JPH04140187A - Carbonless pressure-sensitive copy paper - Google Patents

Abstract

PURPOSE:To enhance printability, the touch and coating properties by taking the balance of developed color density and developed color staining by using a specific associable high-molecular compound in a coating solution. CONSTITUTION:In carbonless pressure-sensitive copy paper formed by applying a coating solution containing a microcapsule including a color former and latex to paper and drying the coating layer, an associable high-molecular compound is used in the coating solution. The associable high-molecular compound has a property associating with the latex or microcapsule within a region of pH=7-14 to partially gather or flocculate the same and interfacially associates by the interaction of hydrophobic groups. As the associable high-molecular compound, a water-soluble high-molecular polymer formed by locally providing hydrophobic groups in a polymer at two or more places or an emulsion thereof or a water-soluble high-molecular polymer formed by locally providing hydrophobic groups to at least both terminals of a polymer or an emulsion thereof is preferable.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a pressure sensitive copying paper having a coating of microcapsules. More specifically, the present invention relates to a Maker-bond pressure-sensitive copying paper which is excellent in color stain resistance, coating suitability, tactility, and printing suitability.

[Conventional technology]

Manufacturer Bonn's pressure-sensitive copying paper is usually manufactured by coating a support with microcapsules containing a colorless leuco dye (coloring agent) and a color developer. Each is coated individually on a support and used as a top paper and a bottom paper, and each coated on both sides is generally used as an inner paper. Self-contained papers have also been used in which one or two layers of each are coated on one side of the support. Multiple sheets of these sheets are combined as appropriate, and physical pressure is applied by writing, typewriter, impact printer, etc. to destroy the microcapsules, and the leuco dye inside the capsules comes into contact with the color developer and develops color. This is a system that can obtain recorded images. In general, the following two items are listed as important quality conditions required for non-carphone pressure-sensitive copying paper. 1. Dark, clear images can be obtained in a short time, and there is no deterioration over time. 2. When color development is not intended, i.e., during the manufacturing process of pressure-sensitive copying paper, during cutting and various printing processes, during storage and handling in sheet form or rolled up form, color development stains should not occur. Above 1. and 2. Since these are contradictory effects, it is generally difficult to fully satisfy both and maintain a balance. In general, a coating layer containing microcapsules consists of microcapsules, a buffer material, a binder, and other additives, including: ■ Manufacturing conditions for microcapsules, ■ Type and amount of buffer material, ■ Type and amount of binder, etc. Partial improvement is possible by modifying the factors, and many proposals have been made regarding this. ■The method for producing microcapsules containing a coloring agent is as follows:
Although many are known, the representative methods include: - Coacervation method using a polyion complex of gelatin-gum arabic.・An interfacial polymerization method that forms an insoluble film at the interface between a hydrophilic liquid as a dispersion medium and a hydrophobic liquid to be included.・After adding a film resin initial condensate such as melamine-formalin resin or urea-formalin resin from the hydrophilic liquid side that will serve as a dispersion medium, it is converted into a resin and encapsulated in s.
An example is the itυ polymerization method. Recently, raw materials are cheap and stably supplied, highly concentrated microcapsule emulsions can be obtained, and the manufacturing process is simple.
For these reasons, synthetic resin capsules, especially capsules made by the n + ilu polymerization method, have come to be used. Regarding the cushioning material (2), glass peas disclosed in U.S. Patent No. 2,711,375 and finely ground cellulose fibers (cellulose flock) disclosed in U.S. Pat.
Or, Japanese Patent Publication No. 47-1178, No. 48-332
Ungelatinized starch particles (wheat starch,
10 to 400 parts by weight of potato starch, peaflower starch, etc. are used per 100 parts by weight of the solid content of the microcapsules. These buffering materials are generally made of inert particles that are slightly larger than microcapsule particles (generally, their diameter is 5
~50 μm). Buffering material is very important to protect microcapsules, but contact smearing methods, such as blade coaters (
With flexible blade coaters (trailing blade coaters, fountain blade coaters, etc.), rod bar coaters, etc., a scraping phenomenon occurs during coating, and the buffer material is often not sufficiently coated. Furthermore, the use of a cushioning material increases the unevenness of the coated surface, reducing tactility and printing suitability (particularly ink transfer). Recently, users are demanding not only the original information recording ability of Bonn pressure-sensitive copying paper, but also aesthetics including tactility. Further, as the uses of pressure-sensitive copying paper become more diverse, opportunities for various types of printing on the surface coated with microcapsules are increasing. As a countermeasure to this problem, formulations that do not use buffering materials (Japanese Patent Application Laid-open No.
