 is preferable, and when curing the smear ink using an ultraviolet irradiation device and an evaporative drying device in combination, 80: A range of 20 to 40:60 is preferred.

Examples of the photopolymerization initiator include aromatic ketones, quinone compounds, ether compounds, nitro compounds and the like,
Specific examples include benzoquinone, phenanthrenequinone, naphthoquinone, diisopropylphenanthrenequinone, benzoin butyl ether, benzoin, furoin butyl ether, Michler's ketone, Michler's thioketone, fluorenone, trinitrofluorenone, and β-benzoylaminonaphthalene.

In addition, the compounding quantity of a photoinitiator is the range of 0.1-10 weight part normally with respect to 100 weight part of ultraviolet curable compounds.

Further adhesives used, acrylic resin, methacrylic resin, vinyl acetate resin, polystyrene resin, xylene resin, coumarone resin, petroleum resin, phenolic resin, resorcinol resin, urea resin, melamine resin, ketone resin, unsaturated polyester resin, Examples include polyamide resin, polyvinyl formal resin, polyvinyl butyral, nitrocellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate. Among them, the use of a cellulosic derivative is particularly preferable because the effect of improving the friction resistance of the present invention is remarkably exhibited. In addition, the compounding quantity of an adhesive is 0.1-500 weight part with respect to 100 weight part of ultraviolet curable compounds, More preferably, it is 1-300 weight part.

To the ink of the present invention, if necessary, a sensitizer for increasing the efficiency of photopolymerization, and further a white pigment, a color desensitizing component, a capsule protective agent, an antioxidant, a fluorescent dye, a plasticizer and the like are added. be able to.

Examples of the sensitizer include triethanolamine, N-
Examples include methyldiethanolamine, N, N-dimethylethanolamine, N-methylmorpholine and the like.

White pigments include zinc oxide, titanium oxide, aluminum hydroxide, magnesium carbonate, calcium carbonate, magnesium silicate, calcium silicate, calcium sulfate,
Examples thereof include inorganic pigments such as calcium phosphate and colloidal silica, and organic pigments such as melamine resin and urea resin.

Examples of the color desensitizing component include various amino compounds in the case of leuco-based recording materials, and in the case of iron chelate-based recording materials, organic phosphorus-based compounds as described in JP-A-59-38089. And a compound having an aminocarboxylic acid group.

When the volatile organic solvent used is a water-miscible solvent such as methanol or ethanol, the dispersion of the microcapsules encapsulating the chromogenic substance in the ink medium containing the above-mentioned components is performed by using an aqueous capsule dispersion. After filtration, water is removed by repeating washing and filtration with this solvent several times to re-disperse a cake-like capsule obtained in an ink medium. However, usually, an aqueous capsule dispersion is used as it is, or after having passed through a concentration step such as filtration, through-flow drying, surface drying, fluid drying, flash drying, spray drying, vacuum drying, and freeze drying. This is accomplished by removing the dispersion medium into powder capsules by means of drying, infrared drying, high frequency drying, ultrasonic drying, fine pulverization drying, or the like, and then dispersing the capsules in an ink medium.

The amount of the capsule to be mixed in the ink medium is usually 100 (volatile organic solvent + ultraviolet curable compound).
The amount is 2 to 100 parts by weight, preferably 7 to 60 parts by weight, based on parts by weight.

The thus prepared capsule ink containing the chromogenic substance can be subjected to flexographic printing, gravure printing, offset printing, letterpress printing, screen printing, or the like, for example, on a suitable support such as paper, synthetic paper, or on a support. Is applied on the back surface or the front surface of the receiving sheet provided with, to form an upper sheet, a middle sheet, or a single pressure-sensitive copying paper. Further, if the other chromogenic substance which reacts with the chromogenic substance contained in the capsule and develops a color is added to the capsule ink and the prepared ink is applied to the support, a single pressure-sensitive copying paper is obtained. .

Drying and curing of the ink is usually performed by using both a small drying device for hot air or infrared rays and an ultraviolet irradiation device. However, depending on the type and amount of the solvent used, only the ultraviolet irradiation device may be sufficient. In particular, when an alcohol is used as a volatile organic solvent, it is easily cured with only an ultraviolet irradiation device, and this is the most preferred embodiment of the present invention.

The coating amount of the capsule ink is appropriately determined depending on the type of the prepared ink, and is not particularly limited, but is generally 0.3 to 10 g / m ² by dry weight, preferably ² to 7 g / m ² . m is ² in the range of about.

