JP2009154448A - Thermosensitive recording body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosensitive recording body having a sufficient color development sensitivity, excellent resistance to water and head tailings, and excellent color development prevention property during storage and surface strength, especially a thermosensitive recording body which does not require providing no protection layer on the thermosensitive recording layer. <P>SOLUTION: The themosensitive recording body having on the support body thereof a thermosensitive recording layer including a colorless or light-colored electron-donating leuco die and an electronreceiving color developing agent characteristically includes an acrylic resin and an alkyl ketene dimer in the thermosensitive recording layer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a heat-sensitive recording material having sufficient color development sensitivity and excellent in water resistance, printing running property (head residue resistance, stick resistance), coloration prevention property during storage, and printing surface strength.

  In general, a recorded image is obtained by utilizing a color development reaction caused by heat between a colorless or light-colored electron-donating leuco dye (hereinafter referred to as a dye) and an electron-accepting developer (hereinafter referred to as a developer). Thermal recording media are widely used in the fields of facsimiles, computers, and various measuring instruments because of their very vivid color development and the advantages of no noise during recording, relatively inexpensive equipment, compactness, and easy maintenance. Has been. Recently, in addition to labels and tickets, applications such as outdoor measurement handy terminals and delivery slips that are used as output media for various printers and plotters have been rapidly expanding. For this reason, higher color sensitivity, printing runnability, and printing surface strength are required for the quality of the thermal recording material. In addition, since labels, tickets, handy terminal paper, delivery slips, etc. are used outdoors, they can withstand use in harsh environments such as moisture, moisture, sunlight, and high temperatures, and are highly water-resistant. Is required to prevent color development.

  In order to improve the water resistance of the heat-sensitive recording medium in response to such demands, a technique for containing an acrylic resin in the heat-sensitive recording layer, and the heat-sensitive recording layer to improve the water resistance and head-casing resistance of the heat-sensitive recording medium In addition, techniques (Patent Documents 1 and 2) in which an acrylic polymer or an acrylic emulsion resin and colloidal silica are used in combination are performed.

JP-A-9-207435 JP 7-266711 A

  When an acrylic resin is contained in the heat-sensitive recording layer and its protective layer, the water resistance is improved, but the problem is that the acrylic resin is softened by the heat from the thermal head of the heat-sensitive recording printer and head debris is generated. For this reason, thermal recording materials that have improved water resistance and printing runnability by containing an acrylic resin and colloidal silica in the thermal recording layer are disclosed in Patent Documents 1 and 2, but the colloidal silica itself has. Under the influence of the activity, it reacts with a dye or a developer contained in the heat-sensitive recording layer during storage, which causes a problem that the white portion is colored.

  Accordingly, the present invention is a heat-sensitive recording material having sufficient color development sensitivity and excellent in water resistance, printing running property (head residue resistance, stick resistance), color development prevention during storage, and printability (surface strength). In particular, it is an object of the present invention to provide a thermosensitive recording material that does not require a protective layer on the thermosensitive recording layer.

  As a result of intensive studies, the present inventors have provided a heat-sensitive recording layer provided with a colorless or light-colored electron-donating leuco dye and an electron-accepting developer on the support. The present inventors have found that the above-mentioned problems can be solved by using a heat-sensitive recording material containing an acrylic resin, colloidal silica, and an alkyl ketene dimer, and have completed the present invention.

  According to the present invention, it is possible to obtain a heat-sensitive recording material having sufficient color development sensitivity, excellent water resistance, printing running property (head residue resistance, stick resistance), color development prevention during storage, and surface strength. I can do it. In particular, an excellent effect is exhibited in a heat-sensitive recording material having no protective layer.

  The heat-sensitive recording material of the present invention is characterized in that an acrylic resin, colloidal silica, and an alkyl ketene dimer are contained in a heat-sensitive recording layer provided on a support.

  In order to prevent color development during production, the thermal recording material is usually produced by controlling the drying so that the maximum temperature of the thermal recording material does not exceed 60 ° C. For this reason, it is preferable to use a resin having a low minimum film forming temperature (MFT) that sufficiently forms a film at about 60 ° C. in order to improve water resistance. Generally, the minimum film forming temperature and the glass transition temperature (Tg) are used. Therefore, if the thermal recording layer contains a resin with a low minimum film forming temperature, that is, a resin with a low glass transition temperature, the resin softens due to the heat from the thermal head of the thermal recording printer. Will occur. For this reason, the apparent glass transition of acrylic resin by mixing colloidal silica around acrylic resin by mixing acrylic resin and colloidal silica with low minimum film-forming temperature (MFT) in the prior art. A technique has been used to control the temperature (Tg) and the minimum film-forming temperature (MFT) to obtain excellent water resistance and head-cass resistance. However, due to the activity of colloidal silica itself, A new problem arises that the white part is colored by reacting with the contained dye or developer. As described above, in the conventional technique, it has been difficult to obtain a heat-sensitive recording material using an acrylic resin and having excellent water resistance, printing runnability, and color-preventing property during storage.

  However, the present inventors have conventionally provided water resistance and printing runnability by blending an alkyl ketene dimer in a heat-sensitive recording layer containing an acrylic resin and colloidal silica provided on a support, The present inventors have found that a heat-sensitive recording layer containing acrylic resin and colloidal silica can be improved in a heat-sensitive recording layer having a problem in surface strength and color-preventing property during storage, and completed the present invention.