No. 151.271, No. 61-192586,
No. 61241185, No. 241186), etc. have been proposed. Regarding the type of binder (2), proposals have recently been made to use various latexes. Latex is also used in the above proposal for a formulation without the addition of buffering material. Latex itself has the advantage of higher cushioning properties than other known binders (polyvinyl alcohol, starch glue, etc.). However, since it is a fine emulsion, its permeability into the support layer is high and sufficient effects may not be obtained in many cases. As a solution to this problem, it has been proposed to use all or part of an alkali-thickened latex with reduced permeability (Japanese Patent Laid-Open Nos. 64-49678, 1-234289,
JP-A-1-234290, JP-A-1-288480, JP-A-2-3367, and other publications). Although a number of proposals have been made as described above, the current situation is that nothing satisfactory has been obtained yet.

[Problems to be solved by the invention]

The present invention simultaneously overcomes the quality and manufacturing problems of conventional manufacturer-bonded pressure sensitive copying papers. In other words, basically, microcapsules containing a coloring agent and latex-containing coating liquid are coated and dried on Manufacturer Bonn pressure-sensitive copying paper. The aim is to significantly reduce it. Specifically, the balance of the following characteristics A and B, which are contradictory characteristics, is improved. Improved color density. A dark and clear copy image can be obtained, and a clear image can be obtained even when copying a large number of sheets. B. Preventing color stains when color development is not intended. The types of colored stains are: ・Dynamic colored stains that occur during rubbing; ・Static pressure colored stains that are applied during storage, transportation, printing, and guillotine cutting in rolled or sheet form; ・Heated and humidified conditions. Examples include colored stains caused by capsule destruction during long-term storage. In any of these cases, it should exhibit excellent resistance to color development and staining. In addition, tactility (that is, the applied surface has few irregularities and feels good to the touch). Printability (i.e. ink transferability or good). Application suitability in contact application method (i.e., no destruction of microcapsules). The purpose is to obtain a coating liquid with excellent properties. The object of the present invention is to obtain a manufacturer's bond pressure-sensitive copying paper that satisfies all of the above requirements.

[Means to solve the problem]

As a result of intensive studies, the present inventors have basically found that in Manufacturer Bonn pressure-sensitive copying paper, which is made by applying and drying a coating liquid containing microcapsules containing a coloring agent and latex, the coating liquid contains We were able to solve this problem by using an associative polymer compound. The associative polymer compound used in the present invention has a pH of 7 to 1.
In the region 4, it has the property of associating with latex, microcapsules, etc. and causing them to partially aggregate or aggregate.
It is a water-soluble polymer or a polymer emulsion. In terms of surface chemistry, it is a high-molecular polymer or a high-molecular emulsion that associates with latex, microcapsules, etc. through hydrophobic interaction. Associative polymer compounds include: 1. A water-soluble polymer or polymer emulsion formed by localizing hydrophobic groups at at least two force points in the polymer. 2. A water-soluble polymer or polymer emulsion in which hydrophobic groups are localized at least at both ends of the polymer. is preferred. Monomers used in polymerization include (olefin derivatives (ethylene, 1-butene, 2-butene, isobutyne,
3-methyl-1-butene, etc.), diene derivatives (propadiene, 1,2-butadiene, 1,3-butadiene, 2,
3-dimethyl-13-butadiene, 1,2-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1
3-pentadiene, 1,4-pentadiene, 2-methyl-
1,4-pentadiene, 1,2-hexadiene, 1.3
-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-15-hexadiene, 3
, 3-dimethyl 1,5-hexadiene, 2-methyl-1
, 5-hexadiene, 3-methyl-1,5-hexadiene, 2,4-hexadiene, 2,5-dimethyl-2,4-hexadiene, 5,5-dimethyl-24-hexadiene,
Octadiene, nonadiene, 1,9-decadiene, 1.
