JPH07144475A - Recording self-adhesive paper - Google Patents

Abstract

PURPOSE:To obtain recording self-adhesive paper mainly utilizing thermal record ing or pressure-sensitive recording, excellent in preservability and low temp. adhesive aptitude, hard to cause a spot of printing even during long-term preser vation before the use as a label, excellent in printing preservability even when the label is bonded to a wrap containing a plasticizer and showing sufficient adhesion even to an adhererd of low temp. CONSTITUTION:A self-adhesive layer and release paper are successively laminated to the rear surface of recording paper wherein a recording layer utilizing the color forming reaction of a basis dye and a coupler is provided on the single surface of base paper and the self-adhesive forming the self-adhesive layer is composed of an acrylic copolymer prepared by emulsifying and copolymerizing a (meth)acryllc ester monomer by using only an anionic surfactant.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pressure-sensitive adhesive paper for recording mainly utilizing heat-sensitive recording and pressure-sensitive recording, and more particularly to a pressure-sensitive adhesive recording paper excellent in preservability and low temperature adhesiveness.

[0002]

2. Description of the Related Art Adhesive labels have been processed into labels, stickers, stickers, patches, etc. over a very wide range for commercial use, office use, household use and the like. A general structure of an adhesive label is formed by laminating a surface base material, an adhesive, a release agent, a primer and a release base material. Paper on the surface substrate,
Synthetic paper, film, metal foil, etc. and their composites are used. As the release substrate, high-density base paper such as glassine paper, clay-coated paper, polyethylene laminated base paper, etc. are used as adhesives such as silicone compounds and fluorine compounds. The one coated with a release agent is used. As the adhesive, various types of adhesives such as rubber type, acrylic type, vinyl ether type emulsion type, solvent type and solventless type are used.

It is to be noted that a thermosensitive recording system or a pressure sensitive recording system in which a recording layer containing both of them is utilized on a base paper by utilizing a color reaction of a colorless or light color basic dye and an organic or inorganic color developing agent. Is well known, and a pressure-sensitive recording system in which one of both components is transferred from the other to obtain a color image is also well known. Of the papers used in such recording systems, thermal recording papers are relatively inexpensive, and the recording equipment is compact and easy to maintain, so it is not only used as a recording medium for facsimiles and various computing equipment, but also widely used. Used in the field. For example, as one of the fields of use thereof, POS (point of sa) at retail stores is
les) The number of cases where it is used as an adhesive label is increasing with the expansion of systemization.

Among these recording papers, the recording paper provided with a recording layer having a self-coloring property is required to have stability of a recorded image. Therefore, a resin having a film forming ability and a chemical resistance is formed on the recording layer. Method of applying aqueous emulsion (JP-A-54-1)
No. 28347) and a method of applying a water-soluble polymer compound such as polyvinyl alcohol (Act. No. Sho 56-12535).
No. 4) has been proposed. However, the pressure-sensitive adhesive paper for recording is often used by being attached to a wrap or the like containing a plasticizer, and there is also a strong demand for preventing the fading of a recorded image by the plasticizer from the back surface. Generally, the pressure-sensitive adhesive paper for recording is provided with an adhesive layer on the back surface of the recording paper and then with a release sheet. Normally, the pressure-sensitive adhesive of the pressure-sensitive adhesive layer is rubber-based, acrylic-based, etc., and when used by sticking to a film that contains a plasticizer, the plasticizer in the film easily causes migration into the pressure-sensitive adhesive layer. , The plasticizer penetrates into the paper and reaches the recording layer. As a result, there is a problem that the storage stability of recording paper is extremely reduced. Further, when the recording pressure-sensitive adhesive paper is stored for a long time before being used as a label, low molecular weight oligomers and plasticizers contained in the pressure-sensitive adhesive layer migrate to the recording layer and cause deterioration of recording performance, There is also a problem that white spots in printing occur.

Therefore, a thermal recording paper provided with a back coat layer mainly composed of a water-soluble polymer has been proposed (Act.
No. 40461 gazette), a sufficient barrier property cannot be obtained, probably because the water-soluble polymer soaks into the base paper, resulting in poor storage stability of recorded images. In addition, problems such as a decrease in whiteness during coating and drying of the back coat layer and an increase in cost due to an increase in manufacturing steps are involved.

[0006]

DISCLOSURE OF THE INVENTION According to the present invention, even if it is stored for a long period of time before being used as a label, white spots in the print are less likely to occur, and further, the label is a wrap containing a plasticizer. It is an object of the present invention to provide a pressure-sensitive adhesive paper for recording, which has excellent print storability even when stuck on a substrate, and exhibits sufficient adhesive performance even on an adherend at a low temperature.

[0007]

Means for Solving the Problems As a result of intensive studies by the present inventors in order to achieve the above object, as a result, an emulsion copolymerization of a pressure-sensitive adhesive constituting a pressure-sensitive adhesive paper for recording using a specific emulsifier. It has been found that by using the above acrylic copolymer, a pressure-sensitive adhesive paper for recording satisfying the above problems can be obtained very efficiently.

According to the present invention, an adhesive layer and a release paper are sequentially laminated on the back surface of a recording paper having a recording layer utilizing a color reaction of a basic dye and a coloring agent on one surface of a base paper. In the adhesive paper for recording, the adhesive that forms the adhesive layer is (meta)
A pressure-sensitive adhesive paper for recording, which is an acrylic copolymer obtained by emulsion copolymerizing an acrylic acid ester monomer using only an anionic surfactant.

[0009]

As described above, in the present invention, the adhesive constituting the adhesive paper for recording is an acrylic copolymer obtained by emulsion copolymerizing a (meth) acrylic acid ester monomer using only an anionic surfactant. Is characterized by. In the case of an adhesive that uses a nonionic surfactant during polymerization, especially a surfactant having a polyoxyethylene chain, if the adhesive paper for recording is stored for a long period of time, remarkable white spots in the print will occur and I can't read it. Examples of the anionic surfactant used in the present invention include fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, alkyl phosphates. , Alkyl allyl sulfate ester salt, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl sulfate ester salt, polyoxyethylene alkylphenyl ether sulfate ester salt, polyoxyethylene alkyl allyl sulfate ester salt, polyoxyethylene alkyl phosphate ester salt, Specific polycarboxylic acid type polymer surfactants, special reaction type surfactants and the like can be mentioned.

Among these, among them, fatty acid salts, alkyl sulfate ester salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfosuccinates, which do not contain a polyoxyethylene moiety among anionic surfactants, More preferably, it is at least one selected from alkyl diphenyl ether disulfonate, alkyl phosphate, alkyl allyl sulfate ester salt, and naphthalene sulfonic acid formalin condensate.

Therefore, the pressure-sensitive adhesive of the present invention is polymerized as follows using only the above-mentioned anionic surfactant.
A polymer containing at least one ester group-containing monomer selected from the group of (meth) acrylic acid esters as a main component is polymerized. This polymer is preferably a polymer having a glass transition temperature (Tg) of 200 to 230K.
This is because if the Tg is lower than 200K, the cohesive force remarkably decreases, and if it is higher than 230K, the adhesive force to an adherend having a low temperature tends to decrease. The above-mentioned polymer is preferably produced by a known emulsion polymerization method (for example, primary charge polymerization method, monomer addition polymerization method, pre-emulsion addition polymerization method, etc.).

The average particle size of the polymer is 0.1 to 0.5 μ.
m, more preferably 0.15 to 0.35 μm. 0.
If it is less than 1 μm, an emulsion having high viscosity and poor coating suitability is produced, and if it is more than 0.5 μm, the adhesive performance of the produced copolymer cannot be sufficiently improved.