  The present invention is a heat-sensitive recording material utilizing a reaction of an alkyl ketene dimer, colloidal silica, and a carboxyl group (including a carbonyl group) of an acrylic resin.

  In the present invention, the colloidal silica contained in the heat-sensitive recording layer reacts with the alkyl ketene dimer, so that the activity of the colloidal silica is reduced (reduction of active sites), and thus the storage stability during storage is improved. Guessed.

In the present invention, the acrylic resin having a carboxyl group contained in the heat-sensitive recording layer reacts with the alkyl ketene dimer to make the hydrophilic portion of the acrylic resin hydrophobic, and the melting point of the alkyl ketene dimer is about 50 ° C. Therefore, it shows good fluidity even in the operation (drying process) of the thermosensitive recording medium controlled so that the paper surface temperature does not exceed 60 ° C., is uniformly distributed in the thermosensitive recording layer, and the entire thermosensitive recording layer It is presumed that the water resistance can be further improved by being able to be hydrophobic.
In addition, the alkyl ketene dimer reacts with the binder having a carboxyl group in the heat-sensitive recording layer, generates a binder having a hydroxyl group and a β-ketoester, and the alkyl ketene dimer is recrystallized. For this reason, the alkyl ketene dimer acts as a kind of cross-linking agent for the binder, so that the binder in the heat-sensitive recording layer appears to be a giant polymer, and the heat-sensitive recording layer as a whole has heat resistance and surface strength. improves. For this reason, it is considered that by including the alkyl ketene dimer in the thermosensitive recording layer, in addition to water resistance, printing runability (head residue resistance, stick resistance) and surface strength are improved.
In addition, since the alkyl ketene dimer is bonded to the binder in the heat-sensitive recording layer or exists as its own crystal, the instantaneous heat from the thermal head causes the bonded portion of the alkyl ketene dimer and the binder, or It is an extent that affects the crystal part of the alkyl ketene dimer, and it is presumed that the alkyl ketene dimer does not elute from the heat-sensitive recording layer. For this reason, even if a low-melting alkyl ketene dimer is contained in the heat-sensitive recording layer, it is considered that there is no problem in print running property (head residue resistance). Since the heat-sensitive recording material of the present invention is excellent in surface strength, printing runnability, water resistance, etc., the protective layer on the heat-sensitive recording layer can be omitted.

  The alkyl ketene dimer contained in the heat-sensitive recording layer in the present invention is a highly reactive substance as shown in the following general formula (1). Regarding the reactivity of this alkyl ketene dimer, the pulp carboxylated to A. Isogai, C. Kitaoka, F. Onabe, J. Pulp Pap. Sci 23 (5): J215-219 (May 1997) It has been reported that, when used in combination with hydrin or alkyl ketene dimer, a higher degree of size can be obtained than when ordinary pulp is used.

（Ｒ、Ｒ’：アルキル基 Ｒ＝Ｒ’を含む）

(Including R and R ′: alkyl group R═R ′)

  The alkyl ketene dimer in the present invention is a compound represented by the above general formula (1) and is usually used as an emulsion emulsified using starch, synthetic polymer, interfacial agent, etc. and dispersed in water. Specific examples of the alkyl ketene dimer include those commercially available from Dick Hercules, Arakawa Chemical Industries, Harima Kasei, BASF, Kao, etc. as neutral sizing agents (for internal and external additives). However, it is not limited to these.

  In the present invention, it is an acrylic resin, and its composition ratio, synthesis method and the like are not particularly limited, and specifically, vinyl acetate-acrylic acid copolymer, vinyl acetate-methacrylic acid copolymer. Polymer, vinyl acetate-alkyl acrylate copolymer, vinyl acetate-alkyl methacrylate copolymer, acrylonitrile-acrylic acid copolymer, acrylonitrile-alkyl acrylate copolymer, acrylonitrile-alkyl methacrylate copolymer, acrylonitrile -Methacrylic acid-alkyl acrylate-alkyl methacrylate-styrene copolymer, acrylonitrile-dialkylaminoalkyl methacrylate-acrylamide copolymer, acrylic acid-methacrylic acid copolymer, acrylic acid-alkyl acrylate copolymer, etc. Metal salt, acrylic acid Alkyl acrylate-acrylamide copolymer, acrylic acid-methacrylamide-styrene acid copolymer, methacrylic acid-alkyl acrylate-alkyl methacrylate copolymer, methacrylic acid metal salt-alkyl acrylate-alkyl methacrylate copolymer , Methacrylic acid-alkyl acrylate-alkyl methacrylate-acrylamide copolymer, methacrylic acid-alkyl methacrylate, acrylic acid, methacrylic acid, acrylic acid and methacrylic acid derivatives (acrylamide, acrylonitrile, etc.) maleic acid and its derivatives Polymers copolymerized with styrene and its derivatives as main components are emeraldyl copolymer, alkyl acrylate-acrylamide-styrene copolymer, alkyl methacrylate-alkyl acrylate-maleic anhydride copolymer, Alkyl acrylate-alkyl acrylate-maleic anhydride metal salt copolymer, alkyl acrylate-styrene-maleic anhydride metal salt copolymer, alkyl methacrylate-fumaric acid copolymer, alkyl acrylate-itaconic acid metal salt Examples of the copolymer and the modified products thereof may include water-based emulsions using an emulsifier as necessary, and these may be used alone or in combination of two or more. In the above acrylic emulsion, alkyl is a saturated hydrocarbon having 10 or less carbon atoms such as methyl, ethyl, propyl, butyl, 2-ethylhexyl, and the metal salt is ammonium, Li, Na, K, Means salts of Mg, Ca, Al and the like.