10-undecadiene, etc.), styrene derivatives (styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, dimethylstyrene, trimethylstyrene, isopropylstyrene, methoxystyrene, nitrostyrene, aminostyrene, p-vinylbenzene Sulfonic acid, p-vinylbenzenesulfonic acid Nap-vinylbenzenesulfonic acid, 1α-methylstyrene, α-ethylstyrene, etc.), vinyl ester derivatives (vinyl acetate, vinyl butyrate, vinyl pivalate, vinyl caprylate, vinyl laurate, Vinyl palmitate, vinyl stearate, vinyl methacrylate, vinyl crotonate, vinyl cinnamate, vinyl benzoate, vinyl nitrobenzoate, vinyl formate, etc.), vinyl ether derivatives (methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl) vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether-ethylhexyl vinyl ether, n-octadecyl vinyl ether, vinyl vinyl ether, allyl vinyl ether, benzyl vinyl ether, phenyl vinyl ether, 2-methoxyethyl vinyl ether, diethylene glycol divinyl ether, etc.), acrylic acid rust conductors (
Acrylic acid, acrylic anhydride, acrolein, crotonic acid, isocrotonic acid, angelic acid, tiglic acid, dimethylacrylic acid, methylethyl acrylic acid, α-[N
-acrylocoaminoacrylic acid, α-acetoxyacrylic acid, α-trimethylsilylacrylic acid, Na acrylate, etc.), methacrylic acid derivatives (methacrylic acid, methacrylic anhydride, methacrolein, Na methacrylate, etc.)
, acrylic acid ester derivatives (methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 10-undecyl acrylate, 2-ethyl butyl acrylate, vinyl acrylate, 2-ethylhexyl acrylate, 2- ethoxyethyl acrylate, octadecyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, phenyl acrylate, etc.), methacrylic acid ester derivatives (methyl methacrylate, ethyl methacrylate, propyl methacrylate,
n-octyl methacrylate, 2-ethylhexyl methacrylate, 2-cyanoethyl methacrylate, isobutyl methacrylate, tridecyl methacrylate, vinyl methacrylate, etc.), acrylamide derivatives (acrylamide, N-methylacrylamide, N-fert-
butylacrylamide, N-benzylacrylamide, etc.), methacrylamide derivatives (methacrylamide, N-
Methyl methacrylamide, N-ferf-butyl methacrylamide, N-benzyl methacrylamide, etc.), acrylonitrile derivatives (acrylonitrile, 2-ethyl acrylonitrile, 2-phenylacrylonitrile, etc.),
Methacrylamide derivatives, maleic acid derivatives (maleic anhydride, methyl maleic anhydride, dimethyl maleic anhydride, phenyl maleic anhydride, maleic acid, methyl maleic acid, dimethyl maleic acid, phenyl maleic acid, etc.)
, maleate ester derivatives (monomethyl maleate,
dimethyl maleate, monoethyl maleate, diethyl maleate, monobutyl maleate, dibutyl maleate, etc.), maleamide derivatives (maleamic acid, maleic diamide, etc.), maleimide derivatives (maleimide, N-methylmaleimide, N-ethylmaleimide, etc.) , dicarboxylic acid derivatives (oxalic acid, malonic acid, succinic acid, tartaric acid,
Itaconic acid, acetylene dicarboxylic acid, glutaric acid, 3
-methylglutaric acid, etc.), dicarboxylic acid ester derivatives (monoethyl oxalate, monophenyl oxalate, monoethyl malonate, monophenyl malonate, monoethyl succinate, monophenyl succinate, monoethyl tartrate, monoethyl itaconate, monoethyl fumarate, Monoethyl acetylene monocarboxylate, monoethyl glutarate, diethyl oxalate, diphenyl oxalate, diethyl malonate, diphenyl malonate, diethyl succinate, diphenyl succinate, diethyl tartrate, diethyl itaconate, diethyl fumarate, diethyl acetylene dicarboxylate, Among these, particularly highly hydrophobic monomers include styrene derivatives (styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, dimethylstyrene, trimethylstyrene, isopropylstyrene, methoxystyrene, etc.). styrene, nitrostyrene, aminostyrene, α-methylstyrene, α-ethylstyrene, etc.), vinyl ether derivatives (allyl vinyl ether, benzyl vinyl ether, phenyl vinyl ether, etc.), acrylic ester derivatives (phenylacrylate, etc.), methacrylic ester derivatives, Examples include dicarboxylic acid ester derivatives (monophenyl oxalate, monophenyl malonate, monophenyl succinate, diphenyl oxalate, diphenyl malonate, diphenyl succinate, etc.). The above examples are just a few, and for more details, please refer to "Polymer Data Handbook, Basic Edition" (edited by the Society of Polymer Science and Technology).