The chromogenic substance forming the receiving layer is a substance that develops a color by reacting with the chromogenic substance encapsulated in the capsule, and these are crushed by a ball mill, an attritor, a sand mill or the like as necessary. After that, normal white pigments, binders and, if necessary, dispersants, colored dyes, fluorescent brighteners, ultraviolet absorbers, antioxidants, deoxidizers and various auxiliaries are added, and as an aqueous coating liquid Prepared.

As the white pigment, the same kinds of substances as those exemplified as the substance added to the capsule ink coating layer can be used, and as the binder, various binders such as water-soluble or latex-based binders are used.

Examples of the water-soluble binder include gelatin, albumin,
Proteins such as casein, starches such as cereal starch, pregelatinized starch, oxidized starch, etherified starch, and esterified starch; celluloses such as carboxymethylcellulose and hydroxyethylcellulose; saccharoses such as agar, sodium alginate, and gum arabic. Water-soluble natural polymer compounds such as polyvinyl alcohol, polyvinylpyrrolidone, sodium polyacrylate, polyacrylamide, maleic acid copolymer salts such as sodium acetate of vinyl acetate-maleic anhydride, ammonium salt of styrene-maleic anhydride, butadiene Water-soluble synthetic polymer compounds such as methacrylic acid sodium salt and the like.

Examples of the latex binder include styrene-butadiene latex, acrylonitrile-butadiene latex, acrylate latex, vinyl acetate latex, methyl methacrylate-butadiene latex, and carboxy-modified (for example, acrylic acid) latex thereof.

The thus-prepared coating liquid for forming a receiving layer is coated with various known coating methods such as an air knife coater, a roll coater, a blade coater, a size press coater, a curtain coater, a bill blade coater, and a short dwell coater, such as paper and synthetic paper. Coated on various supports.

The coating amount of the receiving layer forming coating liquid is appropriately determined according to the kind of the prepared coating liquid and the like, and is not particularly limited, but is generally ² to 15 g / m ² by dry weight, preferably It is about 3 to 7 g / m ² .

"Examples" Examples and comparative examples are set forth below in order to further clarify the effects of the present invention, but the present invention is not limited to these examples.

In the examples, parts and% represent parts by weight and% by weight, respectively, unless otherwise specified.

Example 1 (Preparation of capsule) 8 parts of crystal violet lactone was heated and dissolved in 100 parts of alkyl diphenylethane (trade name: Hisol SAS-296, manufactured by Nippon Petrochemical Co., Ltd.) to obtain an internal phase oil. Ethylene-maleic anhydride copolymer (trade name EMA31, manufactured by Monsanto Co.) was emulsified with 200 parts of a 3.0% aqueous solution of 20% caustic soda aqueous solution to pH 6.0 by emulsifying the internal phase oil.
The system was heated to 55 ° C.

Separately, melamine 15 was added to 45 parts of 37% aqueous formaldehyde solution.
The mixture was added and reacted at 60 ° C. for 15 minutes to prepare a prepolymer aqueous solution.

The aqueous prepolymer solution was added dropwise to the emulsion, and 0.1N-hydrochloric acid was added dropwise with stirring to adjust the pH to 5.3. The mixture was heated to 80 ° C., and kept at that temperature for 1 hour. −
The pH was lowered to 3.5 with hydrochloric acid, and the mixture was further kept warm for 3 hours and then allowed to cool to obtain a capsule dispersion having an average particle size of 3.0 μm.

Next, the capsule dispersion was filtered and air-dried to obtain a powder capsule.

(Preparation of capsule ink) Ethyl cellulose (trade name N-4,
100 parts of the above powder capsules were dispersed in a solution obtained by adding 15 parts (manufactured by Hercules), and 300 parts of pentaerythritol triacrylate and 10 parts of benzoin were added to obtain a capsule ink.

After the capsule ink was flexo printing base paper (the above creation of the paper) 40 g / m ^2, and curing the ink by ultraviolet irradiation device, the amount of ink 4.
A spot print of 0 g / m ² was obtained. In addition, the obtained printed matter had no wrinkles at all, and the opacity of the printed portion was good. Further, even when printing was performed at a speed of 130 m / min, no stain was generated on the guide roll.

(Preparation of lower paper) 65 parts of light calcium carbonate, 20 parts of zinc oxide, mixed melt of zinc 3,5-di (α-methylbenzene) salicylate and α-methylstyrene / styrene copolymer (mixing ratio 80 / 20) 1
5 parts, 5 parts of polyvinyl alcohol aqueous solution (solid part) and 300 parts of water were dispersed in a ball mill for 24 hours to obtain a dispersion,
A developer coating solution prepared by adding 20 parts (solid part) of a carboxy-modified styrene / butadiene copolymer latex is applied to a base paper of a developer coating solution 40 g / m ^{2 by} an air knife coater so that the dry weight becomes 5 g / m ^2. I got the bottom paper.