In the present invention, the acrylic resin preferably has a minimum film-forming temperature (MFT) of 10 ° C. or higher and lower than 50 ° C. from the viewpoint of good film-forming properties, heat resistance and water resistance. Examples of acrylic resins having a minimum film-forming temperature (MFT) of 10 ° C. or more and 50 ° C. are mobile 727, mobile 735, mobile 747, mobile 767, mobile 1430, mobile 9000, mobile 9001, mobile DM 772, mobile 774 (and above, Clariant). (Manufactured by Polymer Co., Ltd.) and the like, but are not limited thereto.

As the colloidal silica used in the present invention, colloidal silica having various shapes such as a spherical shape and a chain shape can be used singly or in combination of two or more types, but it is preferable to use a colloidal silica having a chain structure. From the viewpoint of water resistance, it is preferable. The chain colloidal silica is a specific number of spherical colloidal silica particles that are primary particles, connected in series or partially branched, and the size (length) is not particularly limited. 40 to 200 nm (laser scattering method). When the size (length) of the chain colloidal silica is less than 40 nm, the porosity is lowered, and it may be difficult to obtain a sufficient effect on both the head residue and water resistance.

The colloidal silica used in the present invention is preferably anionic from the viewpoint of paint stability, and the colloidal solution preferably has a pH of about 7 to 11. Typical examples of such chain colloidal silica include Snowtex PS-P, Snowtex PS-M, and Snowtex UP (manufactured by Nissan Chemical Industries, Ltd.).

  The blending amount of the alkyl ketene dimer used in the present invention is preferably 0.1 to 5 parts by weight (hereinafter, the parts by weight are converted into solids) with respect to 100 parts by weight of the total solid content of the heat sensitive layer. 5 to 2 parts by weight is more preferable. When the blending amount of the alkyl ketene dimer is 0.1 parts by weight or less, good water resistance and printability cannot be obtained, and when it is 5 parts by weight or more, high color development sensitivity is difficult to obtain, and the viscosity of the paint is remarkably increased. .

  As a compounding quantity of the acrylic emulsion used by this invention, it is preferable to mix | blend 3-50 weight part with respect to 100 weight part of heat-sensitive layer total solids, More preferably, it is 5-30 weight part. If the amount is too small, the water resistance is insufficient. If the amount is too large, the sensitivity is likely to decrease.

  The blending amount of the colloidal silica used in the present invention is preferably 1 to 100 parts by weight, more preferably 10 to 60 parts by weight with respect to 100 parts by weight of the acrylic emulsion, from the viewpoint of printing runnability and storage stability during storage. It is.

  In the present invention, the glass transition temperature (Tg) is determined based on the scanning differential calorimeter (10 mg sample at 25 ° C./nitrogen atmosphere) according to JIS K-7122. Change in specific heat associated with the second order transition measured at (temperature rise in minutes) as glass transition temperature, glass transition temperature (Tg) of resin = Tg1 × α1 + Tg2 × α2 +... + Tgn × αn (Tg1, Tg2,... Tgn : Actually measured glass transition temperature of each composition simple substance, α1, α2,... Αn: Calculated from a calculation formula of weight fraction (%) of each composition simple substance with respect to the total weight of the resin.

  In the present invention, the minimum film increasing temperature (MFT) is based on JIS K-6828, a resin adjusted to 20% by weight is spread over the entire surface of the slide glass, dried at a predetermined temperature, and the dried resin is uniform. The minimum temperature was a continuous film and the film was not clouded.

  The blending amount of the acrylic resin used in the present invention is preferably 1 to 30% by weight (hereinafter, parts by weight are converted to solids) with respect to the total solid content of the heat-sensitive recording layer, and more preferably 2 to 10% by weight. preferable. When the blending amount of the acrylic resin is 1% by weight or less, water resistance cannot be obtained, and when it is 30% by weight or more, high color development sensitivity is hardly obtained.

In the present invention, it is also possible to use a colloidal silica / acrylic composite emulsion, which is a composite particle type in which colloidal silica is introduced into an acrylic resin component, as a colloidal silica / acrylic emulsion. , Mobile 8010, Mobile 8030 (both made of Clariant Polymer) and the like. However, in order to obtain high water resistance, it is preferable to use a mixed acrylic resin and colloidal silica.

  Examples of various materials used in the heat-sensitive color developing layer of the present invention include a binder and a cross-linking agent that can be used in combination as long as the desired effects on the above-mentioned problems are not impaired. Not only can it be used for each coating layer provided as needed, including the under layer.