Baifukan Publishing, 1986). In addition, Japanese Unexamined Patent Publication No. 51-90251, No. 5
No. 5-108411, No. 56-47477,
No. 58-189299, No. 59-73540, No. 59-89313, No. 59-108075
In addition to the hydrophilic monomers and hydrophobic monomers described in No. 61-228081, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, long chain α-olefin oxide, etc.) Preferably, pH=
This is not the case as long as it is a high molecular weight polymer or high molecular emulsion that associates with latex, microcapsules, etc. through hydrophobic group interaction in the region 7 to 14. Furthermore, the above-mentioned associative polymer compound can have alkaline thickening properties by containing monomers used in known water-soluble thickeners such as acrylic acid, methacrylic acid, and itaconic acid as its monomer units. Can be granted. Alkaline thickening means that the viscosity of the coating liquid changes from acidic to alkaline (p
This is a behavior in which the B-type viscosity increases as H=7 to 14). The amount of the associative polymer compound to be used varies depending on its associative force, but is preferably in the range of 0.1 to 20 parts by solid weight per 100 parts by solid weight of the microcapsule. Furthermore, 0
Particularly preferred is a range of 1 to 10 parts by solid weight. When the above-mentioned associative polymer compound is used in an alkali-thickened form,
A range of 0.1 to 5 parts by solid weight is preferred. The present invention differs from the above-mentioned proposals (JP-A-61-151271, JP-A No. 61-192586, JP-A No. 61241185, JP-A No. 241186), and the present invention efficiently spreads latex around microcapsules using an associative polymer compound. It became possible to localize it well to the extent that it did not inhibit color development. Therefore, with a smaller amount of binder used, it was possible to apply without destroying the microcapsules during coating, and it was possible to obtain a Manufacturerbon pressure-sensitive paper with excellent color development and stain resistance. Furthermore, by significantly preventing latex from penetrating into the support, a suitable support covering effect was obtained, eliminating unevenness on the coated surface and greatly improving aesthetics and ink transfer. . If only the permeability is to be suppressed, it is possible to some extent by using the alkali-thickened latex mentioned above, but it is not possible to localize the latex efficiently around the microcapsules to the extent that it does not inhibit color development. There wasn't. In this respect, the present invention has an effect different from the conventional one, and furthermore, it coats and dries a coating liquid that does not contain particles (buffering material, etc.) with a volume average diameter 50% value of 10 μm or more by the Coulter-Counter method. This is carbon-free pressure-sensitive copying paper. The type B viscosity of the coating liquid is preferably adjusted to, for example, 1 to 1000 cps when the solid content concentration is 20% (liquid temperature = 20°C). Note that this is an example of measurement conditions, and the effects of the present invention are not limited to this coating liquid concentration and coating liquid temperature. If the viscosity is below this range, it is difficult to obtain the effects of the present invention, and if it is above this range, the coating suitability is poor. As the latex, styrene-butadiene copolymer latex, vinyl acetate-based, acrylic-based various latexes, and alkali-thickened latexes thereof are preferable. Furthermore, mixtures thereof are also preferred. As the alkaline thickening latex, the commonly used ones mentioned above can be used. The amount used is 1 microcapsule
00 fan parts by weight, in the case of non-alkali thickening latexes, the range of 5 to 100 parts by solid weight is desirable. In alkaline thickening latex (preferably in the range of 5 to 70 parts by solid weight), in addition, binder components other than latex include water-soluble polymers such as soluble starch, casein, gelatin, gum arabic, polyvinyl alcohol, and methylcellulose CMC. There is no problem in using appropriate amounts of substances.Usually,
The amount of the binder other than latex used in combination is preferably in the range of 0 to 100 parts by solid weight per 100 parts by weight of the microcapsules. Particularly preferred is a range of 0 to 50 parts by solid weight. Coulter in the microcapsule coating layer in the present invention.