(Evaluation of color development and friction resistance) When the obtained upper paper and lower paper were overlaid and printed with a typewriter, a good color development image was obtained. Further, the upper paper and the lower paper were overlapped and rubbed against each other for 10 reciprocating surfaces under a pressure of 100 g / m ^2. As a result, the contamination of the lower paper was at a practically acceptable level.

Comparative Example 1 Ethyl cellulose (trade name N-4, manufactured by Hercules)
A capsule ink was prepared in the same manner as in Example 1 except that 15 parts were not added, and an upper paper was obtained in the same manner as in Example 1.

(Evaluation) The obtained upper paper had no wrinkles at all and the opacity of the printed portion was good. Also, even when printing was performed at a speed of 130 m / min, almost no stain was generated on the guide roll.

In addition, when the upper sheet and the lower sheet obtained in the same manner as in Example 1 were overlaid and printed by a typewriter, a good color image was obtained. However, the top and bottom sheets are stacked 100g
As a result of friction between the 10 reciprocating surfaces under a pressure of / m ² , a problematic level of stain was generated on the lower paper.

Example 2 (Preparation of capsule ink) Nitrocellulose (trade name: nitrated cotton) was added to 700 parts of ethanol.
Powder capsule obtained in the same manner as in Example 1 to a solution obtained by adding 50 parts of FQ type SS1 / 4, manufactured by Daicel Chemical Industries, Ltd.
100 parts were dispersed, and 200 parts of trimethylolpropatriacrylate, 10 parts of benzoin butyl ether, 1 part of N, N-dimethylethanolamine and 50 parts of an acrylic resin (trade name: ARON S-4080, manufactured by Toagosei Co., Ltd.) were added. Thus, a capsule ink was obtained.

(Preparation of upper paper) Flexographic printing of the obtained capsule ink on 40 g / m ² base paper, curing of the ink with a small hot air drying device and ultraviolet irradiation device, and spot printing of 4.5 g / m ² of ink. To get the paper. No wrinkles were observed on the obtained upper paper, and the opacity of the printed portion was good. Also
Even when printing was performed at a speed of 130 m / min, no stain was generated on the guide roll.

(Evaluation of Coloring Property and Friction Resistance) When the obtained upper paper and the lower paper obtained in the same manner as in Example 1 were overlaid and printed with a typewriter, a good color-developed image was obtained. Further, the upper paper and the lower paper were overlapped and rubbed against each other for 10 reciprocating surfaces under a pressure of 100 g / m ^2. As a result, the contamination of the lower paper was at a practically acceptable level.

Comparative Example 2 The same procedure as in Example 2 was carried out except that 50 parts of nitrocellulose (nitrified cotton SS1 / 4) and acrylic resin (Aron S-4080) were not added in the preparation of the capsule ink of Example 2. Obtained.

(Evaluation) The obtained upper paper had no wrinkles at all and the opacity of the printed portion was good. Also, even when printing was performed at a speed of 130 m / min, almost no stain was generated on the guide roll.

Further, when the upper sheet and the lower sheet obtained in the same manner as in Example 1 were superimposed and printed by a typewriter, a good color image was obtained. However, 100g / m
Friction between the 10 reciprocating surfaces under the pressure of ² resulted in a problematic level of contamination on the underlying paper.

〔effect〕

According to the method of the present invention, pressure-sensitive copying paper having good performance could be produced very efficiently.

────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-3-202394 (JP, A) JP-A-4-211985 (JP, A) JP-A-3-261588 (JP, A) (58) Field (Int.Cl. ⁶ , DB name) B41M 5/124

Claims (4)

(57) [Claims] 1. A microcapsule containing (a) a chromogenic substance, (b) a volatile organic solvent, (c) an adhesive, (d) an ultraviolet curable compound, and (e) a photopolymerization initiator. A method for producing pressure-sensitive copying paper, comprising printing a capsule ink as a component on a support and curing the ink. 2. The method for producing pressure-sensitive copying paper according to claim 1, wherein the volatile organic solvent is an alcohol. 3. The method according to claim 1, wherein the mixing ratio of the volatile organic solvent and the ultraviolet curable compound is in the range of 65:35 to 20:80, and the smear ink is cured only by the ultraviolet irradiation device. Pressure-sensitive copying paper manufacturing method. 4. The method according to claim 1, wherein the mixing ratio of the volatile organic solvent and the ultraviolet-curable compound is in the range of 80:20 to 40:60, and the evaporative drying device and the ultraviolet irradiation device are used together to cure the smeared ink. ) Or (2).