  As the developer used in the present invention, any known ones in the field of conventional pressure-sensitive or heat-sensitive recording paper can be used and are not particularly limited. For example, 4,4′-isopropyl Dendiphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 4,4′-dihydroxydiphenyl sulfide, hydroquinone monobenzyl ether, 4-hydroxy Benzyl benzoate, 4,4′-dihydroxydiphenylsulfone, 2,4′-dihydroxydiphenylsulfone, 4-hydroxy-4′-isopropoxydiphenylsulfone, 4-hydroxy-4′-n-propoxydiphenylsulfone, bis (3 -Allyl-4-hydroxyphenyl) sulfone, 4-hydroxy-4'- Allyloxydiphenylsulfone, 4-hydroxy-4'-methyldiphenylsulfone, 4-hydroxyphenyl-4'-benzyloxyphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, JP-A-8-59603 Aminobenzenesulfonamide derivatives, bis (4-hydroxyphenylthioethoxy) methane, 1,5-di (4-hydroxyphenylthio) -3-oxapentane, butyl bis (p-hydroxyphenyl) acetate, bis (p -Hydroxyphenyl) acetic acid methyl, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,4-bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] benzene, 1,3 -Bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] benzene , Di (4-hydroxy-3-methylphenyl) sulfide, 2,2′-thiobis (3-tert-octylphenol), 2,2′-thiobis (4-tert-octylphenol), described in International Publication No. WO 97/16420 Phenolic compounds such as diphenylsulfone cross-linking compounds, developer compositions described in International Publication WO 02/098674, compounds described in International Publication WO 02/081229 or JP-A No. 2002-301873, 4,4′- Bis-3- (phenoxycarbonylamino) methylphenylureido) diphenylsulfone (trade name: UU manufactured by Asahi Kasei Corporation), thiourea compounds such as N, N′-di-m-chlorophenylthiourea, p-chlorobenzoic acid, stearyl gallate Bis [4- (n-octyloxycarbonylamino) salicylate zinc] 2 Japanese, 4- [2- (p-methoxyphenoxy) ethyloxy] salicylic acid, 4- [3- (p-tolylsulfonyl) propyloxy] salicylic acid, 5- [p- (2-p-methoxyphenoxyethoxy) cumyl] Aromatic carboxylic acids of salicylic acid, and salts of these aromatic carboxylic acids with polyvalent metal salts such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, nickel, as well as antipyrine complexes of zinc thiocyanate, terephthalate Examples include complex zinc salts of aldehyde acid and other aromatic carboxylic acid. A phenolic compound such as the diphenylsulfone cross-linking compound described in International Publication No. WO 97/16420 is available as a trade name D-90 manufactured by Nippon Soda Co., Ltd. The compounds described in International Publication No. WO02 / 081229 or JP-A-2002-301873 are available as trade names D-102 and D-100 manufactured by Nippon Soda Co., Ltd. These developers can be used alone or in combination of two or more. Among these, 4-hydroxy-4′-isopropoxydiphenyl sulfone is particularly preferable because of excellent color development sensitivity. In addition, a metal chelate color-developing component such as a higher fatty acid metal double salt and a polyvalent hydroxyaromatic compound described in JP-A-10-258577 can also be contained.

  As the electron-donating leuco dye used in the present invention, those known in the conventional pressure-sensitive or heat-sensitive recording paper field can be used, and are not particularly limited, but include triphenylmethane compounds, fluorane compounds. Compounds, fluorene compounds, divinyl compounds and the like are preferable. Specific examples of typical colorless or light-colored dyes (dye precursors) are shown below. These dye precursors may be used alone or in combination of two or more.

<Triphenylmethane leuco dye>
3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (also known as crystal violet lactone); 3,3-bis (p-dimethylaminophenyl) phthalide (also known as malachite green lactone)