- There is no problem in adding various pigments having a volume average diameter 50% value of 3 μm or less by the counter method to the extent that the surface smoothness is not impaired. The pigment is not particularly limited as long as it satisfies the above conditions and is used in general pressure-sensitive copying paper. Specific examples include various plastic pigments, various plastic hollow pigments, calcium oxide, calcium hydroxide, calcium carbonate, calcium metasilicate, magnesium hydroxide,
Examples include magnesium carbonate, magnesium oxide, aluminum hydroxide, and aluminum silicate. There is no problem in adding an appropriate amount of a substance exhibiting anti-foaming and foam-inhibiting properties to the coating solution in the present invention. The substance exhibiting defoaming and foam-inhibiting properties is not particularly limited as long as it is used in general pressure-sensitive copying paper. Specific examples include: - As alcohols, propyl alcohol, butyl alcohol, amyl alcohol, octyl alcohol, lauryl alcohol, cetyl alcohol, polyalkylene glycol, etc.・As fatty acids and fatty acid esters, sorbitan monolaurate, sorbitan trioleate, polyoxyethylene ether, isoamyl stearate, ethylene glycol laurate, etc. ・As amines and amide types, stearylamide, butanedicetylamide, diacetylamide, etc. Stearyl ethylene diamine, etc.: Ether type ◆ Phosphoric ester type/metal soap type: palmitic acid, stearic acid AI, stearic acid Ca,
Mg stearate, etc.: - Silicon type or a mixture thereof can be mentioned. These are determined by the application and desired properties. The coloring agent (electron-donating coloring agent) used in the present invention is not particularly limited as long as it is used in general pressure-sensitive copying paper. To give a specific example, (I) triarylmethane compounds include 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (crystal violet lactone), 3,3-bis (p
-dimethylaminophenyl) phthalide, 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-methylindole) -3-yl)phthalide, 3-(p-dimethylaminophenyl)-
3-(2-phenylindol-3-yl)phthalide,
3.3-bis-(1,2-dimethylindol-3-yl)-5-dimethylaminophthalide, 3.3-bis-(
1゜2-dimethylindol-3-yl)-6-dimethylaminophthalide, 3.3-bis-(9-ethylcarbazol-3-yl)-5-dimethylaminophthalide, 3
,3-bis-(2-phenylindol-3-yl)-
5-dimethylaminophthalide, 3-p-dimethylaminophenyl-3-(1-methylpyrrol-2-yl-6-
Dimethyl-aminophthalide, etc. (2) As a diphenylmethane compound, 4.4" -
Bis-dimethylaminobenzhydrin benzyl ether, N-halophenylleucoolamine, N-2,4,5
-1 Lichlorophenyl leukoolamine, etc. (3) As xanthine compounds, Rhodamine B-anilinolactam, Rhodamine B-p-
Nitroanilinolactam, Rhodamine Bp-chloroanilinolactam, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-7-octylaminofluorane, 3-diethylamino-7-phenylfluorane, 3-diethylamino- 7-3,4-dichloroanilinofluorane, 3-diethylamino-7-(2chloroanilino)fluorane, 3-diethylamino-6-
Methyl-7-xylidinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3-
Cyclohexylmethylamino-6-methyl-7-anilinofluorane, 3-isobutyl-ethylamino-6-methyl-7-anilinofluorane, 3-piperidino-6-
Methyl-7-anilinofluorane, 3-ethyl-tolylamino-6-methyl-7-anilinofluorane, 3-ethyl-tolylamino-6-methyl-7-phenylfluorane, 3-diethylamino-7-(4 -nitroanilino)fluoran, etc.: (4) As a thiazine compound, benzoylleucomethylene blue, p-nitrobenzoylleucomethylene blue, etc.: (5) As a spiro compound, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran , 3.3°-cyclolosespiro-dinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methylnaphtho-(3methoxy-benzo)-spiropyran, 3-propyl-spiro-dibenzopyran, etc.: In addition, JP-A-63 -230387 publication and “Pressure sensitive,
Pigments for thermal recording paper” (Coloring materials, 61 [5] P292-
302.1988). Alternatively, a mixture of these can be mentioned. These are determined by the application and desired properties. When microencapsulating an electron-donating color former,
These are usually dissolved in a hydrophobic medium and used as a core material, but the hydrophobic medium is not particularly limited as long as it is used in general pressure-sensitive copying paper. Specific examples include (2) aromatic hydrocarbons such as diarylethane, alkylbiphenyl, alkylterphenyl, alkylnaphthalene, triarylmethane,