As the polymer, a (meth) acrylic acid ester such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,
Butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, (meth )
Lauryl acrylate, at least one selected from stearyl (meth) acrylate as a main component, vinyl acetate, styrene, ethylene, vinyl chloride, vinylidene chloride, ethylenically unsaturated carboxylic acid, a crosslinkable monomer,
A copolymer composed of at least one copolymerizable monomer selected from (α-methyl) styrene, N-alkyl (meth) acrylamide, and (meth) acrylonitrile is preferable. As the ethylenically unsaturated carboxylic acid,
For example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride, monoalkyl maleates having 1 to 12 carbon atoms in the alkyl group, hydroxyethyl (propyl) monomalate, phthalic acid, monoalkyl of itaconic acid. (C1-C12) ester etc. are mentioned.
Examples of the crosslinkable monomer include (meth) acrylic acid-2-hydroxyethyl and (meth) acrylic acid-2.
-Hydroxypropyl, 3-hydroxyethyl (meth) acrylate, hydroxyl group-containing monomers such as polyethylene glycol or polypropylene glycol mono (meth) acrylate, epoxy group-containing monomers such as glycidyl (meth) acrylate, (meth) acrylamide,
A monomer having a -CONH ₂ group or a methylol group such as diacetone acrylamide, divinylbenzene, divinylsilane, diallyl phthalate, cyclopentadiene,
Examples thereof include monomers having two or more ethylenically unsaturated bonds such as methylenebisacrylamide, diallylmaleate and tetraallyloxyethane.

The tensile strength (JIS-K-6301) of the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is 5.0 to 15.0 k.
g / cm ² and elongation rate (JIS-K-6301) is 8
It is preferably from 0 to 1,200% because the wettability to the adherend is improved when the recording pressure-sensitive adhesive paper is adhered to the adherend at low temperature. Furthermore, when the gel fraction of the pressure-sensitive adhesive with respect to tetrahydrofuran is 30 to 50%, when the pressure-sensitive adhesive recording paper is stored for a long period of time, it is possible to suppress migration of low molecular weight substances in the pressure-sensitive adhesive layer into the recording layer. , Does not cause deterioration of recording sensitivity.

The JIS-based base paper that constitutes the recording paper
According to the P-8122 method, the sizing degree of the 20% ethyl alcohol aqueous solution is 30 seconds or more, which is one of the preferred embodiments. As a method of evaluating the barrier property of the base paper,
For example, Gurley air permeability according to JIS-P-8117 method, oil resistance according to JIS-P-8146 method, JIS-
Examples include the Steckigt sizing degree based on the P-8122 method, and none of these results shows a large correlation with the storage stability of the recorded image in the present invention. However, as a result of earnest studies, the present inventors have found that the sizing degree of a 20% ethyl alcohol aqueous solution according to the JIS-P-8122 method is greatly related to the storability of a recorded image in the present invention. By the way, JI of 20% ethyl alcohol aqueous solution
If the sizing degree according to the SP-8122 method is less than 30 seconds, sufficient barrier properties cannot be obtained. Therefore, when the recording pressure-sensitive adhesive paper is attached to a film containing a plasticizer for use, recording is performed. The image may be discolored, or the acrylic acid ester oligomer in the pressure-sensitive adhesive layer may migrate into the recording layer during long-term storage as a label, resulting in a decrease in recording sensitivity. Therefore, by specifying the sizing degree of the 20% ethyl alcohol aqueous solution according to the JIS-P-8122 method of the base paper constituting the recording paper to 30 seconds or more, more excellent results can be obtained.

The sizing degree of the 20% ethyl alcohol aqueous solution described here means the above-mentioned JIS-P-8122.
According to the Steckigt sizing test method specified in.
Specifically, the four circumferences of a 50 mm square test piece were folded inward, floated on a colored 20% ethyl alcohol aqueous solution placed in a petri dish, and the time until three colored spots appeared was measured with a second clock. The number of seconds is the size degree.
A commercially available water-based ink or the like can be used for coloring the ethyl alcohol aqueous solution.

As a base paper satisfying the above requirements, for example, a base paper surface coated with a coating solution containing at least starch and a synthetic sizing agent and dried can be mentioned.
As the starch applied to the surface of the base paper, for example, oxidation-modified starch, enzyme-modified starch, cationized starch, acetylated starch,
Examples thereof include etherified starch, aldehydized starch, hydroxyethylated starch, phosphorylated starch, and pregelatinized starch. The concentration of the starch coating solution is preferably adjusted and used in the range of 5.0 to 15.0% by weight. By the way, if it is less than 5.0% by weight, a sufficient effect cannot be obtained for improving the barrier property, while if it exceeds 15.0% by weight, the paper surfaces are joined together at the time of winding and forming, a so-called blocking phenomenon. Tend to cause.

Examples of the synthetic sizing agent include alkyl ketene dimer type, alkenyl succinic anhydride type, styrene-acrylic type, higher fatty acid type, petroleum resin type sizing agent and rosin type sizing agent. The amount added is 0.1 to 1.0 with respect to 100% by weight of the starch coating solution.
It is preferably used in the range of weight%. By the way, 0.
If it is less than 1% by weight, a sufficient effect for improving the barrier property cannot be obtained. On the other hand, if it exceeds 1.0% by weight, no further effect is observed for improving the barrier property and it is economical. There is little need from all aspects.

These coating solutions are applied by a known method such as a two-roll or metering blade type size press, a gravure coater, a gate roll coater, a bill blade and a short dwell coater.
The coating amount is 3.0 to 8.0 g / m ^{2 on} both sides as a dry weight.
The degree is desirable. If necessary, smoothness may be imparted by a smoothing device such as a calender or a super calender.

Examples of the base paper include wood pulp such as softwood and hardwood, non-wood pulp such as kenaf, bamboo and hemp, synthetic pulp such as polyester and polyolefin, organic fiber such as synthetic fiber, glass fiber and ceramics. Examples thereof include those using inorganic fibers such as fibers as a raw material of paper stock. And, in this paper material, for example, talc, kaolin, clay, calcined kaolin, heavy calcium carbonate, light calcium carbonate, magnesium carbonate, titanium dioxide,
Aluminum hydroxide, calcium hydroxide, magnesium hydroxide, zinc hydroxide, magnesium sulfate, calcium silicate, white carbon, aluminosilicate, silica, sericite, bentonite, smectite, polystyrene resin particles, urea formalin resin particles, minute hollow particles Known publicly known inorganic mineral fillers and organic synthetic fillers, and various anionic, nonionic, cationic, or amphoteric retention aids that have been conventionally used within a range that does not impair the desired effects of the present invention. An internally added auxiliary agent for papermaking such as a drainage improving agent, a paper strength enhancer or an internally added sizing agent is appropriately selected and used as necessary. Examples of the internal additive for papermaking include A
1, polyvalent metal compounds such as Fe, Sn and Zn (basic aluminum compounds such as aluminum sulfate, aluminum chloride, sodium aluminate, basic aluminum chloride and basic polyaluminum hydroxide, and alumina sol easily dispersible in water) Water-soluble aluminum compound, or ferrous sulfate,
Ferric chloride, etc.), various sizing agents (alkyl ketene dimer type, alkenyl succinic anhydride type, styrene-acrylic type, higher fatty acid type, petroleum resin type sizing agent, rosin type sizing agent, etc.) and various starches, poly Acrylamide, urea resin, melamine resin, epoxy resin, polyamide resin,
Polyamide / polyamine resin, polyethyleneimine, polyamine, plant gum, polyvinyl alcohol, latex, polyethylene oxide, hydrophilic crosslinked polymer particle dispersion and derivatives thereof, colloidal silica, various compounds such as bentonite, dyes, optical brighteners,
Examples thereof include pH adjusters, defoamers, pitch control agents, slime control agents and the like.