<Fluoran leuco dye>
3-diethylamino-6-methylfluorane; 3-diethylamino-6-methyl-7-anilinofluorane; 3-diethylamino-6-methyl-7- (o, p-dimethylanilino) fluorane; 3-diethylamino- 6-methyl-7-chlorofluorane; 3-diethylamino-6-methyl-7- (m-trifluoromethylanilino) fluorane; 3-diethylamino-6-methyl-7- (o-chloroanilino) fluorane; Diethylamino-6-methyl-7- (p-chloroanilino) fluorane; 3-diethylamino-6-methyl-7- (o-fluoroanilino) fluorane; 3-diethylamino-6-methyl-7- (m-methylanilino) fluorane 3-diethylamino-6-methyl-7-n-octylanilinofluorane; 3-diethylamino-6-methyl-7-n-octylaminofluorane; 3-diethylamino-6-methyl-7-benzylaminofluorane; 3-diethylamino-6-methyl-7-dibenzylaminofluorane;
3-diethylamino-6-chloro-7-methylfluorane; 3-diethylamino-6-chloro-7-anilinofluorane; 3-diethylamino-6-chloro-7-p-methylanilinofluorane; 3-diethylamino -6-ethoxyethyl-7-anilinofluorane; 3-diethylamino-7-methylfluorane; 3-diethylamino-7-chlorofluorane; 3-diethylamino-7- (m-trifluoromethylanilino) fluorane; 3-diethylamino-7- (o-chloroanilino) fluorane; 3-diethylamino-7- (p-chloroanilino) fluorane; 3-diethylamino-7- (o-fluoroanilino) fluorane; 3-diethylamino-benzo [a] fluorane ;
3-dibutylamino-6-methyl-7- (o); 3-dibutylamino-6-methyl-7- (o; 3-dibutylamino-6-methyl-7- (o , P-dimethylanilino) fluorane; 3-dibutylamino-6-methyl-7- (o-chloroanilino) fluorane; 3-dibutylamino-6-methyl-7- (p-chloroanilino) fluorane; 3-dibutylamino- 6-methyl-7- (o-fluoroanilino) fluorane; 3-dibutylamino-6-methyl-7- (m-trifluoromethylanilino) fluorane; 3-dibutylamino-6-methyl-chlorofluorane; 3-dibutylamino-6-ethoxyethyl-7-anilinofluorane; 3-dibutylamino-6-chloro- 7-anilinofluorane; 3-dibutylamino-6-methyl-7-p-methylanilinofluorane; 3-dibutylamino-7- (o-chloroanilino) fluorane; 3-dibutylamino-7- (o- 3-di-n-pentylamino-6-methyl-7-anilinofluorane; 3-di-n-pentylamino-6-methyl-7- (p-chloroanilino) fluorane; Di-n-pentylamino-7- (m-trifluoromethylanilino) fluorane; 3-di-n-pentylamino-6-chloro-7-anilinofluorane; 3-di-n-pentylamino-7 -(P-chloroanilino) fluorane; 3-pyrrolidino-6-methyl-7-anilinofluorane; 3-piperidino-6-methyl-7-anilinofluorane 3- (N-methyl-N-propylamino) -6-methyl-7-anilinofluorane; 3- (N-methyl-N-cyclohexylamino) -6-methyl-7-anilinofluorane; -(N-ethyl-N-cyclohexylamino) -6-methyl-7-anilinofluorane; 3- (N-ethyl-N-xylamino) -6-methyl-7- (p-chloroanilino) fluorane; (N-ethyl-p-toludino) -6-methyl-7-anilinofluorane; 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluorane; 3- (N- Ethyl (N-isoamylamino) -6-chloro-7-anilinofluorane; 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluorane; Til-N-isobutylamino) -6-methyl-7-anilinofluorane; 3- (N-ethyl-N-ethoxypropylamino) -6-methyl-7-anilinofluorane; 3-cyclohexylamino-6 -Chlorofluorane; 2- (4-oxahexyl) -3-dimethylamino-6-methyl-7-anilinofluorane; 2- (4-oxahexyl) -3-diethylamino-6-methyl-7-ani Linofluorane; 2- (4-oxahexyl) -3-dipropylamino-6-methyl-7-anilinofluorane; 2-methyl-6-p- (p-dimethylaminophenyl) aminoanilinofluorane 2-methoxy-6-p- (p-dimethylaminophenyl) aminoanilinofluorane; 2-chloro-3-methyl-6-p- (p-phenylaminophenyl); 2-chloro-6-p- (p-dimethylaminophenyl) aminoanilinofluorane; 2-nitro-6-p- (p-diethylaminophenyl) aminoanilinofluorane; -Amino-6-p- (p-diethylaminophenyl) aminoanilinofluorane; 2-diethylamino-6-p- (p-diethylaminophenyl) aminoanilinofluorane; 2-phenyl-6-methyl-6-p -(P-phenylaminophenyl) aminoanilinofluorane; 2-benzyl-6-p- (p-phenylaminophenyl) aminoanilinofluorane; 2-hydroxy-6-p- (p-phenylaminophenyl) Aminoanilinofluorane; 3-methyl-6-p- (p-dimethylaminophenyl) aminoanilinov Oran; 3-diethylamino-6-p- (p-diethylaminophenyl) aminoanilinofluorane; 3-diethylamino-6-p- (p-dibutylaminophenyl) aminoanilinofluorane; 2,4-dimethyl-6 -[(4-Dimethylamino) anilino] -fluorane

<Fluorene leuco dye>
3,6,6′-tris (dimethylamino) spiro [fluorene-9,3′-phthalide]; 3,6,6′-tris (diethylamino) spiro [fluorene-9,3′-phthalide]

<Divinyl leuco dye>
3,3-bis- [2- (p-dimethylaminophenyl) -2- (p-methoxyphenyl) ethenyl] -4,5,6,7-tetrabromophthalide; 3,3-bis- [2- (P-dimethylaminophenyl) -2- (p-methoxyphenyl) ethenyl] -4,5,6,7-tetrachlorophthalide; 3,3-bis- [1,1-bis (4-pyrrolidinophenyl) ) Ethylene-2-yl] -4,5,6,7-tetrabromophthalide; 3,3-bis- [1- (4-methoxyphenyl) -1- (4-pyrrolidinophenyl) ethylene-2- Yl] -4,5,6,7-tetrachlorophthalide