Diphenylalkane, hydroanthracene, hydrophenanthrene, etc., dibenzyltoluene: (b) Mineral oils such as kerosene, paraffin, naphthenic oil, chlorinated paraffin, etc.; (c) Vegetable oils such as cotton oil, corn oil, coconut oil, etc.: (d) Alcohols such as oleyl alcohol, tridecyl alcohol, benzyl alcohol, 1-phenylethyl alcohol, glycerin, etc.; (e) Organic acids such as oleic acid. (f) As an ester, dimethyl phthalate, diethyl phthalate, dilobityl phthalate, dioctyl phthalate, diethyl adipate, propyl adipate, di-n-butyl adipate, dioctyl adipate, etc. = (g) As an organic phosphoric acid compound, tricle Zyl phosphate, tributyl phosphite,
Tributyl phosphite oxide, etc.: (h) As an ether, phenyl cellosolve, pendyl carbitol, polypropylene glycol, propylene glycol monophenyl ether, etc.: fi) As an amide, N,N-dimethyllauramide, N,N-dimethylstearamide , N,N-dihexyl octylamide, etc. Ketones include diisobutyl ketone, methylhexyl ketone, etc. (k) Alkyl carbonates include ethylene carbonate, propylene carbonate, etc. Or mixtures thereof. It is determined by the use and desired properties.Furthermore, when microencapsulating an electron-donating coloring agent, it is also possible to use substances such as ultraviolet absorbing substances and infrared absorbing substances dissolved in a hydrophobic solvent at the same time. There is no problem.These are not particularly limited as long as they are substances used in general pressure-sensitive copying paper.Specific examples of ultraviolet absorbers include (a) salicylic acid-based substances such as phenyl salicylate, p-tert-butylphenyl; Salicylate, p-octylphenyl salicylate, etc.: (b) As benzophenone type, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
Octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2.2°-dihydroxy-4-methoxybenzophenone, 2,2゛-dihydroxy-4,4°-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5 -Sulfobenzophenone etc. (
c) As the benzotriazole type, 2(2°-hydroxy-5′-methylphenyl)benzotriazole, 2(2′-hydroxy-5′tert-butylphenyl)benzotriazole, 2(
2′-Hydroxy-3′5′-di-tert-butylphenyl)benzotriazole, 2(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5chlorobenzotriazole, 2(2′ -Hydroxy-3"5'di-tert-alumophenyl)benzotriazole,2(2'-hydroxy-4'
-Octoxyphenyl)benzotriazole, etc. (d)cyanoacrylates, such as 2-ethylhexyl-2-cyano-3,3゛diphenylacrylate, ethyl-2-cyano-3,3゛ - diphenyl acrylate, etc.: or Mixtures of these may be mentioned. These are determined by the application and desired properties. The encapsulation method used in the present invention is not particularly limited, but since microcapsules produced by coacervation method generally have a film destroyed in latex, interfacial polymerization method or il 5ilu method is used. It is desirable to use a polymerization encapsulation method. in sselfυ
The emulsifier used in polymerization encapsulation is preferably a polymer electrolyte. Specifically, styrene-maleic anhydride copolymer, styrene-benzyl methacrylate-maleic anhydride copolymer, α-alkyl styrene-maleic anhydride copolymer, nuclear monoalkyl-substituted styrene-maleic anhydride copolymer, nuclear monoalkyl substituted styrene-maleic anhydride copolymer, Dialkyl substituted styrene-maleic anhydride copolymer, styrene-maleic anhydride monoalkyl ester copolymer, ethylene-maleic anhydride copolymer, polystyrene sulfonic acid, polyacrylic acid, acrylic acid-acrylic acid ester. Aqueous solutions of copolymers, etc., and mixed aqueous solutions thereof are used. The emulsifier used for interfacial polymerization encapsulation is
In addition to PVA for n 5 itu encapsulation. Aqueous solutions of CMC, HEC, various (wheat, potato, corn, etc.) starches, and mixed aqueous solutions of these can also be used. It should be noted that there is no problem even if known substances having nonionic, cationic, or amphoteric surfactants are added and used in combination to the extent that they do not cause problems in the encapsulation process. The coating method used in the present invention is a conventional coating machine (
coater) and dried. As a specific coating machine, an air knife coater, a blade coater, a rod coater, a bar coater, a roll coater, a size press coater, a curtain coater, etc. are used. Note that, among these various coating methods, the present invention is particularly effective for contact methods. As the support, acidic paper or neutral paper mainly composed of cellulose fibers is usually used, but synthetic paper may also be used. Furthermore, there is no problem in using recycled paper, various types of recycled paper, etc. Color developers used in combination with the Manufacturer Bonn pressure-sensitive copying paper obtained by the present invention include phenolic resin compounds, salicylic acid metal salt compounds, and various other inorganic and organic solid acid compounds. Or they can be used in combination.