The papermaking method is also not particularly limited. For example, an acidic papermaking method having a papermaking pH of about 4.5, an alkaline filler such as calcium carbonate as a main component,
It can be applied to all papermaking methods such as a neutral papermaking method in which the papermaking pH is weakly acidic to about 6 to weakly alkaline to about 9, and the papermaking machine can be a Fourdrinier paper machine, a twin wire papermaking machine, a round wire papermaking machine,
A Yankee paper machine or the like can be used as appropriate.

Examples of the basic dye constituting the recording layer in the present invention include various known colorless or light-colored basic dyes such as 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalic acid. 3,3-bis (p-dimethylaminophenyl) phthalide, 3- (p-
Dimethylaminophenyl) -3- (1,2-dimethylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindol-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) -6-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -6-dimethylamino Triallylmethane dyes such as phthalide and 3-p-dimethylaminophenyl-3- (1-methylpyrrol-3-yl) -6-dimethylaminophthalide, 4,4'-bis-dimethylaminobenzhydryl Diphenylmethane dyes such as benzyl ether, N-halophenyl-leuco auramine, N-2,4,5-trichlorophenyl leuco auramine, thiazine dyes such as benzoyl leuco methylene blue and p-nitrobenzoyl leuco methylene blue, 3-methyl- Spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran,
3-phenyl-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphtho-
Spiro dyes such as (6′-methoxybenzo) spiropyran and 3-propyl-spiro-dibenzopyran, lactam dyes such as rhodamine-B anilinolactam, rhodamine (p-nitroanilino) lactam and rhodamine (o-chloroanilino) lactam , 3-dimethylamino-7-
Methoxyfluorane, 3-diethylamino-6-methoxyfluorane, 3-diethylamino-7-methoxyfluorane, 3-diethylamino-7-chlorofluorane,
3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-6,7-dimethylfluorane, 3- (N-ethyl-p-toluidino) -7-methylfluorane, 3-diethylamino-7- N-acetyl-
N-methylaminofluorane, 3-diethylamino-7
-N-methylaminofluorane, 3-diethylamino-
7-dibenzylaminofluorane, 3-diethylamino-7-N-methyl-N-benzylaminofluorane, 3
-Diethylamino-7-N-chloroethyl-N-methylaminofluorane, 3-diethylamino-7-N-diethylaminofluorane, 3- (N-ethyl-p-toluidino) -6-methyl-7-phenylaminofluorane ,
3- (N-ethyl-p-toluidino) -6-methyl-7
-(P-toluidino) fluorane, 3-diethylamino-6-methyl-7-phenylaminofluorane, 3-diethylamino-7- (2-carbomethoxy-phenylamino) fluorane, 3- (N-cyclohexyl-N-methyl) Amino) -6-methyl-7-phenylaminofluorane, 3-pyrrolidino-6-methyl-7-phenylaminofluorane, 3-piperidino-6-methyl-7-phenylaminofluorane, 3-diethylamino-6- Methyl-7-xylidinofluorane, 3-diethylamino-
7- (o-chlorophenylamino) fluorane, 3-dibutylamino-7- (o-chlorophenylamino) fluorane, 3-pyrrolidino-6-methyl-7-p-butylphenylaminofluorane, 3-diethylamino-7-
(O-Fluorophenylamino) fluorane, 3-dibutylamino-7- (o-fluorophenylamino) fluorane, 3-dibutylamino-6-methyl-7-phenylaminofluorane, 3-dipentylamino-6-methyl- 7-Phenylaminofluorane, 3- (N-methyl-Nn-amyl) amino-6-methyl-7-phenylaminofluorane, 3- (N-ethyl-Nn-amyl) amino-6- Methyl-7-phenylaminofluorane, 3- (N-ethyl-N-isoamyl) amino-6-
Methyl-7-phenylaminofluorane, 3- (N-methyl-Nn-hexyl) amino-6-methyl-7-phenylaminofluorane, 3- (N-ethyl-Nn-)
Hexyl) amino-6-methyl-7-phenylaminofluorane, 3- (N-ethyl-N-β-ethylhexyl) amino-6-methyl-7-phenylaminofluorane and other fluorane dyes are exemplified. Two or more kinds of these basic dyes can be used in combination, if necessary.

Various materials are known as inorganic or organic acidic substances which develop color upon contact with a basic dye as described above. For example, activated clay, attapulgite, colloidal silica, inorganic silicate and other inorganic acidic substances, 4 −tert−
Butylphenol, 4-hydroxydiphenoxide, α
-Naphthol, β-naphthol, 4-hydroxyacetophenol, 4-tert-octylcatechol, 2,2 '
-Dihydroxydiphenol, 4,4'-isopropylidene bis (2-tert-butylphenol), 4,4'-
sec-butylidene diphenol, 4-phenylphenol, 4,4'-isopropylidene diphenol, 2,2
-Bis (4-hydroxyphenyl) -4-methylpentane, 2,2'-methylenebis (4-chlorophenol), hydroquinone, 4,4'-cyclohexylidene diphenol, 4,4'-dihydroxydiphenyl sulfide, hydroquinone mono Benzyl ether, 4-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, dimethyl 4-hydroxyphthalate, 4-hydroxy Methyl benzoate, propyl 4-hydroxybenzoate,
4-Hydroxybenzoic acid-sec-butyl, 4-hydroxybenzoic acid pentyl, 4-hydroxybenzoic acid phenyl, 4-hydroxybenzoic acid benzyl, 4-hydroxybenzoic acid tolyl, 4-hydroxybenzoic acid chlorophenyl, 4-hydroxybenzoic acid Phenylpropyl, phenethyl 4-hydroxybenzoate, p-chlorobenzyl 4-hydroxybenzoate, 4-hydroxybenzoic acid-p-
Phenolic compounds such as methoxybenzyl, novolac type phenolic resin, phenolic polymer, benzoic acid, p-
tert-Butylbenzoic acid Trichlorobenzoic acid, terephthalic acid, 3-sec-butyl-4-hydroxybenzoic acid, 3-
Cyclohexyl-4-hydroxybenzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid, 3-tert-butylsalicylic acid, 3-benzylsalicylic acid, 3- (α-methylbenzyl) salicylic acid, 3-chloro-5- (α -Methylbenzyl) salicylic acid, 3,5-di-tert-butylsalicylic acid, 3-phenyl-5- (α, α-dimethylbenzyl) salicylic acid, 3,5-di-α-methylbenzylsalicylic acid, 4- (3- aromatic carboxylic acids such as p-tolylsulfonylpropyloxy) salicylic acid, 4,4′-dihydroxydiphenyl sulfone, 4-hydroxy-4′-
Isopropyloxydiphenyl sulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, 4-hydroxy-4'-methyldiphenyl sulfone, 3,4-dihydroxydiphenyl sulfone, 3,4-dihydroxy-
4-hydroxydiphenylsulfone derivative such as 4'-methyldiphenylsulfone, bis (3-tert-butyl-4)
-Hydroxy-6-methylphenyl) sulfide, bis (2-methyl-4-hydroxy-6-tert-butylphenyl) sulfide, di (4-hydroxyphenylthioethoxy) methane, 1,5-di (4-hydroxyphenyl) Thio) -3-oxapentane and other sulfide derivatives, as well as salts of these phenolic compounds and aromatic carboxylic acids with polyvalent metals such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin and nickel Further, organic acid substances such as zinc thiocyanate antipyrine complex are exemplified.

The pressure-sensitive adhesive paper for recording of the present invention has a recording layer utilizing the color reaction of the basic dye and the color developing agent as described above. The recording layer is a heat-sensitive recording layer and a pressure-sensitive recording layer. It may be any of the recording layers.