<Others>
3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide; 3- (4-diethylamino-2-ethoxyphenyl) -3- ( 1-octyl-2-methylindol-3-yl) -4-azaphthalide; 3- (4-cyclohexylethylamino-2-methoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl)- 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide; 3,6-bis (diethylamino) fluorane-γ- (3′-nitro) anilinolactam; -Bis (diethylamino) fluorane-γ- (4'-nitro) anilinolactam; 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p-dimethyla Nophenyl) -ethenyl] -2,2-dinitrileethane; 1,1-bis- [2 ′, 2 ′, 2 ″, 2 ″ -tetrakis- (p-dimethylaminophenyl) -ethenyl] -2- β-naphthoylethane; 1,1-bis- [2 ′, 2 ′, 2 ″, 2 ″ -tetrakis- (p-dimethylaminophenyl) -ethenyl] -2,2-diacetylethane; bis- [2, 2,2 ′, 2′-Tetrakis- (p-dimethylaminophenyl) -ethenyl] -methylmalonic acid dimethyl ester

  As the binder used in the present invention, generally known binders are used, and specifically, fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, amide-modified polyvinyl alcohol having a polymerization degree of 200 to 1900. , Sulfonic acid modified polyvinyl alcohol, butyral modified polyvinyl alcohol, other modified polyvinyl alcohol, cellulose derivatives such as hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, ethyl cellulose, acetyl cellulose, styrene-maleic anhydride copolymer, styrene-butadiene Copolymer, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyacrylic ester, polyvinyl butyllar, polystyrene and the like Copolymers, polyamide resins, silicone resins, petroleum resins, terpene resins, ketone resins, and the Khumalo resin. Among these, use of a saponification degree of 90% or less and / or unmodified polyvinyl alcohol is preferable from the viewpoints of color development sensitivity, water resistance, and surface strength.

These polymer substances are used by dissolving them in water, alcohol, ketones, esters, hydrocarbons and other solvents, and are used in the form of emulsification or paste dispersion in water or other media to achieve the required quality. It is also possible to use it together.
As a compounding quantity of a binder, 1 to 30 weight% is preferable with respect to the heat-sensitive layer total solid. When the blending amount of the binder is 1% by weight or less, the water resistance and surface strength are low, and when it is 30% by weight or more, high color development sensitivity is difficult to obtain.

  In this invention, a conventionally well-known crosslinking agent can be used in the range which does not inhibit the desired effect with respect to the said subject. Such crosslinking agents include glyoxal, methylol melamine, melamine formaldehyde resin, melamine urea resin, polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, potassium persulfate, ammonium persulfate, sodium persulfate, ferric chloride, chloride. Examples thereof include magnesium, borax, boric acid, alum, ammonium chloride and the like.

  Moreover, in this invention, a conventionally well-known lubricant can be used in the range which does not inhibit the desired effect with respect to the said subject. Examples of such lubricants include fatty acid metal salts such as zinc stearate and calcium stearate, waxes, silicon resins and the like. In addition, benzophenone and triazole ultraviolet absorbers, dispersants, antifoaming agents, antioxidants, fluorescent dyes, and the like can be used.

  Moreover, in this invention, a conventionally well-known sensitizer can be used in the range which does not inhibit the desired effect with respect to the said subject. Such sensitizers include ethylene bisamide, montanic acid wax, polyethylene wax, 1,2-di- (3-methylphenoxy) ethane, p-benzylbiphenyl, β-benzyloxynaphthalene, 4-biphenyl-p-tolyl ether. , M-terphenyl, 1,2-diphenoxyethane, 4,4′-ethylenedioxy-bis-benzoic acid dibenzyl ester, dibenzoyloxymethane, 1,2-di (3-methylphenoxy) ethylene, 1 , 2-diphenoxyethylene, bis [2- (4-methoxy-phenoxy) ethyl] ether, methyl p-nitrobenzoate, dibenzyl oxalate, di (p-chlorobenzyl) oxalate, di (p-methyl oxalate) Benzyl), dibenzyl terephthalate, benzyl p-benzyloxybenzoate, di-p-to Carbonate, phenyl-α-naphthyl carbonate, 1,4-diethoxynaphthalene, 1-hydroxy-2-naphthoic acid phenyl ester, 4- (m-methylphenoxymethyl) biphenyl, orthotoluenesulfonamide, paratoluenesulfonamide. Although it can illustrate, it is not restrict | limited in particular to these. These sensitizers may be used alone or in combination of two or more.

  Examples of the filler used in the present invention include inorganic or organic fillers such as silica, calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium oxide and aluminum hydroxide, and these are used alone or in combination of two or more. From the viewpoint of coating layer strength and printing runnability, it is desirable to use calcium carbonate and silica in combination, and further, calcium carbonate having an average particle diameter of 3 μm or more and an average particle diameter of 5 to 10 μm. It is preferable to use silica having an oil absorption of 150 ml / 100 g or more and a specific surface area of 150 m 2 / g or less in combination. When calcium carbonate and silica are used, the weight ratio of calcium carbonate / silica is preferably 20/80 to 80/20, more preferably 40/60 to 60/40. Basic leuco dye 1 About 0.5-10 weight part is preferable with respect to a weight part.

In the present invention, 4,4′-butylidene (6-tert-butyl-3-methylphenol) is used as a stabilizer for imparting oil resistance and the like of recorded images within a range that does not impair the desired effect on the above-described problems. 2,2′-di-t-butyl-5,5′-dimethyl-4,4′-sulfonyldiphenol, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenylbutane, 4-benzyloxy-4 '-(2,3-epoxy-2-methylpropoxy) diphenylsulfone, epoxy resin Etc. can also be added.