【Example】

Next, the features of the present invention will be illustrated in detail through comparative examples and examples, but of course the present invention is not limited to the examples alone, and therefore the materials used, manufacturing conditions, etc. are also limited to those described in the examples. It won't happen. The following parts numbers are expressed in parts by weight of dry solids, unless otherwise specified. Example 1 [Microencapsulation] 4 parts of crystal violet lactone (CVL) was dissolved in a diarylethane-based solvent (Isol SAS N-2).
96 (manufactured by Nippon Petrochemical Co., Ltd.) was prepared. 220 parts of the above hydrophobic liquid was gradually added to 180 parts of a 5% styrene-maleic anhydride copolymer aqueous solution (manufactured by Arayo Kagaku Co., Ltd.) under strong stirring, and the volume average diameter was 50% by Coulter-Counter method. Stirring was continued until the value reached 3 μm to obtain an emulsion. Separately, 11 parts of melamine, 2 parts of 37% formaldehyde aqueous solution
Melamine obtained by heating and dissolving 1.2 parts and 28.2 parts of water.
A formaldehyde initial condensate aqueous solution was added to the emulsion and stirred for 2 hours at a temperature of 70°C to obtain a microcapsule liquid. [Preparation of pressure-sensitive copying paper (CB)] To 100 parts of the above microcapsules, add 19 parts of alkali non-thickening type styrene-butadiene copolymer latex (#0853: manufactured by Nippon Gosei Rubber Co., Ltd.), and add acrylic acid-acrylic acid. One part of an acid ester copolymer-based alkali-thickened associative polymer emulsion (TT-615: manufactured by Rohm and Haas) was added. The pH was adjusted to 9.0 to obtain a coating solution for copying paper manufactured by Bonn. Apply 40g of coating liquid using a fountain blade coater.
/nf high-quality paper so that the dry capsule coating amount was 25 g/m, and
) was obtained. [Measurement of Color Density and Static Pressure Color Contamination] The obtained CB was combined with a commercially available Bonn pressure-sensitive copying paper bottom paper (Mitsubishi NCR Paper Shimokawa Paper 40.40g/rr! Base bottom paper), as shown below. The color density and static pressure color stain were measured.・Top paper and bottom paper with combined color density, 400 kg/cm
The color was developed under a pressure of 2. CF receipt reflectance measurement,
Color difference meter NDI manufactured by Nippon Heavy Industries
This was carried out using an OIDP type. The display is the reflectance of the colored part/
The reflectance of the untreated portion (background portion) is expressed as X100 (%). As this value becomes smaller, the color density becomes deeper. - Static Pressure Colored Stains After holding the combined top paper and bottom paper under a pressure of 20 kg/cm2 for 60 seconds, the dirt on the bottom paper was measured in the same manner as the color density described above. As this value increases, the amount of static pressure colored stains decreases.・According to Dynamic Friction Coloring Stains J 15-L-1048, using a Gakushin type dyed material friction fastness tester, the combined upper paper and lower paper were
Reciprocating friction was performed five times under a load of g. The stain on the bottom paper was measured in the same manner as the color density described above. As this value increases, the amount of dynamic friction colored stains decreases. Microcapsule destruction and scraping of the cushioning material during application were determined using scanning electron micrographs. - Red ink was printed on the microcapsule coating layer (CB layer) using an ink transferability RI printing machine. CB receipt reflectance measurement was carried out using a color difference meter NDIOIDP model manufactured by Nippon Denshoku Kogyo ■. The display is the reflectance of the printed part/the reflectance of the unprinted part (CB background part) x 100 (
%). The smaller this value is, the better the ink transferability becomes.・Comparisons were made based on tactile feel. Example 2 Example 1 except that 95 parts of #0853 and 9.5 parts of alkali-thickened styrene-butadiene copolymer latex (10628: manufactured by Nihon Gosei Rubber Co., Ltd.) were used instead of 19 parts of #0853. I did the same thing. Example 3 The same procedure as in Example 1 was carried out except that 19 parts of #0853 were replaced and 19 parts of #0628 were used. Example 4 The same procedure as Example 3 was carried out except that TT-615 was changed from 1 part to 0.1 part. Example 5 The same procedure as Example 3 was carried out except that TT-615 was changed from 1 part to 2 parts. Example 6 The same procedure as in Example 3 was carried out except that TT-615 was changed from 1 part to 3 parts. Example 7 The same procedure as Example 3 was carried out except that TT-615 was changed from 1 part to 5 parts. Example 8 The same procedure as in Example 3 was carried out except that the coating device was changed to an air knife coater instead of the fountain blade coater. Example 9 The same procedure as in Example 3 was carried out except that the coating device was changed to a curtain coater instead of the fountain blade coater. Example 10 The same procedure as in Example 1 was carried out, except that #0853 was replaced with 19 parts and #0853 was used in an arbitrary amount in the range of 5 to 60 parts. Comparative Example 1 #0853 was replaced with 19 parts and TT-615 was replaced with 1 part, #
The same procedure as in Example 1 was carried out except that 20 parts of 0853 was used. Comparative Example 2 In place of 1 part of TT-615, 1 part of alkali thickened polymer emulsion (ASE-75: manufactured by Rohm & Haas) was added.
The same procedure as in Example 1 was carried out except that 100% of the total amount was used. Comparative Example 3 #0853 was replaced with 19 parts and TT-615 was replaced with 1 part, #
The same procedure as in Example 1 was conducted except that 19 parts of 0628 and 1 part of ASE-75 were used. Comparative Example 4 80853 was replaced with 19 parts and TT-615 was replaced with 1 part, #
The same procedure as in Example 1 was carried out except that 20 parts of 0628 was used. Comparative Example 5 Wheat starch (volume average diameter 50% value by Coulter Counter method = 15 μ
Comparative Example 4 was repeated except that 35 parts of m) was further added. Comparative Example 6 Comparative Example 5 was carried out in the same manner as in Comparative Example 5, except that the coating device was changed to an air knife coater instead of the fountain blade coater. Comparative Example 7 The same procedure as Comparative Example 6 was carried out except that $0628 was replaced with 20 parts and #0853 was replaced with 20 parts. Comparative Example 8 Comparative Example 5 was carried out in the same manner as in Comparative Example 5, except that the coating device was changed to a curtain coater instead of the fountain blade coater. Comparative Example 9 Wheat starch (volume average diameter 50% value by Coulter Counter method = 15 μ
Example 3 was repeated except that 35 parts of m) was further added and the coating device was changed to an air knife coater instead of a fountain blade coater. Comparative Example 10 The same procedure as Comparative Example 9 was carried out except that the coating device was changed to a curtain coater instead of a fountain blade coater. Comparative Example 11 #0853 was replaced with 19 parts and TT-615 was replaced with 1 part, A
SE-75 is unused and fixed in 1 part, 10853 is 5
The same procedure as in Example 1 was carried out except that an arbitrary amount in the range of 60 parts to 60 parts was used. The results of Examples 1 to 9 and Comparative Examples 1 to 10 are shown in Table 1. The results of Example 10 and Comparative Example 11 are shown in Table 2. In Tables 1 and 2, tactility and overall evaluation were evaluated based on the following criteria. - Excellent tactility 112 The feel is very good. Good , , , // are good. Bad , , // is bad.・Comprehensive evaluation ◎900 The purpose of the present invention is fully satisfied. ○011 The purpose of the present invention is met. Δ111 The purpose of the present invention is not met. ×010 Does not meet the purpose of the present invention at all. (Margin below)

【Effect of the invention】

As is clear from the present invention, the color density and color stains (static pressure and dynamic friction color stains) are well balanced, and printability is improved.
Manufacturer Bonn pressure-sensitive copying paper with excellent tactility and coatability was obtained. A further unintended effect is that the amount of binder used can be reduced.

Claims (1)

[Scope of Claims] 1. Basically, in Manufacturer Bonn pressure-sensitive copying paper, which is made by coating and drying a coating liquid containing microcapsules and latex containing a coloring agent, associative properties are present in the coating liquid. Manufacturer Bonn's pressure-sensitive copying paper is characterized by the use of polymeric compounds. 2. The associative polymer compound contains at least 2 in the polymer.
2. The pressure-sensitive copying paper according to claim 1, which is a water-soluble polymer or polymer emulsion having hydrophobic groups localized in more than one location. 3. The Manufacturer's Bonn pressure-sensitive copying paper according to claim 1, wherein the associative polymer compound is a water-soluble polymer or polymer emulsion having hydrophobic groups localized at least at both ends of the polymer. 4. The pressure-sensitive copying paper manufactured by Manufacturer Bonn according to claim 1, 2 or 3, wherein the associative polymer compound is of an alkali thickening type.