When a thermosensitive recording paper is used as the recording paper, the use ratio of the basic dye and the color former in the recording layer is appropriately selected according to the types of the basic dye and the color former used. Although not particularly limited, it is generally 1 to 50 parts by weight, preferably 2 to 10 parts by weight with respect to 1 part by weight of the basic dye.
About a part by weight of the coloring agent is used. A coating material containing these substances is generally prepared by dispersing water and a dye or a coloring agent together or separately with a stirring / pulverizing machine such as a ball mill, an attritor, or a sand mill using water as a dispersion medium.

Starch, hydroxyethylcellulose, methylcellulose, and
Carboxymethyl cellulose, gelatin, casein, gum arabic, polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, diisobutylene / maleic anhydride copolymer salt, styrene / maleic anhydride copolymer salt, ethylene / acrylic Acid copolymer salt, styrene / acrylic acid copolymer salt, styrene / butadiene copolymer emulsion,
Examples thereof include urea resin, melamine resin, amide resin and the like.
In addition, various auxiliary agents can be added to the coating liquid as necessary, and examples thereof include dispersants such as sodium dioctylsulfosuccinate, sodium dodecylbenzenesulfonate, sodium lauryl alcohol sulfate, and fatty acid metal salts. , Zinc stearate, calcium stearate, polyethylene wax, carnauba wax, paraffin wax, ester wax, and other waxes, benzophenone-based ultraviolet absorbers, other defoamers, fluorescent dyes,
A coloring dye or the like is appropriately added.

It is also possible to use various pigments in combination, for example, inorganic pigments such as kaolin, clay, calcium carbonate, calcined clay, calcined kaolin, titanium oxide, diatomaceous earth, fine anhydrous silica, activated clay and styrene microballs. , Nylon powder, polyethylene powder, urea / formalin resin filler, organic pigments such as raw starch particles, and the like.

Further, a sensitizer may be used in combination depending on the purpose. Specific examples of the sensitizer include caproic acid amide, capric acid amide, palmitic acid amide, stearic acid amide, oleic acid amide, erucic acid amide, linoleic acid amide, linolenic acid amide, N-methylstearic acid amide, and stearin. Acid anilide, N-methyloleic acid amide, benzanilide, linoleic acid anilide, N-ethylcapric acid amide, N-butyllauric acid amide, N-octadecylacetamide, N-oleinacetamide, N-oleylbenzamide, N-stearylcyclohexylamide , Polyethylene glycol, 1-benzyloxynaphthalene, 2-benzyloxynaphthalene, 1-hydroxynaphthoic acid phenyl ester, 1,2-diphenoxyethane, 1,4-diphenoxybutane, 1,2-bis (3 Methylphenoxy) ethane, 1,2-bis (4-methoxyphenoxy) ethane, 1-phenoxy-2- (4-chlorophenoxy) ethane, 1-phenoxy-2- (4-methoxyphenoxyethane, 1- (2- Methylphenoxy) -2- (4-methoxyphenoxy) ethane, terephthalic acid dibenzyl ester, oxalic acid dibenzyl ester, oxalic acid di (4
-Methylbenzyl) ester, p-benzyloxybenzoic acid benzyl ester, p-benzylbiphenyl, 1,
Compounds such as 5-bis (p-methoxyphenoxy) -3-oxa-pentane, 1,4-bis (2-vinyloxyethoxy) benzene, p-biphenyl-p-tolyl ether and benzyl-p-methylthiophenyl ether are available. It is illustrated. The amount of these sensitizers used is not particularly limited,
Generally, it is desirable to adjust the amount of the coloring agent in the range of about 4 parts by weight or less relative to 1 part by weight.

The method for forming the recording layer is not particularly limited. For example, the recording layer coating liquid is applied to the support by a suitable coating method such as an air knife coater, a varibar blade coater, a pure blade coater, a short dwell coater, and dried. Formed. The coating amount of the coating liquid is not particularly limited, and usually ² to 12 g / m ² in dry weight, preferably 3 to
It is adjusted within the range of about 10 g / m ² .

On the other hand, when a pressure-sensitive recording paper is used as the recording paper, the above-mentioned basic dyes are generally synthetic oils such as alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane and alkylated terphenyl, cotton oil,
After dissolving it in a solvent consisting of vegetable oil such as castor oil, animal oil, mineral oil or a mixture thereof, the microcapsules can be contained by various capsule production methods such as coacervation method, interfacial polymerization method and in-situ method. used. Then, the coating liquid prepared by dispersing the basic dye-containing microcapsules and the coloring agent separately or together in a binder is laminated or single layer on the same or different base paper to form a pressure-sensitive recording layer. To be done. Then, in the recording layer coating liquid, in addition to the binder as described above, if necessary, cellulose powder, starch particles, talc, a capsule protective agent such as calcined kaolin, a dispersant, an antifoaming agent, a preservative, and a fluorescent agent. Dyes, colored dyes, white pigments, etc. can also be added.

It is preferable to provide a protective layer on the self-coloring recording layer of the recording paper used in the present invention because the storage stability of recording is further improved. As the water-soluble or water-dispersible polymer used for forming the protective layer, for example, polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol,
Silicon-modified polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, starch and its derivatives, casein, sodium alginate, polyvinyl pyrrolidone, polyacrylamide, styrene-maleic acid copolymer salt, polyurethane resin, urea resin, melamine resin, polyamide resin, Examples thereof include synthetic polymer emulsions such as epichlorohydridone modified polyamide resin, styrene / butadiene type emulsion, styrene / acrylic acid ester type emulsion, and acrylic acid ester type emulsion. Of course, two or more kinds of these polymer compounds may be mixed and used. Further, among these polymer compounds, particularly acetoacetyl group-modified polyvinyl alcohol and silicon-modified polyvinyl alcohol,
It is preferably used because it forms a strong resin film.

A pigment may be added to the protective layer,
Specific examples thereof include inorganic pigments such as calcium carbonate, zinc oxide, aluminum oxide, titanium dioxide, silicon dioxide, aluminum hydroxide, barium sulfate, zinc sulfate, talc, kaolin, clay, calcined kaolin, calcined clay, and colloidal silica. Examples thereof include styrene microballs, nylon powder, polyethylene powder, urea / formalin resin filler, and organic pigments such as raw starch particles.
It is generally desirable to adjust the amount used in the range of about 20 to 500 parts by weight with respect to 100 parts by weight of the polymer compound.

Further, in the coating liquid for forming the protective layer, zinc stearate, calcium stearate,
Lubricants such as polyethylene wax, carnauba wax, paraffin wax and ester wax, surfactants such as sodium dioctyl sulfosuccinate, and various auxiliaries such as defoaming agents can be appropriately added. Further, a curing agent such as glyoxal, boric acid, dialdehyde starch, or an epoxy compound can be added to further improve water resistance.

The coating solution for protective layer thus prepared is coated on the recording layer by a suitable coating device. If the coating amount is less than 1 g / m ² on a dry weight basis, the storage stability of printing is improved. It becomes insufficient and sticking to the thermal head easily occurs. On the other hand, since the recording sensitivity Kosu a 20 g / m ² tends to be remarkably lowered, generally from 1 to 20 g / m ^2, preferably is desired to be adjusted in the range of about 2 to 10 g / m ^2.

Various known techniques in the field of recording paper production are required, such as providing an undercoat layer between the recording layer and the specific base paper according to the present invention, and performing a super calendering treatment after forming each layer. It can be added accordingly.
On the back surface of the recording paper thus obtained, an adhesive layer,
By providing a release paper and a release paper, a pressure-sensitive adhesive paper for recording can be obtained.