  The types and amounts of the basic leuco dye, developer, and other various components used in the heat-sensitive recording material of the present invention are determined according to required performance and recording suitability, and are not particularly limited. A developer of 0.5 to 10 parts, a sensitizer of 0.5 to 10 parts, and a filler of about 0.5 to 10 parts are used with respect to 1 part of the functional leuco dye.

By applying the coating liquid having the above composition to any support such as paper, recycled paper, synthetic paper, film, plastic film, foamed plastic film, non-woven fabric, etc., the desired thermal recording material can be obtained. Moreover, you may use the composite sheet which combined these as a support body. Basic leuco dye, color developer, and materials to be added as necessary are finely pulverized to a particle size of several microns or less by a pulverizer such as a ball mill, attritor or sand glider, or an appropriate emulsifying device. Depending on the conditions, various additive materials are added to obtain a coating solution. The means for applying is not particularly limited, and can be applied in accordance with well-known conventional techniques. For example, an off-knife equipped with various coaters such as an air knife coater, a rod blade coater, a bill blade coater, a roll coater, a curtain coater, and a spray coater. A machine coater or an on-machine coater is appropriately selected and used. The coating amount of the heat-sensitive recording layer is not particularly limited and is usually in the range of ² to 12 g / m ^{2 by} dry weight.

  In the heat-sensitive recording material of the present invention, an undercoat layer such as a polymer material containing a filler can be provided under the heat-sensitive recording layer for the purpose of increasing the color development sensitivity. It is also possible to correct the curl by providing a backcoat layer on the opposite side of the support from the thermosensitive recording layer. Also, various known techniques in the heat-sensitive recording material field can be added as appropriate, such as applying a smoothing process such as supercalendering after coating each layer.

EXAMPLES The present invention will be specifically described below with reference to examples, but the scope of the present invention is not limited to these examples. In each example, “parts” means “parts by weight” unless otherwise specified.

[Example 1]
A composition comprising the following composition was stirred and dispersed to prepare an undercoat layer coating solution.
<Undercoat layer coating solution>
Baked kaolin (manufactured by BASF, trade name: Ansilex 93) 100 parts Styrene-butadiene latex (solid content 48%) 40 parts Polyvinyl alcohol aqueous solution (10% solution) 30 parts Water 160 parts Next, undercoat layer coating liquid is supported After coating so that the coating amount was 8.0 g / m ^{2 on} one side (basis weight 50 g / m ² fine paper), drying was performed to obtain an undercoat layer coated paper.
Each of the dye, developer, and sensitizer materials was prepared in advance as a dispersion having the following composition, and wet grinding was performed with a sand grinder until the average particle size became 0.5 μm.

<Liquid A: Developer dispersion>
4-hydroxy-4'-isopropoxydiphenylsulfone
(Product name: NY-DS, manufactured by API Corporation) 6.0 parts Polyvinyl alcohol aqueous solution (10% solution) 18.8 parts Water 11.2 parts <Liquid B: Dye dispersion>
3-di-n-butylamino-6-methyl-7-anilinofluorane (manufactured by Yamamoto Kasei Co., Ltd., trade name: ODB-2) 3.0 parts Polyvinyl alcohol aqueous solution (10% solution) 6.9 parts water 3 .9 parts <C solution: sensitizer dispersion>
1,2-di- (3-methylphenoxy) ethane (trade name: KS232, manufactured by Sanko Co., Ltd.) 6.0 parts Polyvinyl alcohol aqueous solution (10% solution) 18.8 parts Water 11.2 parts

The above dispersions were mixed at the ratio shown below to obtain a thermal recording layer coating solution. The coating solution is applied and dried on the undercoat layer coated paper so that the coating amount after drying is 6.0 g / m ^2, and processed with a super calender so that the Beck smoothness is 200 to 600 seconds. A record was obtained.
Liquid A 36.0 parts Liquid B 13.8 parts Liquid C 36.0 parts Silica (manufactured by Mizusawa Chemical Co., Ltd., trade name: P537) 25% dispersion 26.0 parts Calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name: Tunex) E, average particle size: 4.4 μm) 50% dispersion 13.0 parts Zinc stearate (manufactured by Chukyo Yushi Co., Ltd., trade name: Hydrin Z-7-30) 30% dispersion
6.7 parts polyvinyl alcohol aqueous solution 10% solution (manufactured by Kuraray Co., Ltd., trade name: PVA217, polymerization degree: 1750, saponification degree: 88 mol%) 20.0 parts acrylic resin (manufactured by Clariant Polymer Co., Ltd., trade name: Movinyl 735) , Solid content concentration 43%, minimum film forming temperature 25 ° C.) 5.0 parts chain colloidal silica solid content 20% (manufactured by Nissan Chemical Co., Ltd .: Snowtex PS-M, size (length): 80 to 150 nm, primary Particle size: 18 to 25 nm) 5.0 parts alkyl ketene dimer (manufactured by Seiko PMC, trade name: AD1604, solid content 30%)
1.4 parts [Example 2]
Except for replacing the acrylic resin and colloidal silica of Example 1 with 10.0 parts of colloidal silica / acrylic composite emulsion (manufactured by Clariant Polymer Co., Ltd., trade name: Movinyl 8030, solid content concentration 44%, minimum film forming temperature 30 ° C.). Obtained a heat-sensitive recording material in the same manner as in Example 1.
[Example 3]
A heat-sensitive recording material was obtained in the same manner as in Example 1 except that the number of parts of the alkyl ketene dimer in Example 1 was changed to 4.2 parts.
[Example 4]
A heat-sensitive recording material was obtained in the same manner as in Example 1 except that the number of parts of the alkyl ketene dimer in Example 1 was changed to 0.16 parts.
[Comparative Example 1]
A heat-sensitive recording material was obtained in the same manner as in Example 1 except that the alkyl ketene dimer of Example 1 was not used.
[Comparative Example 2]
A heat-sensitive recording material was obtained in the same manner as in Example 2 except that the alkyl ketene dimer of Example 2 was not used.
[Comparative Example 3]
Thermal recording as in Example 1 except that the acrylic resin of Example 1 was replaced with completely saponified polyvinyl alcohol (Kuraray Co., Ltd., trade name: PVA117, polymerization degree: 1750, saponification degree: 98 mol%). Got the body.
[Comparative Example 4]
Except for replacing the styrene acrylic resin of Example 1 with completely saponified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name: PVA117, polymerization degree: 1750, saponification degree: 98 mol%), and without using an alkyl ketene dimer, A heat-sensitive recording material was obtained in the same manner as in Example 1.