The method of forming the pressure-sensitive adhesive paper for recording is not particularly limited, and after the pressure-sensitive adhesive layer is formed by applying the pressure-sensitive adhesive on the surface of the release agent layer of the release paper and drying it according to a conventional method, The back surface of the recording paper is stuck on the pressure-sensitive adhesive layer for finishing. As the release paper, high-density base paper such as glassine paper, clay-coated paper, kraft paper, or polylaminated paper obtained by laminating polyethylene or the like on high-quality paper, etc., with fluororesin or silicone resin in a dry weight of 0.05 to It is used after being coated with about 3 g / m ² and having a release agent layer formed by heat curing or ionizing radiation curing.

As a method for applying the pressure-sensitive adhesive, for example, a roll coater, a knife coater, a bar coater, a slot die coater or the like is used, and the coating amount is 5 to 50 in dry weight.
It is adjusted within the range of about g / m ² .

[0038]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
In the examples, parts and% are “parts by weight” unless otherwise specified.
"% By weight" is shown.

Example 1 "Production of base paper" NBKP (CSF 550 ml) 2
Kaolin was added to a pulp slurry containing 5 parts and 75 parts of LBKP (C.S.F. 560 ml) with a paper ash content of 5.0%.
Then, 1.5% of rosin size and 2.0% of aluminum sulfate were added to the absolutely dry pulp as a sizing agent to prepare a paper stock. The stock was paper-made by a fourdrinier cylinder dryer paper machine and processed by a 4-stage super calender to obtain a base paper of 58 g / m ² . The sizing degree of the 20% ethyl alcohol aqueous solution of this base paper was 10 seconds.

"Production of thermal recording paper" Preparation of solution A 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-phenylaminofluorane 10 parts, 5% aqueous methylcellulose solution 5 parts, and water 40 parts The composition was pulverized with a sand mill until the average particle size became 3 μm.

Preparation of solution B A composition consisting of 30 parts of 4-hydroxy-4'-isopropyloxydiphenyl sulfone, 5 parts of a 5% aqueous solution of methylcellulose, and 80 parts of water was pulverized with a sand mill until the average particle size became 3 μm.

Preparation of Solution C 1,2-di (3-methylphenoxy) ethane 20 parts, 5
% Methylcellulose aqueous solution (5 parts) and water (55 parts) were pulverized with a sand mill until the average particle size became 3 μm.

Preparation of Solution D 200 parts of 10% acetoacetyl group-modified polyvinyl alcohol aqueous solution, 100 parts of kaolin (trade name: UW-90, manufactured by EMC), 30 parts of 30% zinc stearate dispersion,
A composition comprising 100 parts of water and 100 parts of water was mixed and stirred to prepare a coating liquid.

A coating solution obtained by mixing 55 parts of A solution, 115 parts of B solution, 80 parts of C solution, 80 parts of 10% polyvinyl alcohol aqueous solution, and 35 parts of calcium carbonate on the surface of the obtained base paper and stirring. Was coated and dried so that the coating amount after drying was 6 g / m ² to form a recording layer. Liquid D was applied onto this recording layer so that the coating amount after drying was 5 g / m ^2, and was then calendered to obtain a thermosensitive recording paper.

"Production of pressure-sensitive adhesive" 93 parts of 2-ethylhexyl acrylate, 6.5 parts of vinyl acetate, 0.1 part of acrylic acid.
5 parts of the monomer mixture was added and stirred into an emulsifier aqueous solution containing 1.0 part of an anionic surfactant polyoxyethylene alkylphenyl ether sulfate (trade name: Rebenol WZ / manufactured by Kao) and 30 parts of ion-exchanged water. To give a pre-emulsion.

In a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, 1.0 part of an anionic surfactant polyoxyethylene alkylphenyl ether sulfate (trade name: Rebenol WZ / manufactured by Kao Corporation) and acetic acid Sodium 0.3
Parts, 0.8 parts of potassium persulfate, and 30 parts of ion-exchanged water were charged, and the temperature of the liquid was raised to 75 ° C. with stirring while passing nitrogen gas.
0 was added to carry out initial polymerization for 30 minutes, and then the remaining amount was added dropwise over 4 hours and the polymerization was carried out while maintaining the temperature at 75 to 80 ° C. After the completion of the dropping, the temperature was further maintained at 80 ° C. to carry out the late polymerization to obtain a copolymer emulsion. Then, this copolymer emulsion is treated with aqueous ammonia (concentration 25%).
After neutralizing with, thickener (Brand name: Bissurf 1400 /
(Manufactured by Kao Corporation) was mixed to adjust the viscosity to 5000 cps to obtain an adhesive.

"Production of adhesive paper for thermal recording" 63 g / tsubo
m ² glassine paper with silicone release agent (trade name: KS-
3760 / Shin-Etsu Chemical Co., Ltd.) dry weight 0.9 g / m ²
To obtain a release paper.
The above-mentioned acrylic pressure-sensitive adhesive was applied to the release layer surface of this release paper with a reverse roll coater so as to have a dry weight of 25 g / m ^2, and dried to form a pressure-sensitive adhesive layer. Next, the back surface of the thermosensitive recording paper was overlaid on the surface of the pressure-sensitive adhesive layer and laminated with a press roll to obtain a thermosensitive recording pressure-sensitive adhesive paper.

Example 2 In Example 1, alkylbenzene sulfonate (trade name: Neoperex No. 6 powder / manufactured by Kao Corporation) was used as an anionic surfactant for polymerizing the pressure-sensitive adhesive.
An adhesive paper for heat-sensitive recording was obtained in the same manner as in Example 1 except that the coating was performed with a die coater (trade name: Lip type coater / manufactured by Hirano Techseed).

Example 3 In the production of the base paper of Example 1, NBKP (C.S.
F. 15 parts, LBKP (C.S.F. 48)
Kaolin is added to a pulp slurry containing 85 parts (0 ml) so that the paper ash content is 9.5%, and rosin size is used as a sizing agent in an amount of 1.0 relative to the absolutely dry pulp.
%, And aluminum sulfate 1.5% were added to prepare a paper material.
This stock material was made into paper by a Fourdrinier cylinder cylinder paper machine, and a solution of synthetic sizing agent was added to an oxidized starch solution having a concentration of 9.0%.
The coating solution obtained by adding 5% was applied and dried with a size press so that the dry weight was 5 g / m ^2, and then treated with a 4-stage super calender to produce 58 g / m ² of base paper. The size of the 20% ethyl alcohol aqueous solution of this base paper is 2
It was 00 seconds. Example 2 except that this base paper was used
A thermosensitive recording adhesive paper was obtained in the same manner as in.

Example 4 In the production of the support of Example 1, NBKP (CS
F. 560 ml) 25 parts, LBKP (C.S.F. 48)
(0 ml) 75 parts was used, and the same size press coating solution as in Example 3 was used, except that the size press coating amount was 3 g / m ² in terms of dry weight. I got a base paper. The sizing degree of a 20% ethyl alcohol aqueous solution of this base paper was 50 seconds. Using this base paper, a thermal recording paper was obtained in the same manner as in Example 1.

"Production of pressure-sensitive adhesive" A monomer mixture of 45 parts of 2-ethylhexyl acrylate, 48 parts of butyl acrylate, 6.5 parts of methyl methacrylate and 0.5 part of methacrylic acid was mixed with an anionic surfactant alkyl. Sulfate ester salt (trade name: Emar 10 powder / manufactured by Kao) 1.0
Parts, and 30 parts of ion-exchanged water in an aqueous emulsifier solution and stirred to form a pre-emulsion.

In a reaction vessel equipped with a stirrer, a thermometer and a cooling tube, 1.0 part of an anionic surfactant alkylsulfosuccinate (trade name: Perex OT-P / manufactured by Kao Corporation),
Sodium acetate 0.3 parts, ammonium persulfate 0.8
Parts, 30 parts of ion-exchanged water, an emulsifier aqueous solution was charged, the temperature of the liquid was raised to 75 ° C. while stirring with nitrogen gas, 5/100 of the pre-emulsion was added, and initial polymerization was carried out for 30 minutes, and then the rest. Was added dropwise over 4 hours and maintained at 75 to 80 ° C to carry out polymerization. After the dropping was completed, the temperature was further maintained at 80 ° C. to carry out a late polymerization to obtain a copolymer emulsion. After the copolymer emulsion was neutralized with aqueous ammonia (concentration 25%), a thickener (trade name: Bissurf 1400, manufactured by Kao Corporation) was added to adjust the viscosity to 4500 cps to obtain an adhesive. .

A heat-sensitive recording pressure-sensitive adhesive paper was obtained in the same manner as in Example 1 except that the above heat-sensitive recording paper and the pressure-sensitive adhesive were used.

Example 5 "Production of pressure-sensitive adhesive" A monomer mixture of 93 parts of butyl acrylate, 6.5 parts of methyl methacrylate and 0.5 part of acrylic acid was mixed with a special reaction type anionic surfactant (trade name: Latemur). S-180A / manufactured by Kao) 1.0 part, ion-exchanged water 3
It was added to 0 parts of an emulsifier aqueous solution and stirred to form a pre-emulsion.

In a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, 1.0 part of an anionic surfactant alkylsulfosuccinate (trade name: Perex OT-P / manufactured by Kao Corporation),
Sodium acetate 0.3 parts, ammonium persulfate 0.8
Parts, 30 parts of ion-exchanged water, an emulsifier aqueous solution was charged, the temperature of the liquid was raised to 75 ° C. while stirring with nitrogen gas, 5/100 of the pre-emulsion was added, and initial polymerization was carried out for 30 minutes, and then the rest. Was added dropwise over 4 hours and maintained at 75 to 80 ° C. to carry out polymerization. After the dropping was completed, the temperature was further maintained at 80 ° C. to carry out a late polymerization to obtain a copolymer emulsion. After the copolymer emulsion was neutralized with aqueous ammonia (concentration 25%), a thickener (trade name: Bissurf 1400, manufactured by Kao Corporation) was added to adjust the viscosity to 4500 cps to obtain an adhesive. . In the production of the pressure-sensitive adhesive recording paper of Example 1, a heat-sensitive recording adhesive paper was obtained in the same manner as in Example 1 except that the above-mentioned pressure-sensitive adhesive was used as the acrylic pressure-sensitive adhesive.

Example 6 "Production of adhesive" 2-Ethylhexyl acrylate 83
Parts, 10 parts of methyl methacrylate, 6.5 parts of vinyl acetate,
Acrylic acid 0.5 parts of the monomer mixture was added to an anionic surfactant alkyldiphenyl ether disulfonate (trade name: Perex SS-L / manufactured by Kao Corporation) 1.0 parts and ion exchange water 30 parts in an emulsifier aqueous solution. A pre-emulsion was prepared by adding and stirring.

In a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, 0.8 part of an anionic surfactant dialkylsulfosuccinate (trade name: Perex CS / manufactured by Kao) and 0.3 part of sodium acetate , 0.8 parts of potassium persulfate and 30 parts of ion-exchanged water were charged, and the temperature of the liquid was raised to 75 ° C. while stirring with nitrogen gas, and 5/100 of the pre-emulsion was added for 30 minutes. Initial polymerization is carried out, and then the remaining amount is added dropwise over 4 hours,
Polymerization was carried out while maintaining the temperature at 80 ° C. 80 more after dropping
The temperature was maintained at ℃ to carry out the latter-stage polymerization to obtain a copolymer emulsion. Then, this copolymer emulsion was neutralized with ammonia water (concentration 25%), and then a thickener (trade name: Bissurf 1400 / manufactured by Kao Corporation) was added to obtain a viscosity of 4000c.
The pressure-sensitive adhesive was obtained by adjusting to ps. In the production of the pressure-sensitive adhesive recording paper of Example 1, a heat-sensitive recording adhesive paper was obtained in the same manner as in Example 1 except that the above-mentioned pressure-sensitive adhesive was used as the acrylic pressure-sensitive adhesive.

Comparative Example 1 In Example 1, 2.0 parts of a nonionic surfactant polyoxyethylene alkyl ether (trade name: Emulgen 920 / manufactured by Kao Corporation) was used as the surfactant for the pressure-sensitive adhesive polymerization, and an anionic interface. Activator Sodium polyoxyethylene alkyl ether sulfate (Product name: Rebenol WX / Kao Corporation)
An adhesive paper for heat-sensitive recording was obtained in the same manner as in Example 1 except that 1.2 parts was used.

Comparative Example 2 The same procedure as in Example 1 was carried out except that 3.5 parts of the nonionic surfactant polyoxyethylene alkyl ether (trade name: Emulgen 920 / manufactured by Kao Corporation) was used as the surfactant during the adhesive polymerization. A thermosensitive recording adhesive paper was obtained in the same manner as in Example 1.

Comparative Example 3 “Production of pressure-sensitive adhesive” 2-ethylhexyl acrylate 8
A monomer mixture of 9.0 parts, methyl methacrylate 10.5 parts, and acrylic acid 0.5 parts was added with nonionic surfactant polyoxyethylene alkyl ether (trade name: Emulgen 930 / Kao Corporation) 2.5 parts, It was added to 30 parts of ion-exchanged water in an emulsifier aqueous solution and stirred to form a pre-emulsion.

A nonionic surfactant polyoxyethylene alkyl ether (trade name: Emulgen 930 / manufactured by Kao) is placed in a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube.
1.5 parts, 0.3 parts of sodium acetate, 0.8 parts of potassium persulfate, 30 parts of ion-exchanged water were charged into the emulsifier aqueous solution, and the temperature of the solution was raised to 75 ° C. while stirring with nitrogen gas. 30 by adding 5/100 of emulsion
Initial polymerization was carried out for 1 minute, and then the remaining amount was added dropwise over 4 hours and the polymerization was carried out while maintaining the temperature at 75 to 80 ° C. After the dropping was completed, the temperature was further maintained at 80 ° C. to carry out a late polymerization to obtain a copolymer emulsion. Then, this copolymer emulsion was neutralized with aqueous ammonia (concentration 25%), and then a thickener (trade name: Bissurf 1400 / manufactured by Kao Corporation) was added to adjust the viscosity to 4000 cps to obtain an adhesive. . In the production of the pressure-sensitive adhesive recording paper of Example 1, a heat-sensitive recording adhesive paper was obtained in the same manner as in Example 1 except that the above-mentioned pressure-sensitive adhesive was used as the acrylic pressure-sensitive adhesive.

Comparative Example 4 "Production of pressure-sensitive adhesive" 2-ethylhexyl acrylate 8
A monomer mixture of 9.0 parts, methyl methacrylate 10.5 parts, and acrylic acid 0.5 parts was added to a nonionic surfactant polyoxyethylene alkyl ether (product name: Emulgen 9
20 / manufactured by Kao) 1.0 part, anionic surfactant alkylsulphosuccinate (product name: Perex OT-P / manufactured by Kao) 0.5 part, ion-exchanged water 30 parts in an emulsifier aqueous solution A pre-emulsion was prepared by adding and stirring.

A nonionic surfactant polyoxyethylene alkyl ether (trade name: Emulgen 930 / manufactured by Kao) is placed in a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube.
1.5 parts, anionic surfactant alkyl sulfosuccinate (product name: Perex OT-P / manufactured by Kao) 0.5 parts,
An emulsifier aqueous solution containing 0.3 part of sodium acetate, 0.8 part of potassium persulfate, and 30 parts of ion-exchanged water was charged, and the temperature of the liquid was raised to 75 ° C. with stirring while passing nitrogen gas. Was added to carry out initial polymerization for 30 minutes, and then the remaining amount was added dropwise over 4 hours.
Polymerization was carried out while maintaining at -80 ° C. 8 more after dropping
The temperature was maintained at 0 ° C. and the latter-stage polymerization was carried out to obtain a copolymer emulsion. Then, this copolymer emulsion was neutralized with ammonia water (concentration 25%), and then a thickener (trade name: Bissurf 1400 / manufactured by Kao Corporation) was added to obtain a viscosity of 4000.
The pressure-sensitive adhesive was obtained by adjusting to cps. In the production of the pressure-sensitive adhesive recording paper of Example 1, a heat-sensitive recording adhesive paper was obtained in the same manner as in Example 1 except that the above-mentioned pressure-sensitive adhesive was used as the acrylic pressure-sensitive adhesive.

Example 7 "Production of base paper" NBKP (CSF 450 ml) 2
To a pulp slurry containing 0 part and 80 parts of LBKP (C.S.F. 450 ml), talc (NK-80: manufactured by Chuo Kaolin Co., Ltd.) was added so that the paper ash content was 6%, and the sizing agent was added. As a result, 1.4% of rosin size (SPE: manufactured by Arakawa Chemical Co., Ltd.) was added to the absolutely dry pulp. After adjusting the pH of this stock material to 4.6 with aluminum sulfate, paper was made with a Fourdrinier cylinder cylinder paper machine, and oxidized starch (Ace A: Oji Corn Starch Co., Ltd.) was made with a size press machine inside the paper machine. A size press of the aqueous solution was performed so as to be 1.5 g / m ^2, and the paper was passed through a machine calender to obtain a base paper having a basis weight of 40 g / m ² . 20% of this base paper
The sizing degree of the ethyl alcohol aqueous solution was 10 seconds.

"Production of Pressure Sensitive Recording Paper" Preparation of Liquid A 3 parts of crystal violet lactone was dissolved in 100 parts of diisopropyl naphthalene, and this was emulsified and dispersed in 400 parts of a 5% aqueous solution of acid-treated gelatin at 55 ° C. 5 more
% Aqueous solution of gum arabic was added and the pH of the system was adjusted to 4 by adding 5% aqueous acetic acid solution while maintaining the liquid temperature at 55 ° C.
It was adjusted to 0, and the liquid temperature was cooled to 10 ° C. while continuing stirring. Next, 20 parts of 10% formalin aqueous solution is added, and further 10% sodium hydroxide aqueous solution is added to adjust the pH of the system to 1
It was adjusted to 0.0 and then stirred for 10 hours to obtain a capsule dispersion liquid. Next, 15 parts of pulp powder and 10 parts of acrylic acid ester-acrylic acid copolymer (average degree of polymerization of 300 to 400) were added to the thus obtained capsule dispersion liquid to obtain a capsule coating liquid.

Preparation of Liquid B 100 parts of acid clay and 4 parts of sodium hydroxide were sufficiently dispersed in 400 parts of water, 20 parts of styrene-butadiene copolymer latex (solid content 50%) was added, and further dialkylsulfosuccinic acid was added. Sodium (trade name: Perex O
TP, manufactured by Kao Co., Ltd.) was added to prepare a colorant coating liquid.

Formation of Pressure Sensitive Recording Layer Liquid A was applied to the surface of the obtained base paper by an air knife coater so that the dry weight was 4 g / m ^2, and dried to obtain a capsule-coated paper. Next, the liquid B was coated and dried on the capsule-coated paper so that the dry weight was 5 g / m ² , to obtain a self-coloring pressure-sensitive recording paper.

[Production of Pressure-Sensitive Recording Pressure-Sensitive Paper] A pressure-sensitive recording pressure-sensitive adhesive paper was obtained in the same manner as in Example 2 except that the above self-coloring pressure-sensitive recording paper was used.

Example 8 "Preparation of Top Paper" Vinyl sulfonic acid 15 mol%, styrene
5 mol%, acrylic acid 70 mol%, ethyl acrylate
37.5 parts of a 20% aqueous solution of a copolymer consisting of 10 mol%
112.5 parts of water was added to the mixture, and the pH was adjusted with 20% NaOH aqueous solution.
What was adjusted to 4.6 was used as the aqueous medium for capsule production.
It was Dissolve 5 parts of crystal violet lactone in this
Diisopropyl naphthalene (trade name: K-113,
(Kureha Chemical Co., Ltd.) 105 parts was added to obtain an average particle size of 5 μm.
After emulsifying and dispersing so that the temperature of the emulsion is raised to 70 ℃
did. Next, the methylated methylolmelamine initial contraction was introduced into the system.
Compound (Brand name: Beckamine APM, 80% concentration, Dainippon
Ink Chemical Co., Ltd.) (20 parts) is added, and the system is continuously stirred.
Hold the temperature at 70 ° C for 1 hour and then cool to give a milky white
A Pucsel dispersion was obtained. Wheat demp in this capsule dispersion
70 parts, dissolved oxide starch 20 parts (solid content)
The prepared capsule coating solution was applied to the base paper of Example 7 in a dry weight.
4 g / m ²Of the pressure-sensitive copy recording paper
I made a top paper.

"Creation of lower paper" Aluminum hydroxide 65
Part, 20 parts of zinc oxide, 15 parts of a mixed melt of zinc 3,5-di (α-methylbenzyl) salicylate and an α-methylstyrene / styrene copolymer (blending ratio 80/20), polyvinyl alcohol aqueous solution 5 Example: A coloring agent coating liquid prepared by adding 20 parts (solid content) of carboxy-modified styrene / butadiene copolymer latex to a dispersion obtained by pulverizing 100 parts (solid content) and 300 parts of water with a ball mill for 24 hours. And dried so that the dry weight is 4 g / m ^{2 on} the support of 7,
Further, calendar processing was performed to prepare a lower sheet of pressure-sensitive copy recording paper.

[Production of Pressure-Sensitive Recording Adhesive Paper] Except that the lower sheet of the pressure-sensitive copying recording paper obtained above was used as the surface substrate and the same adhesive as in Example 4 was used as the adhesive. A pressure-sensitive recording adhesive paper was obtained in the same manner as in Example 7.

Example 9 “Production of Pressure Sensitive Recording Paper” The liquid A of Example 7 was applied to the surface of the base paper of Example 3 by an air knife coater so that the dry weight was 4 g / m ² and dried. A capsule coated paper was obtained.
Next, the liquid B of Example 7 was applied to this capsule-coated paper so that the dry weight was 5 g / m ^2, and dried to obtain a self-coloring pressure-sensitive recording paper.

"Production of pressure-sensitive recording pressure-sensitive adhesive paper" A pressure-sensitive recording pressure-sensitive adhesive paper was obtained in the same manner as in Example 3 except that the above-mentioned self-coloring pressure-sensitive recording paper was used.

Example 10 "Preparation of Top Paper" The capsule coating liquid of Example 8 was applied to the base paper of Example 4 so that the dry weight was 5 g / m ^2, and dried to obtain pressure-sensitive copy recording paper. I made a paper sheet.

"Preparation of Top Paper" The coloring material coating liquid of Example 8 was applied to the base paper of Example 4 so that the dry weight was 4 g / m ² , dried and calendered to perform pressure-sensitive copy recording. I made a bottom sheet of paper.

"Production of Pressure-sensitive Recording Adhesive Paper" A pressure-sensitive recording adhesive paper was obtained in the same manner as in Example 3 except that the pressure-sensitive copy recording paper obtained above was used as the surface substrate.

Comparative Example 5 In Example 7, 2.0 parts of a nonionic surface active agent polyoxyethylene alkyl ether (trade name: Emulgen 920 / manufactured by Kao Corporation) was used as the surface active agent in the pressure-sensitive adhesive polymerization, and an anionic surface. Activator Sodium polyoxyethylene alkyl ether sulfate (Product name: Rebenol WX / Kao Corporation)
An adhesive paper for pressure-sensitive recording was obtained in the same manner as in Example 7 except that the amount was 1.2 parts.

Comparative Example 6 In Example 8, 2.0 parts of a nonionic surface active agent polyoxyethylene alkyl ether (trade name: Emulgen 920 / manufactured by Kao Corporation) was used as the surface active agent in the pressure-sensitive adhesive polymerization, and an anionic surface. An adhesive paper for pressure-sensitive recording was obtained in the same manner as in Example 8 except that 1.2 parts of the activator polyoxyethylene alkyl ether sulfate (trade name: Rebenol WX / manufactured by Kao Corporation) was used.

Comparative Example 7 An adhesive paper for pressure-sensitive recording was obtained in the same manner as in Example 9 except that the same self-coloring pressure-sensitive recording paper as in Example 7 and the same adhesive as in Comparative Example 3 were used.

Comparative Example 8 An adhesive paper for pressure-sensitive recording was obtained in the same manner as in Example 10 except that the lower sheet of the pressure-sensitive copying recording paper used in Example 8 and the same adhesive as used in Comparative Example 4 were used.

The 10 types of pressure-sensitive adhesive recording papers and 8 types of pressure-sensitive recording adhesive sheets thus obtained were evaluated as follows, and the results are shown in Tables 1 and 2. In addition,
The evaluation method for each evaluation item is as follows.

[Initial Coloring Density] 12 pieces of thermosensitive recording adhesive paper were used.
The color density of the recorded image developed by pressing on a hot plate at 0 ° C for 5 seconds (4 kg / cm ² ) was measured by a Macbeth densitometer (RD-100).
R type / manufactured by Macbeth).

The pressure-sensitive recording adhesive paper was colored by the following method, and the color density of the recorded image was measured by a Macbeth densitometer (RD-914).
Type, filter visual / manufactured by Macbeth). In the case of self-coloring pressure-sensitive recording adhesive sheet, 6
A recording image was obtained by applying a load of 00 kg / cm ² . In the case of pressure-sensitive recording adhesive paper using lower leaf paper, make sure that the upper sheet of the pressure-sensitive adhesive sheet of the lower sheet is coated with the coloring agent facing surface. The paper and the bottom paper were superposed and a load of 600 kg / cm ² was applied to obtain a recorded image.

[Plasticizer Resistance] Polypropylene Pipe (4
0 mmφ) and a polyvinyl chloride film (manufactured by Mitsui Toatsu Kagaku Co., Ltd.) were wound in three layers, and the heat-sensitive recording pressure-sensitive adhesive paper colored as described above was attached onto the polyvinyl chloride film so that the color-developing surface was on the outside. Furthermore, a polyethylene film containing no plasticizer was wound on it in three layers and left at 40 ° C. for 24 hours (plasticizer resistance-A) and at 40 ° C. for 72 hours (plasticizer resistance). For each of the properties-B), the color density of the recorded image was measured to evaluate the plasticizer resistance.

[Bleaching resistance] Adhesive paper for heat-sensitive recording was treated at 60 ° C.
After treatment for 3 weeks, press the hot plate at 120 ℃ for 5 seconds (4
kg / cm ² ) to develop color, and pressure sensitive recording adhesive paper is 60
After treatment at ℃ for 3 weeks, develop the color by the above method,
White spots in the recorded image were visually evaluated. The evaluation criteria for recording image quality are as follows. ⊚: No white spots are observed. ○: White spots are hardly seen. Δ: Some white spots are observed, but there is no problem in practical use. X: White spots are remarkable.

[Low Temperature Adhesiveness] of the adhesive paper label for recording,
Film at 15 ℃ (Product name: Suntech S Film C
Adhesion to -320F / Asahi Kasei) was evaluated. ○: Adhesion is very strong. Δ: The label can be peeled off, but it is at a level where there is no practical problem. X: The label comes off very easily.

[Tensile Strength, Elongation] The tensile strength and elongation of the pressure-sensitive adhesive film were measured according to the JIS-K-6301 method.

[Gel Fraction] Coating amount of pressure-sensitive adhesive 25 g / m
Apply ² (solid content) on the release sheet,
A sample film is prepared by drying at 0 ° C. for 1 minute. The obtained sample film is cut into a piece of 3 cm × 3 cm, and the weight is measured (W1). This is put in a basket made of a 300-mesh wire mesh whose weight is measured in advance. Next, the wire mesh is soaked in 40 ml of tetrahydrofuran so that the sample film is completely covered, and left for 24 hours. Then, the wire mesh is taken out from tetrahydrofuran, the sample film is washed with fresh tetrahydrofuran several times, and then dried at room temperature for 1 day and further at 120 ° C. for 1 minute. The weight of the obtained film is measured (W2). Gel fraction = W2 / W1 × 100 (%)

[Printing storability] The pressure-sensitive recording pressure-sensitive adhesive paper colored by the above method was dried at 50 ° C. and 95% R.C. H. After processing for 4 days with a Macbeth densitometer (RD-
Model 914, filter visual / manufactured by Macbeth), and the density ratio before and after the treatment was used for the determination. The closer the value is to 100, the better the print storability. Print storability = D1 / D0 × 100 (%) D0: Color density before processing D1: Color density after processing

[0090]

[Table 1]

[0091]

[Table 2]

[0092]

As is clear from the results shown in Tables 1 and 2, the recording pressure-sensitive adhesive paper of the present invention is a recording pressure-sensitive adhesive paper excellent in print storability, plasticity resistance, white spot resistance, and low temperature adhesion suitability. It was

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C09J 7/02 JJW JLE

Claims (5)

[Claims] 1. A recording in which an adhesive layer and a release paper are sequentially laminated on the back surface of a recording paper having a recording layer utilizing a color reaction of a basic dye and a coloring agent on one surface of the base paper. In the pressure-sensitive adhesive paper for recording, the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is an acrylic copolymer obtained by emulsion-polymerizing a (meth) acrylic acid ester monomer using only an anionic surfactant. Adhesive paper. 2. The anionic surfactant is a fatty acid salt, an alkyl sulfate ester salt, an alkylbenzene sulfonate, an alkylnaphthalene sulfonate, an alkyl sulfosuccinate, an alkyl diphenyl ether disulfonate, an alkyl phosphate, an alkyl allyl sulfate. The pressure-sensitive adhesive paper for recording according to claim 1, which is at least one selected from ester salts and condensates of naphthalenesulfonic acid formalin. 3. The adhesive has a tensile strength of 5.0 to 15.0 kg / cm ² and an elongation of 80 according to JIS-K-6301 method.
The pressure-sensitive adhesive paper for recording according to claim 1, which is 0 to 1200%. 4. The gel fraction of tetrahydrofuran of the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is 30 to 50%.
Adhesive paper for recording described. 5. A JIS-P-8 as a base paper constituting a recording paper.
The pressure-sensitive adhesive paper for recording according to claim 1, wherein the sizing degree of a 20% ethyl alcohol aqueous solution according to the 122 method is 30 seconds or more.