  The thermosensitive recording materials obtained in the above-described examples and comparative examples were evaluated as follows. The results are shown in Table 1.

[Color development sensitivity]
Using TH-PMD manufactured by Okura Electric Co., Ltd., printing was performed on the created thermal recording medium at an applied energy of 0.34 mJ / dot and 0.25 mJ / dot. The image density after printing and after the quality test was measured with a Macbeth densitometer (RD-914, using an amber filter).

[water resistant]
-Image remaining rate Using a TH-PMD manufactured by Okura Electric Co., Ltd., a thermal recording medium printed with an applied energy of 0.34 mJ / dot was immersed in water and allowed to stand at 23 ° C. for 24 hours. Measurement was performed with a Macbeth densitometer, and the image residual ratio was calculated by the following formula.
Image residual ratio (%) = density after test / density before test × 100
- Soak the water pressure-sensitive thermosensitive recording material in water for 3 minutes, after the recording surface under a load of 300 g / cm ² in the two-folded such that the inner, stripped While recording surface is wet, at 105 ° C. The color was developed for 2 minutes, and the degree of peeling of the recording surface was visually judged and evaluated according to the following criteria.
A: There is no peeling of the recording surface
○: There is almost no peeling of the recording surface. Δ: Some peeling of the recording surface is observed. X: There is much peeling of the recording surface.

-Water blocking resistance 50 μl of water drops are hung on the surface of the heat-sensitive recording medium, folded in half so that the recording surface is inside, a load of 10 g / cm ² is applied on the recording medium on which the water drops have been dropped, and 23 ° C. and 50% Rh. The recording surface was peeled off for 24 hours, and then the recording surface was peeled off, and the color was developed at 105 ° C. for 2 minutes. The degree of peeling of the recording surface was visually determined and evaluated according to the following criteria.
A: There is no peeling of the recording surface
○: There is almost no peeling of the recording surface. Δ: Some peeling of the recording surface is observed. X: There is much peeling of the recording surface.

[Preservation of white paper during storage]
The heat-sensitive recording material was allowed to stand for 72 hours in a blower dryer maintained at 60 ° C., and the difference in whiteness before and after the test was measured using a Hunter whiteness meter (filter: Am).

○: Decrease in whiteness is less than 2 points Δ: Whiteness is reduced by 2 points or more and less than 10% ×: Whiteness is reduced by 10 points or more

[Surface strength]
Using a Prüfbau printer, 0.25 ml (printing unit pressure: 50 kgf) of sheet-fed ink (manufactured by Toyo Ink Mfg. Co., Ltd., trade name: TK High Unity MZ Ind.) And 0.015 ml of dampening water (dampening water unit) Pressure: 20 kgf) Using the surface of the thermosensitive recording layer (printing speed: 100 m / min) is checked to check the surface condition, visually determining whether the coating layer is peeled off, and evaluating according to the following criteria: did.
○: Almost no peeling of coating layer Δ: Some peeling of coating layer ×: Many peeling of coating layer [Print runnability (head residue)]
30 cm long grid printing was performed with a label printer (printer name: Respre R-8) manufactured by SATO, and the head residue and print samples adhering to the thermal head after printing were visually observed.

○: There is almost no head residue on the thermal head. Δ: Slight head residue is attached to the thermal head, but no fading is observed on the printed part. ×: Head residue is attached to the thermal head and the printed part is faint.
[Print runnability (stick resistance)]
Under an atmosphere of −15 ° C., a black solid print having a length of 5 cm was performed with a handy terminal printer (printer name: HT-180) manufactured by Canon, and the print samples were visually evaluated.
○: No stick is generated △: Stick is slightly generated ×: Stick is generated

Claims (1)

  In a heat-sensitive recording material provided with a heat-sensitive recording layer containing a colorless or light-colored electron-donating leuco dye and an electron-accepting developer on a support, the heat-sensitive recording layer comprises an acrylic resin, colloidal silica, and an alkyl ketene dimer. A heat-sensitive recording material comprising: