Thermosensitive recording laminate and method for producing thermosensitive recording laminate

Abstract

To provide a laminate which not only has water resistance but also has less residual solvent, hardly causes blocking and has anti-scumming property, transparency, color developing density, adhesion, alcohol resistance, scratch resistance before and after color development, head resistance, abrasion resistance and oil resistance.SOLUTION: There is provided a thermosensitive recording laminate which has a thermosensitive color developing layer composed of a thermosensitive color developing agent comprising a leuco dye, at least one color developer of at least one of compounds represented by general formulas (1) to (4), a water-based resin, an alcohol and water on one surface of a plastic film base material, a water-based coating layer composed of a water-based coating agent containing a water-soluble resin and water on the thermosensitive color developing layer and an overcoat layer composed of an overcoat agent containing a thermoplastic resin, a polyisocyanate and an organic solvent on the water-based coating layer.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a heat-sensitive recording laminate and a method for manufacturing the same.

Background Art

[0002] Generally, a heat-sensitive recording medium is obtained by applying a coating liquid containing an electron-donating leuco dye (hereinafter also referred to as "leuco dye"), which is usually colorless or light-colored, and an electron-accepting color developer such as a phenolic compound (hereinafter also referred to as "color developer") to a support such as paper, synthetic paper, film, or plastic. It develops color through an instantaneous chemical reaction caused by heating with a thermal head, hot stamp, thermal pen, laser light, etc., and a recorded image is obtained. Heat-sensitive recording media are widely used as recording media for facsimiles, computer terminal printers, automatic ticket vending machines, measurement recorders, receipts at supermarkets and convenience stores, etc.

[0003] Since it can record in a short time using a relatively simple device and has the advantage of low cost, in recent years, it can contribute to the reliability of images, reduction of conventional labels, designability, and cost reduction of packaging materials. In the food packaging field such as food, bento, and prepared foods, it has come to be rapidly used, and there are demands for label-free, transparency, water resistance, oil resistance, alcohol resistance, scratch resistance, and non-color development at low temperatures (soil stain resistance).

[0004] Patent Document 1 discloses a heat-sensitive recording medium having a heat-sensitive recording layer containing a leuco dye and a urethane-urea compound as a color developer on a plastic film, and a protective layer as the outermost layer on the heat-sensitive recording layer, the protective layer containing an acrylic resin and a polyolefin resin. However, the protective layer uses an aqueous emulsion of an acrylic resin and a polyolefin resin in combination. From the comparative example, it is clear that although the aqueous emulsion of the acrylic resin alone has excellent print running properties (head resistance), it only requires a certain degree of water resistance and slight coating defects (a certain degree of transparency), but may be inferior in alcohol resistance. Since no curing agent or crosslinking agent is used in the protective layer, the oil resistance may be inferior. Also, there is no description or suggestion regarding soil resistance, blocking, residual solvents, adhesion, scratch resistance, and friction resistance.

[0005] Patent Document 2 discloses a thermal recording medium having a support, a color former which is an N,N'- diarylurea derivative, and a thermal recording layer containing a styrene - acrylic resin on the support. Further, it has a protective layer on the thermal recording layer (Example 6). The protective layer uses a water - soluble styrene - acrylic resin and an oxazoline - group - containing polymer as a curing agent, and has water resistance. Also, as for ethanol resistance, after printing an image on the thermal recording medium with a laser marker and evaluating the change in image density before and after immersion in ethanol, the alcohol resistance of the thermal recording medium itself is not evaluated and may be inferior. Also, there is no description or suggestion regarding soil resistance, blocking, residual solvents, adhesion, scratch resistance, head resistance, friction resistance, and oil resistance. Regarding transparency, it is described that the support is preferably a transparent film and there is no problem if the haze (turbidity) is about 10% or less, but this is only about the transparency of the support, not the transparency of the thermal recording medium itself, and there is no description or suggestion regarding the transparency of the thermal recording medium.

[0006] Patent Document 3 discloses a thermal recording medium having a thermal recording layer - forming liquid containing a leuco dye, a color former having a specific solubility, and a solvent, and a thermal recording layer on a part of the region of the support. Further, it has a protective layer on the thermal recording layer (Examples 21 - 28). The protective layer uses an acrylic resin emulsion and has water resistance. It is also excellent in terms of substrate uniformity (less coating unevenness = adhesion) and substrate density (color density). However, since no curing agent or crosslinking agent is used in the protective layer, there is a risk of inferior oil resistance. Furthermore, there is a risk of inferior alcohol resistance. There is also no description or suggestion regarding soil resistance, blocking, transparency, residual solvents, scratch resistance, head resistance, and abrasion resistance.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0008] Therefore, an object of the present invention is to provide a laminate having water resistance, few residual solvents, being difficult to block, and having soil resistance, transparency, color density, adhesion, alcohol resistance, scratch resistance before and after coloring, head resistance, abrasion resistance, and oil resistance.

Means for Solving the Problems

[0009] As a result of intensive studies, the inventors of the present invention have found that the above object can be achieved by providing a heat-sensitive recording laminate having a heat-sensitive coloring layer composed of a heat-sensitive coloring agent containing a leuco dye, at least one color developer among specific compounds, an aqueous resin, an alcohol, and water, on one surface of a plastic film substrate, an aqueous coating layer composed of an aqueous coating agent containing a water-soluble resin and water on the heat-sensitive coloring layer, and an overcoat layer composed of an overcoat agent containing a thermoplastic resin, a polyisocyanate, and an organic solvent on the aqueous coating layer, and thus the present invention has been completed.

[0010] That is, according to the present invention, there are provided a heat-sensitive recording laminate, an overcoat set used for the heat-sensitive recording laminate, and a method for manufacturing the heat-sensitive recording laminate as described below. (1) A heat-sensitive coloring layer composed of a heat-sensitive coloring agent containing a leuco dye, at least one color developer among the compounds represented by the following general formula (1), the compound represented by the following general formula (2), the compound represented by the following general formula (3), and the compound represented by the following general formula (4), an aqueous resin, an alcohol, and water, on one surface of a plastic film substrate, an aqueous coating layer composed of an aqueous coating agent containing a water-soluble resin and water on the heat-sensitive coloring layer, and an overcoat layer composed of an overcoat agent containing a thermoplastic resin, a polyisocyanate, and an organic solvent on the aqueous coating layer. The heat-sensitive recording laminate is characterized by having the above structure.

[0011] [Chemical formula] (R 1 is a linear, branched, or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms substituted with a halogen atom, or an unsubstituted or aryl group having 6 to 12 carbon atoms substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a halogen atom, and they may be the same or different from each other. R 2is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different from each other, and Z 1 is a sulfonyloxy group, a sulfonyl group or a sulfonamide group.)

[0012] [Chemical formula] (R 3 is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkyloxyalkyl group having 3 to 12 carbon atoms, a polyoxyalkylene alkyl group having 3 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkylsulfanyl group having 1 to 12 carbon atoms, an aralkylsulfanyl group having 7 to 12 carbon atoms, an arylsulfanyl group having 6 to 14 carbon atoms, an alkylsulfonyl group having 1 to 12 carbon atoms, an aralkylsulfonyl group having 7 to 12 carbon atoms, an arylsulfonyl group having 6 to 15 carbon atoms, an aralkylsulfonylamino group having 7 to 12 carbon atoms, an arylsulfonylamino group having 6 to 15 carbon atoms, an acyl group having 2 to 10 carbon atoms, an acylamino group having 2 to 10 carbon atoms, an (acyl having 2 to 10 carbon atoms)oxycarbonylamino group, an (alkyl having 1 to 12 carbon atoms)oxycarbonylamino group, an aralkyloxycarbonylamino group, an (aralkyl having 7 to 12 carbon atoms)oxycarbonylamino group, or an (aryl having 6 to 15 carbon atoms)oxycarbonylamino group, and two adjacent Rs 3 may be bonded to each other to form an aromatic ring or a non-aromatic ring together with the carbon atoms to which they are respectively bonded, and R 4 R 5 is a hydrogen atom or a methyl group, a, b, c are independently integers from 0 to 4, a + c is an integer from 0 to 5, n is 0 or 1, Y is a divalent organic group, and Z 2 is a sulfonyloxy group or a sulfonyl group.)

[0013] [Chemical formula] (R 6is a linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms substituted with a halogen atom, or an unsubstituted or aryl group having 6 to 12 carbon atoms substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom, and R 7 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, l and m are 0 or 1, and Z 3 is a sulfonyloxy group, a sulfonyl group or a sulfonamide group.)

[0014] [Chemical formula] (R 8 is a linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms substituted with a halogen atom, or an unsubstituted or aryl group having 6 to 12 carbon atoms substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom, and they may be the same or different, and R 9 is a methyl group, d is an integer of 0 to 4, and Z 4 and Z 5 are a sulfonyloxy group, a sulfonyl group or a sulfonamide group, and they may be the same or different.)

[0015] (2) A heat-sensitive recording laminate characterized by having, on one surface of a plastic film substrate, a heat-sensitive coloring layer composed of a heat-sensitive color former containing a leuco dye, a compound represented by the following general formula (5), an aqueous resin, an alcohol and water, an aqueous coating layer composed of an aqueous coating agent containing a water-soluble resin and water on the heat-sensitive coloring layer, and an overcoat layer composed of an overcoat agent containing a thermoplastic resin, a polyisocyanate and an organic solvent on the aqueous coating layer.)

[0016]

Chem.

[0017] (3) The heat-sensitive recording laminate according to (1) or (2), wherein the aqueous resin is a water-soluble resin or an aqueous emulsion resin, (4) The heat-sensitive recording laminate according to any one of (1) to (3), wherein the thermoplastic resin is an acrylic resin, a polyurethane resin, a vinyl chloride-vinyl acetate copolymer, or a fiber-based resin, (5) An overcoat set used for the heat-sensitive recording laminate according to any one of (1) to (3), a coating agent A containing a thermoplastic resin and an organic solvent, a curing agent B containing a polyisocyanate and an organic solvent, and an overcoat set characterized by containing the same, (6) A method for producing a heat-sensitive recording laminate, comprising a step of preparing a plastic film substrate, a gravure printing step of forming a heat-sensitive coloring layer provided with a heat-sensitive color former containing a leuco dye, a developer, an aqueous resin, an alcohol, and water on one side of the plastic film substrate, a coating step of forming an aqueous coating layer provided with an aqueous coating agent containing a water-soluble resin and water on the heat-sensitive coloring layer, a coating step of forming an overcoat layer provided with an overcoat agent containing a thermoplastic resin, a polyisocyanate, and an organic solvent on the aqueous coating layer, The method for producing a heat-sensitive recording laminate is characterized in that the colorant is at least one of a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), and a compound represented by the following general formula (4).

[0018]

Chemical formula

[0019]

Chemical formula

[0020]

Chemical formula

[0021]

Chemical formula

[0022] (7) A step of preparing a plastic film substrate, A gravure printing step of forming a heat-sensitive coloring layer provided with a leuco dye, a developer, an aqueous resin, an alcohol, and a heat-sensitive color former containing water on one side of the plastic film substrate, A coating step of forming an aqueous coating layer provided with an aqueous coating agent containing a water-soluble resin and water on the heat-sensitive coloring layer, In a method for producing a heat-sensitive recording laminate comprising a coating step of forming an overcoat layer provided with an overcoat agent containing a thermoplastic resin, a polyisocyanate, and an organic solvent on the aqueous coating layer, A method for producing a heat-sensitive recording laminate, characterized in that the developer is a compound represented by the following general formula (5),

[0023]

Chemical formula

[0024] (8) The method for producing a thermosensitive recording laminate according to (6) or (7), characterized in that the aqueous resin is a water-soluble resin or an aqueous emulsion resin, (9) The method for producing a thermosensitive recording laminate according to any one of (6) to (8), characterized in that the thermoplastic resin is an acrylic resin, a polyurethane resin, a vinyl chloride-vinyl acetate copolymer, or a fiber-based resin, (10) The method for producing a thermosensitive recording laminate according to any one of (6) to (9), characterized by comprising a coating step of forming an anchor coat layer provided by an anchor coat agent between the plastic film substrate and the thermosensitive coloring layer, (11) The method for producing a thermosensitive recording laminate according to any one of (6) to (10), characterized by comprising a laminating step or a coating step of forming a seal layer on the plastic film substrate on the side opposite to the thermosensitive coloring layer, (12) The method for producing a thermosensitive recording laminate according to any one of (6) to (11), characterized by comprising a gravure printing step of forming a pattern layer on the plastic film substrate or on the plastic film substrate on the side opposite to the thermosensitive coloring layer, (13) The method for producing a thermosensitive recording laminate according to any one of (6) to (12), further characterized by comprising a gravure printing step of forming a colored ink layer, is as follows. [Effect of the Invention]

[0025] According to the present invention, it is possible to provide a laminate having excellent water resistance, low residual solvent content, low blocking tendency, soil resistance, transparency, color density, adhesion, alcohol resistance, scratch resistance before and after color development, head resistance, friction resistance, and oil resistance.

Embodiments for Carrying Out the Invention

[0026] Hereinafter, embodiments for carrying out the present invention will be described in detail. Note that this embodiment is merely one form for carrying out the present invention, and the present invention is not limited by this embodiment, and various modified embodiments are possible without departing from the gist of the present invention.

[0027] The thermosensitive recording laminate of the present invention has, on one surface of a plastic film substrate, a thermosensitive coloring layer composed of a leuco dye, at least one color former selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), and a compound represented by the following general formula (4), an aqueous resin, an alcohol, and water, an aqueous coat layer composed of an aqueous coating agent containing a water-soluble resin and water on the thermosensitive coloring layer, and an overcoat layer composed of an overcoat agent containing a thermoplastic resin, a polyisocyanate, and an organic solvent on the aqueous coat layer.

[0028] It is preferable that the thermosensitive coloring agent of the present invention contains a compound represented by the general formula (1). Examples of the compound represented by the general formula (1) are as follows.

[0029]

Chemical formula

[0030] R 1is a linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms substituted with a halogen atom, or an unsubstituted or aryl group having 6 to 12 carbon atoms substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom, and they may be the same or different from each other.

[0031] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a 2-ethylhexyl group, a lauryl group and the like.

[0032] Examples of the aralkyl group include an unsubstituted or aralkyl group substituted with an alkyl group, an alkoxy group, an aralkyl group, an aryl group or a halogen atom such as a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 3-phenylpropyl group, a p-methylbenzyl group, an m-methylbenzyl group, an m-ethylbenzyl group, a p-ethylbenzyl group, a p-isopropylbenzyl group, a p-t-butylbenzyl group, a p-methoxybenzyl group, an m-methoxybenzyl group, an o-methoxybenzyl group, an m,p-di-methoxybenzyl group, a p-ethoxy-m-methoxybenzyl group, a p-phenylmethylbenzyl group, a p-cumylbenzyl group, a p-phenylbenzyl group, an o-phenylbenzyl group, an m-phenylbenzyl group, a p-tolylbenzyl group, an m-tolylbenzyl group, an o-tolylbenzyl group, a p-chlorobenzyl group and the like.

[0033] Examples of the aryl group include unsubstituted or substituted aryl groups with an alkyl group, an alkoxy group, an aralkyl group, an aryl group, or a halogen atom, such as a phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, 2,5-dimethylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3-dimethylphenyl group, 3,4-dimethylphenyl group, mesitylene group, p-ethylphenyl group, p-isopropylphenyl group, p-t-butylphenyl group, p-methoxyphenyl group, 3,4-dimethoxyphenyl group, p-ethoxyphenyl group, p-chlorophenyl group, 1-naphthyl group, 2-naphthyl group, t-butylated naphthyl group, etc.

[0034] R 2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and they may be the same or different from each other. The position of R in the benzene ring of the general formula (1) 2 may be the same or different, and is the 3-position, 4-position or 5-position. Examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, t-butyl group, etc. Among them, a hydrogen atom is more preferable.

[0035] Z 1 includes a sulfonyloxy group, a sulfonyl group or a sulfonamide group. Among them, a compound containing a sulfonyloxy group represented by the following general formula (5) is more preferable. The position of -SO2-O- in the benzene ring of the general formula (5) 10 may be the same or different, and is the 3-position, 4-position or 5-position, and more preferably the 3-position.

[0036] It is more preferable that the heat-sensitive color former of the present invention contains a compound represented by the general formula (5). Examples of the compound represented by the general formula (5) include the following.

[0037]

Chemical formula

[0038] R 10 is a linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms substituted with a halogen atom, or an unsubstituted or aryl group having 6 to 12 carbon atoms substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom, and they may be the same or different from each other.

[0039] Said R 10 As for, those similar to said R 1 are mentioned, among which, a phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, mesitylene group, 2-naphthyl group, methyl group, ethyl group, benzyl group, p-ethylbenzyl group, p-methoxybenzyl group and the like are more preferable.

[0040] More specifically, N,N'-di-[3-(p-toluenesulfonyloxy)phenyl]urea, N,N'-di-[3-(o-toluenesulfonyloxy)phenyl]urea, N,N'-Di-[3-(benzenesulfonyloxy)phenyl]urea, N,N'-di-[(3-benzenesulfonyloxy)phenyl]urea, N,N'-di-[3-(mesitylenesulfonyloxy)phenyl]urea, N,N'-di-[3-(4-ethylbenzenesulfonyloxy)phenyl]urea, N,N'-di-[3-(2-naphthalenesulfonyloxy)phenyl]urea, N,N'-di-[3-(p-methoxybenzenesulfonyloxy)phenyl]urea, N,N'-di-[3-(benzylsulfonyloxy)phenyl]urea, N,N'-di-[3-(ethanesulfonyloxy)phenyl]urea, N,N'-di-[3-(p-toluenesulfonyloxy)-4-methyl-phenyl]urea, N,N'-di-[4-(p-toluenesulfonyloxy)phenyl]urea, N,N'-di-[4-(benzenesulfonyloxy)phenyl]urea, N,N'-di-[4-(ethanesulfonyloxy)phenyl]urea, N,N'-di-[2-(p-toluenesulfonyloxy)]phenylurea and the like can be mentioned.

[0041] It is preferable that the heat-sensitive color former of the present invention contains a compound represented by the general formula (2). Examples of the compound represented by the general formula (2) are as follows.

[0042] [Chemical formula]

[0043] R 3is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkyloxyalkyl group having 3 to 12 carbon atoms, a polyoxyalkylene alkyl group having 3 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkylsulfanyl group having 1 to 12 carbon atoms, an aralkylsulfanyl group having 7 to 12 carbon atoms, an arylsulfanyl group having 6 to 14 carbon atoms, an alkylsulfonyl group having 1 to 12 carbon atoms, an aralkylsulfonyl group having 7 to 12 carbon atoms, an arylsulfonyl group having 6 to 15 carbon atoms, an aralkylsulfonylamino group having 7 to 12 carbon atoms, an arylsulfonylamino group having 6 to 15 carbon atoms, an acyl group having 2 to 10 carbon atoms, an acylamino group having 2 to 10 carbon atoms, an (acyl having 2 to 10 carbon atoms) oxycarbonylamino group, an (alkyl having 1 to 12 carbon atoms) oxycarbonylamino group, an aralkyloxycarbonylamino group, an (aralkyl having 7 to 12 carbon atoms) oxycarbonylamino group, or an (aryl having 6 to 15 carbon atoms) oxycarbonylamino group.

[0044] Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a lauryl group and the like.

[0045] Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group and the like.

[0046] Examples of the alkyloxyalkyl group include C2H5O-C2H4-, C3H7O-C3H6- and the like.

[0047] Examples of the polyoxyalkylene alkyl group include O-(C2H4O)n-C2H4- (n = 1 to 3), HO-(C3H6O) n -C3H6- (n = 1 to 3) and the like.

[0048] Examples of the aralkyl group include benzyl group, p-methylbenzyl group, p-isopropylbenzyl group, p-t-butylbenzyl group, p-chlorobenzyl group, p-methoxybenzyl group, m-methoxybenzyl group, m, p-dimethoxybenzyl group, phenethyl group, α-phenethyl group, phenylpropyl group and the like.

[0049] Examples of the aryl group include phenyl group, tolyl group, p-ethylphenyl group, p-xylyl group, m-xylyl group, 1,2,3-trimethylphenyl group, mesitylene group, 1,2,4-trimethylphenyl group (pseudocumene group), 1-naphthyl group, 2-naphthyl group, biphenyl group, dimethylbiphenyl group and the like.

[0050] Examples of the alkylsulfanyl group include methylsulfanyl group, butylsulfanyl group and the like.

[0051] Examples of the aralkylsulfanyl group include benzylsulfanyl group, 1-phenylethylsulfanyl group, 2-phenylethylsulfanyl group, 1-phenylpropylsulfanyl group, 2-phenylpropylsulfanyl group, 1-phenylbutylsulfanyl group, 2-phenylbutylsulfanyl group, 1-naphthylmethylsulfanyl group, 2-naphthylmethylsulfanyl group, (1-naphthyl)ethylsulfanyl group, (2-naphthyl)ethylsulfanyl group and the like.

[0052] Examples of the arylsulfanyl group include phenylsulfanyl group and the like.

[0053] Examples of the alkylsulfonyl group include methanesulfonyl group, ethanesulfonyl group, propanesulfonyl group, butanesulfonyl group and the like.

[0054] Examples of the aralkylsulfonyl group include benzylsulfonyl group and the like.

[0055] Examples of the arylsulfonyl group include benzenesulfonyl group, toluenesulfonyl group, 2-p-xylylsulfonyl group, mesitylenesulfonyl group, 2,4,6-triisopropylbenzenesulfonyl group, 1-naphthalenesulfonyl group, 2-naphthalenesulfonyl group, 4-biphenylsulfonyl group and the like.

[0056] Examples of the aralkylsulfonylamino group include benzylsulfonylamino group and the like.

[0057] Examples of the arylsulfonylamino group include benzenesulfonylamino group, toluenesulfonylamino group and the like.

[0058] Examples of the acyl group include acetyl group, propionyl group, acryloyl group, methacryloyl group, benzoyl group, toluoyl group, 2-naphthoyl group and the like.

[0059] Examples of the acylamino group include acetylamino group, propionylamino group, benzoylamino group, toluoylamino group and the like.

[0060] Examples of the (acyl having 2 to 10 carbon atoms)oxycarbonylamino group include acetyloxycarbonylamino group, propionyloxycarbonylamino group, benzoyloxycarbonylamino group, toluoyloxycarbonylamino group and the like.

[0061] Examples of the (alkyl having 1 to 12 carbon atoms)oxycarbonylamino group include methoxycarbonylamino group, butoxycarbonylamino group and the like.

[0062] Examples of the aralkyloxycarbonylamino group include benzyloxycarbonylamino group, p-methoxybenzyloxycarbonylamino group, p-nitrobenzyloxycarbonylamino group and the like.

[0063] Examples of the (arylalkyl having 7 to 12 carbon atoms) aryloxycarbonylamino group include a phenethyloxycarbonylamino group, a 3-phenylpropyloxycarbonylamino group, a 4-phenylbutyloxycarbonylamino group, a (1-naphthyl)methyloxycarbonylamino group, a (2-naphthyl)methyloxycarbonylamino group, and the like.

[0064] Examples of the (aryl having 6 to 15 carbon atoms) oxycarbonylamino group include a phenoxycarbonylamino group, a tolyloxycarbonylamino group, and the like.

[0065] Two adjacent Rs in general formula (2) 3 may be bonded to each other to form an aromatic ring or a non-aromatic ring together with the carbon atoms to which they are respectively bonded, preferably an aromatic ring. For example, together with the aromatic ring to which R 3 is bonded, a naphthalene ring may be formed.

[0066] Among them, an alkyl group having 1 to 4 carbon atoms is more preferable.

[0067] R 4 and R 5 are preferably a hydrogen atom or a methyl group.

[0068] a, b, and c are independently integers from 0 to 4, and a + c is an integer from 0 to 5. It is more preferable that a and b are 0, and it is preferable that c is 0 or 1.

[0069] n is preferably 0 or 1, and more preferably 0.

[0070] Y is preferably a divalent organic group, which is a divalent organic group formed by removing two hydrogen atoms from a saturated or unsaturated aliphatic hydrocarbon or alicyclic hydrocarbon, a divalent organic group formed by removing two hydrogen atoms from an aliphatic hydrocarbon or alicyclic hydrocarbon linked by a linking group containing a hetero element, a divalent organic group formed by removing two hydrogen atoms from a monocyclic aromatic hydrocarbon, a divalent organic group formed by removing two hydrogen atoms from a polycyclic aromatic hydrocarbon, a divalent organic group formed by removing two hydrogen atoms from a plurality of aromatic hydrocarbons linked by a single bond, a divalent organic group formed by removing two hydrogen atoms from a plurality of aromatic hydrocarbons linked by a linking group formed by removing two hydrogen atoms from a saturated or unsaturated aliphatic hydrocarbon, a divalent organic group formed by removing two hydrogen atoms from a plurality of aromatic hydrocarbons linked by a linking group containing a hetero element, or a divalent organic group formed by removing two hydrogen atoms from a plurality of aromatic hydrocarbons linked by a linking group formed by removing two hydrogen atoms from an aromatic hydrocarbon, and the like.

[0071] Examples of the divalent organic group formed by removing two hydrogen atoms from the saturated or unsaturated aliphatic hydrocarbon or alicyclic hydrocarbon include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, an octamethylene group, an isopropylidene group, a cyclohexanediyl group, a vinylene group, a propenylene group, a 1-butenylene group, and the like.

[0072] Examples of the divalent organic group formed by removing two hydrogen atoms from an aliphatic hydrocarbon or alicyclic hydrocarbon linked by a linking group containing a hetero element such as -O-, -S-, -SO2-, -C(=O)- include -C2H4OC2H4-, -C2H4OC2H4OC2H4-, -C2H4SC2H4-, -C2H4-SO2-C2H4-, -C2H4COC2H4-, and the like.

[0073] Examples of the divalent organic group formed by removing two hydrogen atoms from a monocyclic aromatic hydrocarbon include benzene, toluene, xylene, mesitylene, benzyl, ethylbenzene, and the like.

[0074] Examples of the divalent organic group formed by removing two hydrogen atoms from polycyclic aromatic hydrocarbons such as naphthalene and substituted naphthalene include a naphthalenediyl group, 2,6-naphthalenediyl group, 1,8-naphthalenediyl group, 2,3-naphthalenediyl group, and the like.

[0075] Examples of the divalent organic group formed by removing two hydrogen atoms from a plurality of aromatic hydrocarbons linked by a single bond such as biphenyl and substituted biphenyl include a biphenyldiyl group and the like.

[0076] Examples of the divalent organic group formed by removing two hydrogen atoms from a plurality of aromatic hydrocarbons linked by a linking group formed by removing two hydrogen atoms from a saturated or unsaturated aliphatic hydrocarbon include diphenylmethane, 2,2-diphenylpropane, and the like.

[0077] Examples of the divalent organic group formed by removing two hydrogen atoms from a plurality of aromatic hydrocarbons linked by a linking group containing a hetero element include diphenyl ether, diphenoxyethane, di(phenoxyethyl) ether, diphenyl sulfide, diphenyl sulfone, and the like.

[0078] More preferable Y includes a divalent organic group formed by removing two hydrogen atoms from a monocyclic or polycyclic aromatic hydrocarbon such as a phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,2-phenylene group, biphenyl group, 4,4'-biphenyl group, 3,4'-biphenyl group, 3,3'-biphenyl group, oxydiphenyl group, 4,4'-oxydiphenyl group, 3,4'-oxydiphenyl group, 3,3'-oxydiphenyl group; a divalent organic group formed by removing two hydrogen atoms from a plurality of aromatic hydrocarbons linked by a single bond; and a divalent organic group formed by removing two hydrogen atoms from a plurality of aromatic hydrocarbons linked by a linking group containing a hetero element.

[0079] Z 2is a sulfonyloxy group or a sulfonyl group, which may be the same or different from each other. Among them, it is more preferably a sulfonyloxy group, and it is even more preferably the same for each.

[0080] More specifically, 1,3-bis-(3-[3-phenylureido]phenyloxysulfonyl)benzene, 1,3-bis-(3-[3-{m-tolyl}ureido]phenyloxysulfonyl)benzene, 1,3-bis-(4-[3-{m-tolyl}ureido]phenyloxysulfonyl)benzene, 4,4’-bis-(3-[3-{m-tolyl}ureido]phenyloxysulfonyl)biphenyl, 4,4’-bis-(3-[3-{m-tolyl}ureido]phenyloxysulfonyl)diphenyl ether, 4,4’-bis-(3-[3-phenylureido]phenyloxysulfonyl)diphenyl ether, 4,4’-bis-(3-[3-phenylureido]phenyloxysulfonyl)biphenyl, 1,3-bis-(3-[3-{p-tolyl}ureido]phenyloxysulfonyl)benzene, 1,3-bis-(3-[3-{1-naphthyl}ureido]phenyloxysulfonyl)benzene, etc. can be mentioned.

[0081] It is preferable that the heat-sensitive color former of the present invention contains a compound represented by the general formula (3). Examples of the compound represented by the general formula (3) are as follows.

[0082] [Chemical formula]

[0083] R 6 is a linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms substituted with a halogen atom, or an unsubstituted or aryl group having 6 to 12 carbon atoms substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom.

[0084] R 6 As for the above R 1 The same ones as those described above can be mentioned. Among them, a linear or branched alkyl group having 1 to 12 carbon atoms, a phenyl group substituted with an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, a benzyl group, etc. are more preferable.

[0085] R 7 is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, etc. can be mentioned. Among them, a methyl group is more preferable.

[0086] l and m are preferably 0 or 1, and more preferably 0.

[0087] Z 3 is preferably a sulfonyloxy group, a sulfonyl group or a sulfonamide group, and more preferably a sulfonyloxy group or a sulfonamide group.

[0088] More specifically, N-[2-(3-phenylureido)phenyl]benzenesulfonamide, N-benzyl-N'-3-(p-toluenesulfonyloxyphenyl)urea, 3-[(4-methylbenzenesulfonyl)methyl]-1-phenylurea, 3-[4-(octane-1-sulfonyl)phenyl]-1-phenylurea, 1-(benzenesulfonyl)-3-phenylurea, 1-(4-methylphenylsulfonyl)-3-phenylurea, etc. can be mentioned.

[0089] It is preferable that the heat-sensitive color former of the present invention contains a compound represented by the general formula (4). Examples of the compound represented by the general formula (4) are as follows.

[0090]

Chemical formula

[0091] R 8 is a linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms substituted with a halogen atom, or an unsubstituted or aryl group having 6 to 12 carbon atoms substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom, and they may be the same or different from each other.

[0092] R 8 Examples of 1 R

[0093] are the same as those of the above-mentioned 9 R 9 , and among them, a phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, mesitylene group, 2-naphthyl group, methyl group, ethyl group, benzyl group, p-ethylbenzyl group, p-methoxybenzyl group and the like are more preferable.

[0094] d is an integer of 0 to 4, and more preferably 0.

[0095] Z 4 and Z 5 are preferably a sulfonyloxy group, a sulfonyl group or a sulfonamide group, more preferably a sulfonyloxy group or a sulfonyl group, and the position of -Z 5 - in the benzene ring of the general formula (4) is the 3-position, 4-position or 5-position, and more preferably the 3-position.

[0096] More specifically, N-p-toluenesulfonyl-N'-3-(p-toluenesulfonyloxy)phenylurea, N-benzyl-N'-3-(p-toluenesulfonyloxy)phenylurea and the like can be mentioned.

[0097] Among the compounds represented by the general formulas (1) to (5), at least one color former is preferably contained in the thermosensitive color former in an amount of 1 to 70% by mass, more preferably 5 to 50% by mass, and even more preferably 10 to 40% by mass. If the amount of at least one of the compounds represented by the general formulas (1) to (5) is less than 1% by mass, the coloring effect is hardly exhibited. If it exceeds 70% by mass, the dispersion stability of the thermosensitive color former itself may be inferior, or the heat resistance or solvent resistance during printing may decrease.

[0098] The thermosensitive color former of the present invention preferably contains a leuco dye. As the leuco dye, all those known in the fields of conventional pressure-sensitive or thermosensitive recording materials can be used, and there is no particular limitation, but triarylmethane compounds, fluoran compounds, fluorene compounds, divinyl compounds, diphenylmethane compounds, thiazine compounds, spiro compounds, etc. are preferred. These leuco dyes can be used alone or in combination of two or more.

[0099] Examples of the triarylmethane compound include 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide and 3,3-bis(p-dimethylaminophenyl)phthalide.

[0100] Examples of the fluoran compound include 3 - diethylamino - 6 - methylfluoran, 3 - diethylamino - 6 - methyl - 7 - anilinofluoran, 3 - diethylamino - 6 - methyl - 7-(o,p - dimethylanilino)fluoran, 3 - diethylamino - 6 - methyl - 7 - chlorofluoran, 3 - diethylamino - 6 - methyl - 7-(m - trifluoromethylanilino)fluoran, 3 - diethylamino - 6 - methyl - 7-(o - chloroanilino)fluoran, 3 - diethylamino - 6 - methyl - 7-(p - chloroanilino)fluoran, 3 - diethylamino - 6 - methyl - 7-(o - fluoroanilino)fluoran, 3 - diethylamino - 6 - methyl - 7-(m - methylanilino)fluoran, 3 - diethylamino - 6 - methyl - 7 - n - octylanilinofluoran, 3 - diethylamino - 6 - methyl - 7 - n - octylaminofluoran, 3 - diethylamino - 6 - methyl - 7 - benzylaminofluoran, 3 - diethylamino - 6 - methyl - 7 - dibenzylaminofluoran, 3 - diethylamino - 6 - methyl - 7-(3 - methylphenylamino)fluoran, 3 - diethylamino - 6 - chloro - 7 - methylfluoran, 3 - diethylamino - 6 - chloro - 7 - anilinofluoran, 3 - diethylamino - 6 - chloro - 7 - p - methylanilinofluoran, 3 - diethylamino - 6 - ethoxyethyl - 7 - anilinofluoran, 3 - diethylamino - 7 - methylfluoran, 3 - diethylamino - 7 - octylaminofluoran, 3 - diethylamino - 7 - benzylaminofluoran, 3 - diethylamino - 7 - chlorofluoran, 3 - diethylamino - 7 - bromofluoran, 3 - diethylamino - 7 - phenoxyfluoran, 3 - diethylamino - 7 - phenylfluoran, 3 - diethylamino - 7-(m - trifluoromethylanilino)fluoran, 3 - diethylamino - 7-(o - chloroanilino)fluoran, 3 - diethylamino - 7-(p - chloroanilino)fluoran, 3 - diethylamino - 7-(o - fluoroanilino)fluoran, 3 - diethylamino - 7-(4 - nitroanilino)fluoran, 3 - diethylamino - 7-(3,4 - dichloroanilino)fluoran, 3 - diethylamino - benzo〔a〕fluoran, 3 - diethylamino - benzo〔c〕fluoran,3-Diethylamino-7,8-dibenzofluorane, 3-dibutylamino-6-methyl-fluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 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-7-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-fluoroanilino)fluorane, 3-di-n-pentylamino-6-methyl-7-anilinofluorane, 3-di-n-pentylamino-6-methyl-7-(p-chloroanilino)fluorane, 3-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, 3-(N-methyl-N-isoamylamino)-7-phenoxyfluorane, 3-(N-ethyl-N-cyclohexylamino)-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-hexylamino)-6-methyl-7-(p-chloroanilino)fluorane, 3-(N-ethyl-N-tolyl)amino-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-isoamylamino)-6-chloro-7-anilinofluorane3-(N-Ethyl-N-tetrahydrofurfurylamino)-6-methyl-7-anilinofluoran, 3-(N-ethyl-N-isobutylamino)-6-methyl-7-anilinofluoran, 3-(N-ethyl-N-ethoxypropylamino)-6-methyl-7-anilinofluoran, 3-(N-ethyl-N-tolyl)amino-6-methyl-7-phenethylaminofluoran, 3-(N-ethyl-N-n-hexylamino)-7-(o-chloroanilino)fluoran, 3-(N-ethyl-N-p-tolylamino)-7-(N-phenyl-N-methylamino)fluoran, 3-(N-methyl-N-isoamylamino)-7,8-benzofluoran, 3-cyclohexylamino-6-chlorofluoran, 3-pyrrolidino-6-chlorofluoran, 3-pyrrolidino-7-dibenzylaminofluoran, 2-(4-oxahexyl)-3-dimethylamino-6-methyl-7-anilinofluoran, 2-(4-oxahexyl)-3-diethylamino-6-methyl-7-anilinofluoran, 2-(4-oxahexyl)-3-dipropylamino-6-methyl-7-anilinofluoran, 2-methyl-6-p-(p-dimethylaminophenyl)aminoanilinofluoran, 2-methoxy-6-p-(p-dimethylaminophenyl)aminoanilinofluoran, 2-chloro-3-methyl-6-p-(p-phenylaminophenyl)aminoanilinofluoran, 2-chloro-6-p-(p-dimethylaminophenyl)aminoanilinofluoran, 2-nitro-6-p-(p-diethylaminophenyl)aminoanilinofluoran, 2-amino-6-p-(p-diethylaminophenyl)aminoanilinofluoran, 2-diethylamino-6-p-(p-diethylaminophenyl)aminoanilinofluoran, 2-phenyl-6-methyl-6-p-(p-phenylaminophenyl)aminoanilinofluoran, 2-benzyl-6-p-(p-phenylaminophenyl)aminoanilinofluoran, 2-hydroxy-6-p-(p-phenylaminophenyl)aminoanilinofluoran, 3-methyl-6-p-(p-dimethylaminophenyl)aminoanilinofluoran, 3-diethylamino-6-p-(p-diethylaminophenyl)aminoanilinofluoran3-Diethylamino-6-p-(p-dibutylaminophenyl)aminoanilinofluoran, 2,4-dimethyl-6-[(4-dimethylamino)anilino]-fluorane, 3,6-dimethoxyfluorane, etc. can be mentioned.

[0101] Examples of the fluorene-based compounds include 3,6,6'-tris(dimethylamino)spiro[fluorene-9,3'-phthalide], 3,6,6'-tris(diethylamino)spiro[fluorene-9,3'-phthalide], etc.

[0102] Examples of the divinyl-based compounds include 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, etc.

[0103] Examples of the diphenylmethane-based compounds include 4,4'-bisdimethylaminobenzhydrin benzyl ether, N-halophenyl leucoauramine, N-2,4,5-trichlorophenyl leucoauramine, etc.

[0104] Examples of the thiazine-based compounds include benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue, etc.

[0105] Examples of the spiro-based compounds include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3,3'-dichloro-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methylnaphtho-(3-methoxybenzene)-spiropyran, 3-propyl-spiro-dibenzopyran, etc.

[0106] Among 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)-4-azaphthalide, 3-(1-ethyl-2-methylindol-3-yl)-3-(4-diethylamino-2-n-hexyloxyphenyl)-4-azaphthalide, 3-(1-ethyl-2-methylindol-3-yl)-3-(4-diethylamino)-2-methylphenyl-4-azaphthalide, 3-(2-methyl-1-n-octylindol-3-yl)-3-(4-diethylamino-2-ethoxyphenyl)-4-azaphthalide, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl-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)-5-dimethylaminophthalide, 3,3-bis(2-phenylindol-3-yl)-5-dimethylaminophthalide, 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-methylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-phenylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(1-methylpyrrol-2-yl)-6-dimethylaminophthalide, 3-(p-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3,6-bis(diethylamino)fluorane-γ-(3'-nitro)anilinolactam, 3,6-bis(diethylamino)fluorane-γ-(4'-nitro)anilinolactam, 1,1-bis-[2',2',2'',2''-tetrakis-(p-dimethylaminophenyl)-ethenyl]-2,2-dinitrilethane, 1,1-bis-[2',2',2'',2''-Tetrakis-(p-dimethylaminophenyl)-ethenyl]-2-β-naphthoyl ethane, 1,1-bis-[2',2',2'',2''-tetrakis-(p-dimethylaminophenyl)-ethenyl]-2,2-diacetyl ethane, bis-[2,2,2',2'-tetrakis-(p-dimethylaminophenyl)-ethenyl]-dimethyl methylmalonate, 2,2-bis{4-[6'-(N-cyclohexyl-N-methylamino)-3'-methylspiro[phthalide-3,9'-xanthene]-2'-ylamino]phenyl}propane and the like can be mentioned.,

[0107] It is preferable that the leuco dye is contained in the heat-sensitive color former in an amount of 1 to 20% by mass, more preferably 3 to 15% by mass, and even more preferably 5 to 10% by mass. When the amount of the leuco dye is less than 1% by mass, the color development effect is hardly exhibited. When it exceeds 20% by mass, the dispersibility of the heat-sensitive color former itself is poor, so that the cohesive force of the heat-sensitive color developing layer film may not be obtained or poor adhesion to the plastic film substrate may occur., The content ratio of the color developer and the leuco dye contained in the heat-sensitive color former is preferably color developer / leuco dye = 7 / 1 to 0.5 / 1, more preferably 5 / 1 to 1 / 1, and even more preferably 4 / 1 to 2 / 1. When the content ratio is within the above range, the heat-sensitive color developability is excellent.,

[0108] It is preferable that the heat-sensitive color former of the present invention contains an aqueous resin. As the aqueous resin, a conventionally known resin can be used as long as it can be dissolved or dispersed in an aqueous medium. The aqueous medium refers to one containing water or a hydrophilic solvent as a component. Among them, a water-soluble resin or an aqueous emulsion resin is more preferable.,

[0109] The water-soluble resin has ionic groups such as sulfonyl groups and carboxyl groups, and water-soluble substituents such as hydroxyl groups in the molecule, and is soluble in water. For example, water-soluble polyacrylamide, water-soluble acrylic resins, water-soluble polyester resins, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral and other polyvinyl alcohol-based resins, water-soluble nylon resins, water-soluble alkyd resins, water-soluble melamine resins, water-soluble urea resins, water-soluble phenolic resins, water-soluble epoxy resins, water-soluble polybutadiene resins, water-soluble urethane resins, water-soluble acrylic / styrene resins, water-soluble vinyl acetate / acrylic copolymer resins, water-soluble styrene / maleic acid copolymer resins, water-soluble fluorine resins, water-soluble polyisocyanate resins, polystyrene-based resins, polyvinyl pyrrolidone, polyethylene oxide, polyvinyl acetate, carboxymethyl cellulose, water-soluble polyether resins and their copolymers, and natural polymer compounds such as starch, gelatin, casein, gum arabic, chitosan, dextran and guar gum. Among them, water-soluble acrylic resins and water-soluble polyester resins are more preferable. In particular, water-soluble polyester resins are even more preferable.

[0110] The aqueous emulsion resin refers to a state in which resin particles are dispersed in an aqueous medium or the like, and it does not matter whether the resin particles are solid or liquid. Examples of the resin particles include polyamides, polyimides, low-density polyethylene, high-density polyethylene, poly(meth)acrylate esters, polystyrenes and their derivatives such as polystyrene, polyvinyl chloride, phenolic resins, melamine resins, urea resins, epoxy resins, polybutadiene resins, polycarbonates, alkyd resins, fluorine resins, vinyl acetate resins, polyisocyanate resins, chlorinated polyolefin resins and their copolymers. Among them, poly(meth)acrylate esters, polystyrenes and their derivatives such as polystyrene are more preferable. In particular, polystyrenes are even more preferable, and it is preferable to contain acidic monomer units such as acrylic acid units and methacrylic acid units.

[0111] The aqueous resin is preferably contained in the thermosensitive color former in an amount of 1 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass. If the amount of the aqueous resin is less than 1% by mass, the dispersibility of the thermosensitive color former itself is poor, so that the cohesive force of the thermosensitive color developing layer film may not be obtained or poor adhesion to the plastic film substrate may occur. If it exceeds 50% by mass, there is a possibility of a decrease in printing density and poor fluidity.

[0112] It is preferable that the thermosensitive color former of the present invention contains alcohol. Examples of the alcohol include methanol, ethanol, propyl alcohol, isopropyl alcohol, normal propyl alcohol, 1-butanol, 2-butanol, isobutanol, tert-butanol, ethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,4-pentanediol, 2,5-hexanediol, 1,6-hexanediol, triethylene glycol, 1-methyl-1,3-butylene glycol, 2-methyl-1,3-butylene glycol, 2,4-diethyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, tripropylene glycol, 1,2-propylene glycol, 2-methyl-1,5-pentanediol, 2-methyl-1,4-pentanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,2,4-trimethyl-1,6-hexanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc. Among them, methanol, ethanol, propyl alcohol, isopropyl alcohol, normal propyl alcohol, and propylene glycol monomethyl ether are more preferable.

[0113] It is preferable that the alcohol is contained in the thermosensitive color former in an amount of 1 to 50% by mass, more preferably 2 to 40% by mass, and even more preferably 5 to 20% by mass. If the amount of the alcohol is less than 1% by mass, it may be difficult to dry and the high-speed printing suitability may be poor. If it exceeds 50% by mass, there may be a decrease in printing density and poor fluidity.

[0114] In the heat-sensitive color former of the present invention, a sensitizer can be used as necessary, and conventionally known sensitizers can be used. For example, fatty acid amides such as stearic acid amide, bisstearic acid amide, N-hydroxymethyl stearic acid amide, N-stearyl stearic acid amide, ethylene bisstearic acid amide, methylene bisstearic acid amide, methylol stearic acid amide, palmitic acid amide, p-toluenesulfonamide, calcium, zinc or aluminum fatty acid metal salts such as stearic acid, behenic acid and palmitic acid, N-stearyl urea, benzyl-2-naphthyl ether, 4-benzylbiphenyl, 2,2'-bis(4-methoxyphenoxy)diethyl ether, α,α'-diphenoxyxylene, bis(4-methoxyphenyl)ether, p-benzylbiphenyl, diphenyl sulfone, benzyl benzyloxybenzoate, 2-benzyloxynaphthalene, 1,2-bis(m-tolyloxy)ethane, 1,2-bis(p-tolyloxy)ethane, 1,2-bis(phenoxy)ethane, 1,2-bis(3-methylphenoxy)ethane, 1,3-bis(phenoxy)propane, dibenzyl oxalate, p-methylbenzyl oxalate, bis(4-methylbenzyl) oxalate ester, bis(4-chlorobenzyl) oxalate ester, diphenyl adipate, dimethyl terephthalate, dibenzyl terephthalate, phenyl benzenesulfonate, bis(4-allyloxyphenyl) sulfone, 1,2-diphenoxyethane, 4-acetylacetophenone, m-terphenyl, 1-hydroxy-2-naphthoic acid, acetacetic acid anilides, fatty acid anilides, etc. can be mentioned. Among them, 1,2-bis(3-methylphenoxy)ethane, 1,2-bis(m-tolyloxy)ethane, 1,2-bis(p-tolyloxy)ethane, 1,2-bis(phenoxy)ethane are more preferable.

[0115] It is preferable that the heat-sensitive color former of the present invention contains water. The water is not particularly limited, and tap water, well water, distilled water, ion-exchanged water, pure water, etc. can be used. Among them, it is more preferable to use distilled water, ion-exchanged water, pure water.

[0116] The water content is the remainder of each of the above-described components.

[0117] In the heat-sensitive color former of the present invention, a colorant, an inorganic filler, an organic filler, an antifoaming agent, a leveling agent, an antiblocking agent, a pigment dispersant, an antistatic agent, a slip agent, a plasticizer, a tackifier, a curing agent, a silane coupling agent, a wax, etc. can also be contained as necessary. Any known and commonly used ones can be appropriately selected as long as the characteristics as a heat-sensitive color former are not impaired.

[0118] Examples of the colorant include inorganic or organic pigments such as amorphous silica, amorphous calcium silicate, heavy calcium carbonate, light calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium dioxide, zinc oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, colloidal silica, polystyrene powder, nylon powder, urea-formalin resin filler, styrene-methacrylic acid copolymer, styrene-butadiene copolymer, and hollow plastic pigment.

[0119] The heat-sensitive color former of the present invention is preferably used in gravure printing. It can be applied as it is, but depending on the coating conditions and coating effect, it can be adjusted to a desired viscosity by diluting with a diluting solvent using a Zahn cup #3 (manufactured by Riai Co., Ltd.) and then used. In this case, the viscosity is preferably 10 to 40 seconds at 25°C. If it is less than 10 seconds, it is likely to spread, and if it is more than 40 seconds, the transferability during printing deteriorates.

[0120] Any diluting solvent may be used as long as it can adjust the viscosity of the ink composition. Examples include organic solvents and water, and commercially available products can also be used, with no particular limitation. Commercially available products include WA734 solvent (alcohol-based solvent), WA735 solvent (alcohol-based solvent), WA736 solvent (alcohol-based solvent), TA50 solvent (alcohol-based solvent), TA52 solvent (alcohol-based solvent) (all manufactured by Tokyo Ink Co., Ltd.).

[0121] The heat-sensitive recording laminate of the present invention preferably has a heat-sensitive coloring layer composed of the above-mentioned heat-sensitive coloring agent.

[0122] The thickness of the heat-sensitive coloring layer is preferably 0.1 to 5 μm, more preferably 0.2 to 3 μm. If the thickness of the heat-sensitive coloring layer is less than 0.1 μm, the coloring density after printing may be insufficient, and if it exceeds 5 μm, there is a risk of blocking.

[0123] The heat-sensitive recording laminate of the present invention preferably has an aqueous coating layer composed of an aqueous coating agent on the heat-sensitive coloring layer.

[0124] The aqueous coating agent preferably contains a water-soluble resin and water.

[0125] As the water-soluble resin used in the aqueous coating agent, the same water-soluble resin as the heat-sensitive coloring agent can be used. Among them, polyvinyl alcohols are more preferable. These water-soluble resins can be used alone or in combination of two or more.

[0126] The water-soluble resin is preferably contained in the aqueous coating agent in an amount of 1 to 50% by mass, more preferably 2 to 30% by mass. If the amount of the water-soluble resin is less than 1% by mass, the film-forming property of the aqueous coating layer is poor, and if it exceeds 50% by mass, the fluidity of the ink is poor and the manufacturing suitability is poor.

[0127] The water is not particularly limited, and tap water, well water, distilled water, ion-exchanged water, pure water, etc. can be used. Further, it may contain a solvent usually used in gravure ink. For example, aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane, alcohol solvents such as methanol, ethanol, isopropyl alcohol, normal propyl alcohol, 1-butanol, 2-butanol, isobutanol, and tert-butanol, ester solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, and tert-butyl acetate, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether, and esterified products thereof. As the esterified products, mainly acetylated ones are selected, and examples include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Among them, from the viewpoints of printing suitability and versatility, toluene, ethyl acetate, n-propyl acetate, isopropyl alcohol, propylene glycol monomethyl ether, methyl ethyl ketone, etc. are more preferable. These can be used alone or in combination of two or more.

[0128] In the aqueous coating agent, it is preferable that the water is in the range of 1 to 50% by mass. If it is less than 1% by mass, wetting during printing deteriorates, and if it exceeds 50% by mass, the viscosity increases and the production suitability deteriorates.

[0129] In the aqueous coating agent of the present invention, a colorant, an inorganic filler, an organic filler, an antifoaming agent, a leveling agent, an antiblocking agent, a pigment dispersant, an antistatic agent, a slip agent, a plasticizer, a tackifier, a curing agent, a silane coupling agent, a wax, etc. can also be contained as necessary. Any known and commonly used ones can be appropriately selected as long as the characteristics as an aqueous coating agent are not impaired.

[0130] The aqueous coating agent of the present invention is preferably used in gravure printing, and can be directly coated, but depending on the coating conditions and coating effect, it can be adjusted to a desired viscosity by diluting with a diluting solvent using a Zahn cup #3 (manufactured by Reika Co., Ltd.) and then used. In this case, the viscosity is preferably 10 to 40 seconds at 25°C. If it is less than 10 seconds, it is likely to spread, and if it is more than 40 seconds, the transferability during printing deteriorates.

[0131] Any diluting solvent may be used as long as it can adjust the viscosity of the aqueous coating agent, and examples include organic solvents and water. Commercially available products can also be used, and there is no particular limitation. Commercially available products include WA734 solvent (alcohol-based solvent), WA735 solvent (alcohol-based solvent), WA736 solvent (alcohol-based solvent), TA50 solvent (alcohol-based solvent), TA52 solvent (alcohol-based solvent) (all of the above are manufactured by Tokyo Ink Co., Ltd.), etc.

[0132] The thickness of the aqueous coating layer is preferably 0.01 to 2 μm, more preferably 0.05 to 1.4 μm, and even more preferably 0.1 to 1.2 μm. If the thickness of the aqueous coating layer is less than 0.01 μm, the film-forming property of the aqueous coating layer is poor, and if it exceeds 2 μm, it is difficult to dry and there is a risk of poor suitability for high-speed printing.

[0133] The heat-sensitive recording laminate of the present invention preferably has an overcoat layer made of an overcoating agent on the aqueous coating layer.

[0134] The overcoat agent preferably contains a thermoplastic resin, a polyisocyanate, and an organic solvent.

[0135] The thermoplastic resin is preferably an acrylic resin, a polyurethane resin, a vinyl chloride-vinyl acetate copolymer, or a fiber-based resin. Among them, an acrylic resin, a polyurethane resin, and a vinyl chloride-vinyl acetate copolymer are more preferable. These can be used alone or in combination of two or more.

[0136] The thermoplastic resin is preferably contained in the overcoat agent in an amount of 1 to 50% by mass, more preferably 2 to 45% by mass. When the amount of the thermoplastic resin is less than 1% by mass, the film-forming property of the overcoat layer is poor, and the protective effect on the heat-sensitive coloring layer is hardly exhibited. When it exceeds 50% by mass, there is a risk of blocking.

[0137] Examples of the polyisocyanate include alicyclic diisocyanates such as isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and methylcyclohexylene diisocyanate; aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, butane-1,4-diisocyanate, pentane-1,5-diisocyanate, and xylylene diisocyanate (XDI), and trimethylolpropane trimers thereof; aromatic diisocyanates such as tolylene diisocyanate (TDI), α,α,α',α'-tetramethylxylylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, and tetraalkyldiphenylmethane diisocyanate, and modified products thereof. Among these, alicyclic diisocyanates, aliphatic diisocyanates, and aromatic aliphatic diisocyanates are more preferable. These may be used alone or in admixture of two or more.

[0138] The polyisocyanate is preferably contained in the overcoat agent in an amount of 1 to 50% by mass, more preferably 2 to 45% by mass. If the amount of the polyisocyanate is less than 1% by mass, it is difficult to obtain a crosslinking effect, and if it exceeds 50% by mass, there is a risk of blocking.

[0139] The content ratio of the thermoplastic resin and the polyisocyanate contained in the overcoat agent is preferably such that the solid content of the polyisocyanate is 1 / 100 to 50 / 100, more preferably 5 / 100 to 40 / 100, and even more preferably 15 / 100 to 35 / 100 with respect to 100 of the solid content of the thermoplastic resin contained in the overcoat agent. When the content ratio is within the above range, it is excellent in alcohol resistance, scratch resistance, water resistance, and oil resistance.

[0140] As the organic solvent, solvents usually used in gravure inks can be used. For example, aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane, alcohol solvents such as methanol, ethanol, isopropyl alcohol, normal propyl alcohol, 1-butanol, 2-butanol, isobutanol, and tert-butanol, ester solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, and tert-butyl acetate, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether, and their esterified products. As the esterified products, mainly acetylated ones are selected. For example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate can be mentioned. Among them, from the viewpoints of printing suitability and versatility, toluene, ethyl acetate, n-propyl acetate, isopropyl alcohol, propylene glycol monomethyl ether, methyl ethyl ketone, etc. are more preferable. These can be used alone or in combination of two or more kinds.

[0141] In the overcoat agent, the organic solvent is preferably in the range of 45 to 90% by mass, more preferably in the range of 60 to 80% by mass. If it is less than 45% by mass, the solid content increases, the fluidity deteriorates, and the manufacturability of the overcoat agent is inferior. If it exceeds 90% by mass, the viscosity decreases, and there is a risk that a beautiful printing effect cannot be obtained.

[0142] In the overcoat agent of the present invention, if necessary, a colorant, an inorganic filler, an organic filler, an antifoaming agent, a leveling agent, a pigment dispersant, an antistatic agent, a slip agent, a plasticizer, a tackifier, a silane coupling agent, etc. can also be contained. Any known and commonly used ones can be appropriately selected as long as the characteristics as an overcoat agent are not impaired.

[0143] The overcoat agent of the present invention is preferably used in gravure printing. It can be applied as it is, but depending on the coating conditions and coating effect, it can be adjusted to a desired viscosity by diluting with a diluting solvent using a Zahn cup #3 (manufactured by Reika Co., Ltd.) and then used. In this case, the viscosity at 25°C is preferably 10 to 40 seconds. If it is less than 10 seconds, it is likely to swim, and if it is more than 40 seconds, the transferability during printing deteriorates.

[0144] The diluting solvent may be any as long as it can adjust the viscosity of the overcoat agent. Examples include organic solvents, and commercially available products can also be used, with no particular limitation. Commercially available products include TS32 solvent (ester-based solvent), PU533 solvent (toluene-containing solvent), PU515 solvent (non-toluene solvent), SL9155 solvent (non-toluene solvent), CN104 solvent (non-toluene solvent), AC372 solvent (non-toluene solvent), PP575 solvent (toluene-containing solvent), SL9164 solvent (non-ketone solvent), SL9170 solvent (non-ketone solvent) (all of the above are manufactured by Tokyo Ink Co., Ltd.), etc.

[0145] The thickness of the overcoat layer is preferably 0.05 to 5 μm, more preferably 0.1 to 3 μm. If the thickness of the overcoat layer is less than 0.05 μm, the protective effect on the aqueous coat layer is insufficient, and if it exceeds 5 μm, there is a risk of blocking.

[0146] The thermosensitive recording laminate of the present invention can be used to produce a printed matter by causing the thermosensitive coloring layer to develop color using a thermal printer (for example, TH-M2 / PP, manufactured by Ohkura Engineering Co., Ltd.). Regarding the coloring density, a heat sealer (manufactured by Tester Sangyo Co., Ltd.) etc. is used to cause the thermosensitive recording laminate to develop color, and L * a * b * It can be evaluated by the L value measured by the method defined in the color system (CIE1976). The lower the L value, the higher the blackness degree, and it can be judged as good. As the device for measuring the coloring density, a reflection densitometer, a spectral densitometer, a spectrophotometer, etc. can be used. For example, a portable spectral density / colorimeter eXact 2 (manufactured by X-Rite) etc. can be mentioned.

[0147] The thermosensitive recording laminate of the present invention may have an anchor coat layer between the plastic film substrate and the thermosensitive coloring layer.

[0148] The anchor coat layer is made of an anchor coating agent, and a resin can be used for the anchor coating agent. Examples of the resin include starches such as oxidized starch, esterified starch, and etherified starch; cellulose resins such as methyl cellulose, carboxymethyl cellulose, methoxy cellulose, hydroxyethyl cellulose, etc.; casein, gelatin, fully (or partially) saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, silicon-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, etc.; polyvinyl alcohols; styrene-maleic anhydride copolymer latex, styrene-butadiene copolymer latex, vinyl acetate resin latex, urethane resin latex, acrylic resin latex, etc. These can be used alone or in combination of two or more.

[0149] The same organic solvents as those used in the aqueous coating agent or the overcoat agent can be used for the anchor coating agent. Among them, from the viewpoints of printability and versatility, toluene, ethyl acetate, n-propyl acetate, isopropyl alcohol, propylene glycol monomethyl ether, methyl ethyl ketone, etc. can be mentioned. These can be used alone or in combination of two or more.

[0150] In the anchor coating agent of the present invention, a colorant, an inorganic filler, an organic filler, an antifoaming agent, a leveling agent, an antiblocking agent, a pigment dispersant, an antistatic agent, a slip agent, a plasticizer, a tackifier, a system curing agent, a silane coupling agent, a wax, etc. can also be contained as required. Any known and commonly used ones can be appropriately selected as long as the characteristics as an anchor coating agent are not impaired. Commercially available products can also be used without particular limitation. Examples of commercially available products include LG-OX Anchor Agent D (manufactured by Tokyo Ink Co., Ltd.).

[0151] The anchor coat agent of the present invention is preferably used in gravure printing. It can be applied as it is, but depending on the coating conditions and coating effect, it can be adjusted to a desired viscosity by diluting with a diluting solvent in a Zahn cup #3 (manufactured by Reika Co., Ltd.) and then used. In this case, the viscosity is preferably 10 to 40 seconds at 25°C. If it is less than 10 seconds, it is likely to run, and if it is more than 40 seconds, the transferability during printing deteriorates.

[0152] The diluting solvent may be any as long as it can adjust the viscosity of the anchor coat agent. Examples include organic solvents, and commercially available products can also be used, with no particular limitation. Commercially available products include TS32 solvent (ester-based solvent), PU533 solvent (toluene-containing solvent), PU515 solvent (non-toluene solvent), SL9155 solvent (non-toluene solvent), CN104 solvent (non-toluene solvent), AC372 solvent (non-toluene solvent), PP575 solvent (toluene-containing solvent), SL9164 solvent (non-ketone solvent), SL9170 solvent (non-ketone solvent) (all of the above are manufactured by Tokyo Ink Co., Ltd.), etc.

[0153] The thickness of the anchor coat layer is preferably 0.05 to 3 μm, and more preferably 0.1 to 2 μm. If the thickness of the anchor coat layer is less than 0.05 μm, the coating amount is small and there is a risk that the plastic film substrate cannot be covered. If it exceeds 3 μm, there is a risk of blocking.

[0154] As the plastic film base material, it is preferably at least one selected from plastic films or sheets and laminates thereof. For example, polyester films such as polyethylene terephthalate (PET), polyethylene naphthalate, polybutylene terephthalate, polyolefin films such as polyethylene, polypropylene, ethylene-vinyl acetate, polystyrene films, alcohol-based films such as ethylene-vinyl alcohol, polyvinyl alcohol, polyamide films or barrier polyamide films with a barrier layer in the middle, polycarbonate films, polyacrylonitrile films, polyimide films, cellophane, moisture-proof cellophane, transparent vapor-deposited polyester films or transparent vapor-deposited polyamide films obtained by providing a vapor-deposited layer of alumina or silica on a PET film or polyamide film, various coating films coated with polyvinylidene chloride resin, polyvinyl alcohol resin, polyacrylic acid resin, etc., co-extruded films of PET and nylon, polylactic acid films, etc. These may be either stretched or unstretched, and one type or two or more types may be laminated. An appropriate one can be selected in consideration of mechanical strength, dimensional stability, etc. Also, in order to improve the adhesion of the anchor coat layer or laminate layer on the surface, corona treatment, low-temperature plasma treatment, flame treatment, solvent treatment, coating treatment, etc. can be applied, or those previously applied can be selected. Among them, PET films, polypropylene films, polyamide films, coating films, transparent vapor-deposited polyester films or transparent vapor-deposited polyamide films, co-extruded films, etc. are preferred. The thickness of the plastic film base material is not particularly limited as long as it does not interfere with printing suitability, winding suitability, etc., but is preferably 5 to 300 μm, and more preferably 6 to 250 μm. Also, a plastic film base material obtained by previously printing the anchor coat agent on the plastic film base material may be used.

[0155] The heat-sensitive color-developing layer, the aqueous coating layer, the overcoat layer, and the anchor coat layer are preferably formed on one surface of the plastic film substrate by gravure printing. In particular, it is more preferable to form them by gravure printing using a multicolor gravure printing machine. Since they can be formed by gravure printing, each layer can be formed over the entire surface, or each layer can be easily formed partially.

[0156] The heat-sensitive recording laminate of the present invention may have a seal layer on the plastic film substrate on the side opposite to the heat-sensitive color-developing layer.

[0157] Examples of the seal layer include layers formed by laminating a laminate imparted with heat-sealability or a known sealant film (dry lamination method, non-solvent lamination method, wet lamination method), resin coating by an extrusion lamination method (extrusion lamination method, co-extrusion lamination method, PE sandwich lamination method), heat bonding (heat lamination method), etc., and layers formed by coating a heat-sealing agent or a hot melt agent. Further, layers formed by coating an adhesive or an adhesive are also included.

[0158] The thickness of the seal layer is not particularly limited, but in the case of a sealant film, it is preferably 2 to 200 μm, in the case of resin coating by an extrusion lamination method, it is preferably 1 to 100 μm, in the case of coating a heat-sealing agent, it is preferably 0.01 to 30 μm, and in the case of coating a hot melt adhesive, it is preferably 1 to 50 μm.

[0159] Examples of the sealant film include polyolefin films such as polyethylene, polypropylene, ethylene-vinyl acetate, and copolymers thereof, co-extruded films and colored films thereof, polystyrene films, polyacrylonitrile films, ethylene-vinyl alcohol resin films, etc. It may be stretched or unstretched, and one type or two or more types may be laminated.

[0160] When using an adhesive in the dry lamination method, non-solvent lamination method, wet lamination method, extrusion lamination method, etc., commercially available ones may be used. For example, two-component or one-component urethane-based resin adhesives, acrylic-based, epoxy-based, polyester-based, polyethyleneimine-based, polybutadiene-based, water-based urethane-based, isocyanate-based, organic titanium-based, starch-based water-soluble adhesives, and aqueous adhesives such as vinyl acetate emulsions can be mentioned. As the coating method of the adhesive for forming the sealant layer, known coating methods can be used. For example, a roll coater, reverse roll coater, gravure offset coater, gravure coater, microgravure coater, knife coater, bar coater, wire bar coater, die coater, dip coater, etc. can be used. The thickness of the adhesive is not particularly limited, but a range of about 0.001 to 10 μm is preferable, and a range of 0.01 to 5 μm is particularly preferable.

[0161] Examples of the resin that can be used for the resin coating by the extrusion lamination method include thermoplastic resins such as polyethylene resins such as LDPE, LLDPE, and HDPE, polypropylene resin, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, and acid-modified polyolefin resins obtained by modifying polyethylene or polypropylene with maleic acid or fumaric acid, polystyrene resin, and polybutylene terephthalate resin. These resins can be used alone or in combination of two or more.

[0162] Examples of the resin of the heat-sealing agent include, for example, thermoplastic resins such as vinylidene chloride, shellacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, nitrocellulose, cellulose acetate, cellulose acetyl propionate, cellulose acetyl butyrate, chlorinated rubber, cyclized rubber, polyamide resins, vinyl chloride-vinyl acetate copolymers, polyester resins, ketone resins, butyral resins, chlorinated polypropylene resins, chlorinated polyethylene resins, chlorinated ethylene vinyl acetate resins, ethylene vinyl acetate resins, (meth)acrylic resins, urethane resins, ethylene-vinyl alcohol resins, styrene maleic acid resins, casein, alkyd resins, etc. These may be used alone or in combination of two or more. Types in which these resins are dissolved in a solvent, or those dispersed in water such as acrylic emulsions, urethane emulsions, ethylene-vinyl alcohol emulsions, polyethylene emulsions, polypropylene emulsions, ethylene vinyl acetate emulsions, etc. may be mentioned.

[0163] The thermosensitive recording laminate of the present invention may have a pattern layer on the plastic film substrate or on the plastic film substrate on the opposite side of the thermosensitive coloring layer. Further, it may have a colored ink layer. The formation order of the pattern layer and the colored ink layer is not limited. Also, it may be provided over the entire surface or in a part, and may be in the form of halftone dots. The pattern layer is usually a layer formed using a color printing ink composition used for gravure printing, and is a layer on which patterns, characters, etc. are printed. Also, the colored ink layer is usually a layer formed using a white ink composition used for gravure printing, etc., and is a layer used for providing contrast with the pattern layer, etc. in a solid or halftone dot form to make it easier to see.

[0164] The thermosensitive recording laminate of the present invention is preferably used for packaging applications, food preservation applications, retort applications, microwave oven applications, agricultural applications, civil engineering applications, fishery applications, interior and exterior automotive applications, ship applications, daily necessities applications, interior and exterior building material applications, housing equipment applications, medical and medical device applications, pharmaceutical applications, home appliance applications, furniture applications, stationery and office supply applications, sales promotion applications, commercial applications, electrical and electronic industry applications, and industrial material applications. Among them, it is more preferably used for packaging applications, retort applications, and microwave oven applications.

[0165] The overcoat set of the present invention is an overcoat set used for a thermosensitive recording laminate, and preferably includes a coating agent A containing a thermoplastic resin and an organic solvent, and a curing agent B containing a polyisocyanate and an organic solvent.

[0166] Among them, the overcoat set is more preferably used to provide an overcoat layer on one surface of the plastic film substrate constituting the thermosensitive recording laminate, on the thermosensitive coloring layer and on the aqueous coating layer provided on the thermosensitive coloring layer.

[0167] The thermoplastic resin contained in the coating agent A is preferably an acrylic resin, a polyurethane resin, a vinyl chloride-vinyl acetate copolymer, or a fiber-based resin. Among them, an acrylic resin, a polyurethane resin, and a vinyl chloride-vinyl acetate copolymer are more preferable. These can be used alone or in combination of two or more.

[0168] The thermoplastic resin is preferably contained in the coating agent A in an amount of 1 to 50% by mass, and more preferably 2 to 45% by mass. If the amount of the thermoplastic resin is less than 1% by mass, the film-forming property of the overcoat layer is poor, and the protective effect on the thermosensitive coloring layer is difficult to exhibit. If it exceeds 50% by mass, there is a risk of blocking.

[0169] As the organic solvent, solvents usually used in gravure inks can be used. For example, aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane, alcohol solvents such as methanol, ethanol, isopropyl alcohol, normal propyl alcohol, 1-butanol, 2-butanol, isobutanol, and tert-butanol, ester solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, and tert-butyl acetate, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether, and esterified products thereof can be mentioned. As the esterified products, mainly acetylated ones are selected, and examples include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Among them, from the viewpoints of printing suitability and versatility, toluene, ethyl acetate, n-propyl acetate, isopropyl alcohol, propylene glycol monomethyl ether, methyl ethyl ketone, etc. are more preferable. These can be used alone or in combination of two or more kinds.

[0170] In the coating agent A, the organic solvent is preferably in the range of 45 to 90% by mass, more preferably in the range of 60 to 80% by mass. If it is less than 45% by mass, the solid content increases, the fluidity deteriorates, and the manufacturability of the coating agent A is inferior. If it exceeds 90% by mass, the viscosity becomes low and there is a risk that a beautiful printing effect cannot be obtained.

[0171] In the coating agent A of the present invention, if necessary, a coloring material, an inorganic filler, an organic filler, an antifoaming agent, a leveling agent, a pigment dispersant, an antistatic agent, a slip agent, a plasticizer, a tackifier, a silane coupling agent, etc. can also be contained. Any well-known and commonly used ones can be appropriately selected as long as the properties as a coating agent are not impaired.

[0172] The polyisocyanate contained in the hardener B includes, as polyisocyanates, alicyclic diisocyanates such as isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexylene diisocyanate, aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, butane-1,4-diisocyanate, pentane-1,5-diisocyanate, xylylene diisocyanate (XDI), and trimethylolpropane trimers thereof, tolylene diisocyanate (TDI), α,α,α',α'-tetramethylxylylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate and other aromatic diisocyanates and modified products thereof. Among them, alicyclic diisocyanates, aliphatic diisocyanates and araliphatic diisocyanates are more preferred. These can be used alone or in admixture of two or more.

[0173] The polyisocyanate is preferably contained in the curing agent B in an amount of 1 to 50% by mass, more preferably 2 to 45% by mass. If the amount of the polyisocyanate is less than 1% by mass, it is difficult to obtain a crosslinking effect, and if it exceeds 50% by mass, there is a risk of blocking.

[0174] As the organic solvent contained in the curing agent B, the same organic solvent as that of the coating agent A can be used.

[0175] In the curing agent, the organic solvent is preferably in the range of 45 to 90% by mass, more preferably in the range of 60 to 80% by mass. If it is less than 45% by mass, the solid content increases, the fluidity deteriorates, and the manufacturability of the overcoating agent is inferior. If it exceeds 90% by mass, the viscosity decreases, and there is a risk that a beautiful printing effect cannot be obtained.

[0176] In the curing agent B of the present invention, a colorant, an inorganic filler, an organic filler, an antifoaming agent, a leveling agent, a pigment dispersant, an antistatic agent, a slip agent, a plasticizer, a tackifier, a silane coupling agent, etc. can be contained as necessary. Any publicly known and commonly used ones can be appropriately selected as long as the properties as a curing agent are not impaired.

[0177] The overcoat set of the present invention uses both the coating agent A and the curing agent B. That is, it is used as a two-component mixture. The content ratio of the thermoplastic resin and the polyisocyanate contained in the two-component mixture is preferably such that the solid content of the polyisocyanate is 100 / 1 to 100 / 50, more preferably 100 / 5 to 100 / 40, and even more preferably 100 / 15 to 100 / 35 with respect to 100 of the solid content of the thermoplastic resin contained in the two-component mixture. When the content ratio is within the above range, it is excellent in alcohol resistance, scratch resistance, oil resistance, water resistance, and solvent resistance. It is preferable to mix the coating agent A and the curing agent B so that their content ratios are the same as those of the thermoplastic resin and the polyisocyanate. Preferably, the ratio of coating agent A / curing agent B is 100 / 1 to 100 / 30, and more preferably 100 / 5 to 100 / 15. By using the coating agent A and the curing agent B in two components within the above range, excellent alcohol resistance, scratch resistance, oil resistance, water resistance, and solvent resistance can be obtained.

[0178] The two-component mixture can be produced by mixing or dispersing the coating agent A and the curing agent B by a known method. In particular, it is more preferable to mix or disperse them in a printing factory or the like. Mixing or dispersing can be easily achieved by manual stirring, but various stirrers or dispersers such as a dissolver, a paint shaker, and a homomixer can also be used. These devices may be used alone or in combination of two or more.

[0179] The two-component mixture is preferably used in gravure printing. It can be directly applied, but depending on the coating conditions and coating effect, it can be adjusted to a desired viscosity by diluting with a diluting solvent using a Zahn cup #3 (manufactured by Reika Co., Ltd.) and then used. In this case, the viscosity at 25 °C is preferably 10 to 40 seconds. If it is less than 10 seconds, it is likely to spread, and if it is more than 40 seconds, the transferability during printing deteriorates.

[0180] Any diluting solvent may be used as long as it can adjust the viscosity of the two-component mixture. Examples include organic solvents, and commercially available products can also be used, with no particular limitation. Commercially available products include TS32 solvent (ester-based solvent), PU533 solvent (toluene-containing solvent), PU515 solvent (non-toluene solvent), SL9155 solvent (non-toluene solvent), CN104 solvent (non-toluene solvent), AC372 solvent (non-toluene solvent), PP575 solvent (toluene-containing solvent), SL9164 solvent (non-ketone solvent), SL9170 solvent (non-ketone solvent) (all of the above are manufactured by Tokyo Ink Co., Ltd.), etc.

[0181] The coating agent A can be produced by a known method by uniformly dissolving or dispersing a thermoplastic resin and various additives in the above-described organic solvent. Dissolution or dispersion can be carried out using various stirrers or dispersers such as a dissolver, a roll mill, a ball mill, a bead mill, a sand mill, an attritor, a paint shaker, an agitator, a Henschel mixer, a colloid mill, a pearl mill, an ultrasonic homogenizer, a wet jet mill, a kneader, and a homomixer. These devices may be used alone or in combination of two or more types. When the ink composition contains air bubbles or coarse particles, it is preferable to remove them using a known filter or centrifuge in order to reduce printability and print quality.

[0182] The viscosity of the coating agent A is not particularly limited as long as it does not interfere with printing. Considering the manufacturing suitability, handling, etc. of the coating agent used in gravure printing, it is preferably 10 to 1,000 mPa·s at 25°C. If it is less than 10 mPa·s, the viscosity is too low and the pigment tends to settle. If it is greater than 1,000 mPa·s, the fluidity is poor, which may cause problems during ink production or make it difficult to fill the container. In this case, it can be measured using a commercially available viscometer such as a Brookfield viscometer, a cone and plate viscometer, or a B-type viscometer.

[0183] The coating agent A is preferably used in gravure printing. It can be applied as it is, but depending on the coating conditions and coating effect, it can be adjusted to a desired viscosity by diluting with a diluting solvent using a Zahn cup #3 (manufactured by Reika Co., Ltd.) and then used. The viscosity in this case is preferably 10 to 40 seconds at 25°C. If it is less than 10 seconds, it is likely to spread, and if it is greater than 40 seconds, the transferability during printing deteriorates.

[0184] The curing agent B can be produced by a known method by uniformly dissolving or dispersing polyisocyanate, various additives, etc. in the above-described organic solvent. Dissolution or dispersion can be carried out using various stirrers or dispersers such as a dissolver, a roll mill, a ball mill, a bead mill, a sand mill, an attritor, a paint shaker, an agitator, a Henschel mixer, a colloid mill, a pearl mill, an ultrasonic homogenizer, a wet jet mill, a kneader, a homomixer, etc. These apparatuses may be used alone or in combination of two or more kinds. When the curing agent contains air bubbles or coarse particles, it is preferable to remove them using a known filter, a centrifuge, etc. because it deteriorates the printability and the printed article quality.

[0185] A method for producing a thermosensitive recording laminate includes a step of preparing a plastic film substrate, a gravure printing step of forming a thermosensitive coloring layer provided with a thermosensitive color former containing a leuco dye, a developer, an aqueous resin, an alcohol, and water on one side of the plastic film substrate, a coating step of forming an aqueous coating layer provided with an aqueous coating agent containing a water-soluble resin and water on the thermosensitive coloring layer, and a coating step of forming an overcoat layer provided with an overcoat agent containing a thermoplastic resin, a polyisocyanate, and an organic solvent on the aqueous coating layer. In the method for producing a thermosensitive recording laminate, it is preferable that the developer is at least one of a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), and a compound represented by the following general formula (4). Among them, it is more preferable that the developer is a compound represented by the following general formula (5).

[0186] It is preferable that the thermosensitive color former of the present invention contains a compound represented by the general formula (1). Examples of the compound represented by the general formula (1) are as follows.

[0187]

Chemical formula

[0188] R 1is a linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms substituted with a halogen atom, or an unsubstituted or aryl group having 6 to 12 carbon atoms substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom, and they may be the same or different from each other.

[0189] Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, cyclopentyl group, hexyl group, cyclohexyl group, 2-ethylhexyl group, lauryl group and the like.

[0190] Examples of the aralkyl group include benzyl group, 1-phenylethyl group, 2-phenylethyl group, 3-phenylpropyl group, p-methylbenzyl group, m-methylbenzyl group, m-ethylbenzyl group, p-ethylbenzyl group, p-isopropylbenzyl group, p-t-butylbenzyl group, p-methoxybenzyl group, m-methoxybenzyl group, o-methoxybenzyl group, m,p-di-methoxybenzyl group, p-ethoxy-m-methoxybenzyl group, p-phenylmethylbenzyl group, p-cumylbenzyl group, p-phenylbenzyl group, o-phenylbenzyl group, m-phenylbenzyl group, p-tolylbenzyl group, m-tolylbenzyl group, o-tolylbenzyl group, p-chlorobenzyl group and the like, which are unsubstituted or aralkyl groups substituted with an alkyl group, an alkoxy group, an aralkyl group, an aryl group or a halogen atom.

[0191] Examples of the aryl group include unsubstituted or substituted aryl groups with an alkyl group, an alkoxy group, an aralkyl group, an aryl group, or a halogen atom, such as a phenyl group, a p-tolyl group, an m-tolyl group, an o-tolyl group, a 2,5-dimethylphenyl group, a 2,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 2,3-dimethylphenyl group, a 3,4-dimethylphenyl group, a mesitylene group, a p-ethylphenyl group, a p-isopropylphenyl group, a p-t-butylphenyl group, a p-methoxyphenyl group, a 3,4-dimethoxyphenyl group, a p-ethoxyphenyl group, a p-chlorophenyl group, a 1-naphthyl group, a 2-naphthyl group, and a t-butylated naphthyl group.

[0192] R 2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and they may be the same or different from each other. The position of R in the benzene ring of the general formula (1) 2 may be the same or different, and is the 3-position, 4-position, or 5-position. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. Among them, a hydrogen atom is more preferable.

[0193] Z 1 includes a sulfonyloxy group, a sulfonyl group, or a sulfonamide group. Among them, a compound containing a sulfonyloxy group represented by the following general formula (5) is more preferable. The position of -SO2-O- in the benzene ring of the general formula (5) 10 may be the same or different, and is the 3-position, 4-position, or 5-position, and more preferably the 3-position.

[0194] It is more preferable that the thermochromic dye of the present invention contains a compound represented by the general formula (5). Examples of the compound represented by the general formula (5) include the following.

[0195]

Chemical formula

[0196] R 10 is a linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms substituted with a halogen atom, or an unsubstituted or aryl group having 6 to 12 carbon atoms substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom, and they may be the same or different from each other.

[0197] Said R 10 As, those similar to said R 1 are mentioned, and among them, a phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, mesitylene group, 2-naphthyl group, methyl group, ethyl group, benzyl group, p-ethylbenzyl group, p-methoxybenzyl group and the like are more preferable.

[0198] More specifically, N,N'-di-[3-(p-toluenesulfonyloxy)phenyl]urea, N,N'-di-[3-(o-toluenesulfonyloxy)phenyl]urea, N,N'-di-[3-(benzenesulfonyloxy)phenyl]urea, N,N'-di-[(3-benzenesulfonyloxy)phenyl]urea, N,N'-di-[3-(mesitylenesulfonyloxy)phenyl]urea, N,N'-di-[3-(4-ethylbenzenesulfonyloxy)phenyl]urea, N,N'-di-[3-(2-naphthalenesulfonyloxy)phenyl]urea, N,N'-di-[3-(p-methoxybenzenesulfonyloxy)phenyl]urea, N,N'-di-[3-(benzylsulfonyloxy)phenyl]urea, N,N'-di-[3-(ethanesulfonyloxy)phenyl]urea, N,N'-di-[3-(p-toluenesulfonyloxy)-4-methyl-phenyl]urea, N,N'-di-[4-(p-toluenesulfonyloxy)phenyl]urea, N,N'-di-[4-(benzenesulfonyloxy)phenyl]urea, N,N'-di-[4-(ethanesulfonyloxy)phenyl]urea, N,N'-di-[2-(p-toluenesulfonyloxy)]phenylurea and the like are mentioned.

[0199] It is preferable that the heat-sensitive color former of the present invention contains a compound represented by the general formula (2). Examples of the compound represented by the general formula (2) are as follows.

[0200]

Chemical formula

[0201] R 3 is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkyloxyalkyl group having 3 to 12 carbon atoms, a polyoxyalkylene alkyl group having 3 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkylsulfanyl group having 1 to 12 carbon atoms, an aralkylsulfanyl group having 7 to 12 carbon atoms, an arylsulfanyl group having 6 to 14 carbon atoms, an alkylsulfonyl group having 1 to 12 carbon atoms, an aralkylsulfonyl group having 7 to 12 carbon atoms, an arylsulfonyl group having 6 to 15 carbon atoms, an aralkylsulfonylamino group having 7 to 12 carbon atoms, an arylsulfonylamino group having 6 to 15 carbon atoms, an acyl group having 2 to 10 carbon atoms, an acylamino group having 2 to 10 carbon atoms, an (acyl having 2 to 10 carbon atoms) oxycarbonylamino group, an (alkyl having 1 to 12 carbon atoms) oxycarbonylamino group, an aralkyloxycarbonylamino group, an (aralkyl having 7 to 12 carbon atoms) oxycarbonylamino group, or an (aryl having 6 to 15 carbon atoms) oxycarbonylamino group.

[0202] Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a lauryl group, and the like.

[0203] Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, and the like.

[0204] Examples of the alkyloxyalkyl group include C2H5O-C2H4-, C3H7O-C3H6-, and the like.

[0205] Examples of the polyoxyalkylene alkyl group include O-(C2H4O)n-C2H4- (n = 1 to 3) and HO-(C3H6O) n -C3H6- (n = 1 to 3).

[0206] Examples of the aralkyl group include benzyl group, p-methylbenzyl group, p-isopropylbenzyl group, p-t-butylbenzyl group, p-chlorobenzyl group, p-methoxybenzyl group, m-methoxybenzyl group, m,p-dimethoxybenzyl group, phenethyl group, α-phenethyl group, phenylpropyl group and the like.

[0207] Examples of the aryl group include phenyl group, tolyl group, p-ethylphenyl group, p-xylyl group, m-xylyl group, 1,2,3-trimethylphenyl group, mesitylene group, 1,2,4-trimethylphenyl group (pseudocumene group), 1-naphthyl group, 2-naphthyl group, biphenyl group, dimethylbiphenyl group and the like.

[0208] Examples of the alkylsulfanyl group include methylsulfanyl group, butylsulfanyl group and the like.

[0209] Examples of the aralkylsulfanyl group include benzylsulfanyl group, 1-phenylethylsulfanyl group, 2-phenylethylsulfanyl group, 1-phenylpropylsulfanyl group, 2-phenylpropylsulfanyl group, 1-phenylbutylsulfanyl group, 2-phenylbutylsulfanyl group, 1-naphthylmethylsulfanyl group, 2-naphthylmethylsulfanyl group, (1-naphthyl)ethylsulfanyl group, (2-naphthyl)ethylsulfanyl group and the like.

[0210] Examples of the arylsulfanyl group include phenylsulfanyl group and the like.

[0211] Examples of the alkylsulfonyl group include methanesulfonyl group, ethanesulfonyl group, propanesulfonyl group, butanesulfonyl group and the like.

[0212] Examples of the aralkylsulfonyl group include a benzylsulfonyl group.

[0213] Examples of the arylsulfonyl group include a benzenesulfonyl group, a toluenesulfonyl group, a 2-p-xylenesulfonyl group, a mesitylenesulfonyl group, a 2,4,6-triisopropylbenzenesulfonyl group, a 1-naphthalenesulfonyl group, a 2-naphthalenesulfonyl group, and a 4-biphenylsulfonyl group.

[0214] Examples of the aralkylsulfonylamino group include a benzylsulfonylamino group.

[0215] Examples of the arylsulfonylamino group include a benzenesulfonylamino group and a toluenesulfonylamino group.

[0216] Examples of the acyl group include an acetyl group, a propionyl group, an acryloyl group, a methacryloyl group, a benzoyl group, a toluoyl group, and a 2-naphthoyl group.

[0217] Examples of the acylamino group include an acetylamino group, a propionylamino group, a benzoylamino group, and a toluoylamino group.

[0218] Examples of the (acyl having 2 to 10 carbon atoms)oxycarbonylamino group include an acetyloxycarbonylamino group, a propionyloxycarbonylamino group, a benzoyloxycarbonylamino group, and a toluoyloxycarbonylamino group.

[0219] Examples of the (alkyl having 1 to 12 carbon atoms)oxycarbonylamino group include a methoxycarbonylamino group and a butoxycarbonylamino group.

[0220] Examples of the aralkyloxycarbonylamino group include a benzyloxycarbonylamino group.

[0221] Examples of the (arylalkyl having 7 to 12 carbon atoms) aryloxycarbonylamino group include a phenethyloxycarbonylamino group, a 3-phenylpropyloxycarbonylamino group, a 4-phenylbutyloxycarbonylamino group, a (1-naphthyl)methyloxycarbonylamino group, a (2-naphthyl)methyloxycarbonylamino group, and the like.

[0222] Examples of the (aryl having 6 to 15 carbon atoms) oxycarbonylamino group include a phenoxycarbonylamino group, a tolyloxycarbonylamino group, and the like.

[0223] Two adjacent Rs in the general formula (2) 3 may be bonded to each other to form an aromatic ring or a non-aromatic ring together with the carbon atoms to which they are respectively bonded, preferably an aromatic ring. For example, they may form a naphthalene ring together with the aromatic ring to which R 3 is bonded.

[0224] Among them, an alkyl group having 1 to 4 carbon atoms is more preferable.

[0225] R 4 and R 5 are preferably a hydrogen atom or a methyl group.

[0226] a, b, and c are independently integers from 0 to 4, and a + c is an integer from 0 to 5. It is more preferable that a and b are 0, and it is preferable that c is 0 or 1.

[0227] n is preferably 0 or 1, and more preferably 0.

[0228] Y is preferably a divalent organic group, which is a divalent organic group formed by removing two hydrogen atoms from a saturated or unsaturated aliphatic hydrocarbon or alicyclic hydrocarbon, a divalent organic group formed by removing two hydrogen atoms from an aliphatic hydrocarbon or alicyclic hydrocarbon linked by a linking group containing a hetero element, a divalent organic group formed by removing two hydrogen atoms from a monocyclic aromatic hydrocarbon, a divalent organic group formed by removing two hydrogen atoms from a polycyclic aromatic hydrocarbon, a divalent organic group formed by removing two hydrogen atoms from a plurality of aromatic hydrocarbons linked by a single bond, a divalent organic group formed by removing two hydrogen atoms from a plurality of aromatic hydrocarbons linked by a linking group formed by removing two hydrogen atoms from a saturated or unsaturated aliphatic hydrocarbon, a divalent organic group formed by removing two hydrogen atoms from a plurality of aromatic hydrocarbons linked by a linking group containing a hetero element, or a divalent organic group formed by removing two hydrogen atoms from a plurality of aromatic hydrocarbons linked by a linking group formed by removing two hydrogen atoms from an aromatic hydrocarbon, and the like.

[0229] Examples of the divalent organic group formed by removing two hydrogen atoms from the saturated or unsaturated aliphatic hydrocarbon or alicyclic hydrocarbon include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, an octamethylene group, an isopropylidene group, a cyclohexanediyl group, a vinylene group, a propenylene group, a 1-butenylene group, and the like.

[0230] Examples of the divalent organic group formed by removing two hydrogen atoms from an aliphatic hydrocarbon or alicyclic hydrocarbon linked by a linking group containing a hetero element such as -O-, -S-, -SO2-, -C(=O)- include -C2H4OC2H4-, -C2H4OC2H4OC2H4-, -C2H4SC2H4-, -C2H4-SO2-C2H4-, -C2H4COC2H4-, and the like.

[0231] Examples of the divalent organic group formed by removing two hydrogen atoms from a monocyclic aromatic hydrocarbon include benzene, toluene, xylene, mesitylene, benzyl, ethylbenzene, and the like.

[0232] Examples of the divalent organic group obtained by removing two hydrogen atoms from a polycyclic aromatic hydrocarbon such as naphthalene or a substituted naphthalene include a naphthalenediyl group, a 2,6-naphthalenediyl group, a 1,8-naphthalenediyl group, and a 2,3-naphthalenediyl group.

[0233] Examples of the divalent organic group obtained by removing two hydrogen atoms from a plurality of aromatic hydrocarbons linked by single bonds, such as biphenyl and substituted biphenyl, include a biphenyldiyl group.

[0234] Examples of divalent organic groups obtained by removing two hydrogen atoms from a plurality of aromatic hydrocarbons linked by a linking group obtained by removing two hydrogen atoms from the saturated or unsaturated aliphatic hydrocarbon include diphenylmethane and 2,2-diphenylpropane.

[0235] Examples of the divalent organic group obtained by removing two hydrogen atoms from a plurality of aromatic hydrocarbons linked by a linking group containing a heteroatom include diphenyl ether, diphenoxyethane, di(phenoxyethyl) ether, diphenyl sulfide, and diphenyl sulfone.

[0236] More preferred examples of Y include divalent organic groups obtained by removing two hydrogen atoms from a monocyclic or polycyclic aromatic hydrocarbon such as a phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,2-phenylene group, biphenyl group, 4,4'-biphenyl group, 3,4'-biphenyl group, 3,3'-biphenyl group, oxydiphenyl group, 4,4'-oxydiphenyl group, 3,4'-oxydiphenyl group, and 3,3'-oxydiphenyl group; divalent organic groups obtained by removing two hydrogen atoms from multiple aromatic hydrocarbons linked by single bonds; and divalent organic groups obtained by removing two hydrogen atoms from multiple aromatic hydrocarbons linked by a linking group containing a hetero element.

[0237] Z 2is a sulfonyloxy group or a sulfonyl group, which may be the same or different from each other. Among them, it is more preferably a sulfonyloxy group, and it is even more preferably the same for each.

[0238] More specifically, 1,3-bis-(3-[3-phenylureido]phenyloxysulfonyl)benzene, 1,3-bis-(3-[3-{m-tolyl}ureido]phenyloxysulfonyl)benzene, 1,3-bis-(4-[3-{m-tolyl}ureido]phenyloxysulfonyl)benzene, 4,4'-bis-(3-[3-{m-tolyl}ureido]phenyloxysulfonyl)biphenyl, 4,4'-bis-(3-[3-{m-tolyl}ureido]phenyloxysulfonyl)diphenyl ether, 4,4'-bis-(3-[3-phenylureido]phenyloxysulfonyl)diphenyl ether, 4,4'-bis-(3-[3-phenylureido]phenyloxysulfonyl)biphenyl, 1,3-bis-(3-[3-{p-tolyl}ureido]phenyloxysulfonyl)benzene, 1,3-bis-(3-[3-{1-naphthyl}ureido]phenyloxysulfonyl)benzene, etc. can be mentioned.

[0239] It is preferable that the heat-sensitive color former of the present invention contains a compound represented by the general formula (3). Examples of the compound represented by the general formula (3) are as follows.

[0240]

Chemical formula

[0241] R 6 is a linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms substituted with a halogen atom, or an unsubstituted or aryl group having 6 to 12 carbon atoms substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom.

[0242] R 6 Examples of the group represented by R 1 are the same as those of the above R, and among them, a linear or branched alkyl group having 1 to 12 carbon atoms, a phenyl group substituted with an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, a benzyl group, etc. are more preferable.

[0243] R 7 is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, etc. can be mentioned, and among them, a methyl group is more preferable.

[0244] l and m are preferably 0 or 1, and more preferably 0.

[0245] Z 3 is preferably a sulfonyloxy group, a sulfonyl group or a sulfonamide group, and more preferably a sulfonyloxy group or a sulfonamide group.

[0246] More specifically, N-[2-(3-phenylureido)phenyl]benzenesulfonamide, N-benzyl-N'-3-(p-toluenesulfonyloxyphenyl)urea, 3-[(4-methylbenzenesulfonyl)methyl]-1-phenylurea, 3-[4-(octane-1-sulfonyl)phenyl]-1-phenylurea, 1-(benzenesulfonyl)-3-phenylurea, 1-(4-methylphenylsulfonyl)-3-phenylurea, etc. can be mentioned.

[0247] It is preferable that the thermochromic dye of the present invention contains a compound represented by the general formula (4). Examples of the compound represented by the general formula (4) are as follows.

[0248]

Chemical formula

[0249] R 8 is a linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms substituted with a halogen atom, or an aryl group having 6 to 12 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom, and they may be the same or different from each other.

[0250] R 8 Examples of 1 R

[0251] R 9 are the same as those of the above 9 R, and among them, a phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, mesitylene group, 2-naphthyl group, methyl group, ethyl group, benzyl group, p-ethylbenzyl group, p-methoxybenzyl group and the like are more preferable.

[0252] d is an integer of 0 to 4, and more preferably 0.

[0253] Z 4 and Z 5 are preferably a sulfonyloxy group, a sulfonyl group or a sulfonamide group, more preferably a sulfonyloxy group or a sulfonyl group, and the position of -Z 5 - in the benzene ring of the general formula (4) is the 3-position, 4-position or 5-position, and more preferably the 3-position.

[0254] More specifically, N-p-toluenesulfonyl-N'-3-(p-toluenesulfonyloxy)phenylurea, N-benzyl-N'-3-(p-toluenesulfonyloxy)phenylurea and the like can be mentioned.

[0255] Among the compounds represented by the general formulas (1) to (5), at least one color former is preferably contained in the thermosensitive color former in an amount of 1 to 70% by mass, more preferably 5 to 50% by mass, and even more preferably 10 to 40% by mass. If the amount of at least one of the compounds represented by the general formulas (1) to (5) is less than 1% by mass, the color development effect is difficult to appear. If it exceeds 70% by mass, there is a risk that the dispersion stability of the thermosensitive color former itself will deteriorate, or the heat resistance or solvent resistance during printing will decrease.

[0256] The thermosensitive color former of the present invention preferably contains a leuco dye. As the leuco dye, all those known in the conventional pressure-sensitive or thermosensitive recording material field can be used, and there is no particular limitation. However, triarylmethane compounds, fluoran compounds, fluorene compounds, divinyl compounds, diphenylmethane compounds, thiazine compounds, spiro compounds, etc. are preferred. These leuco dyes can be used alone or in admixture of two or more.

[0257] Examples of the triarylmethane compound include 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)phthalide, and the like.

[0258] Examples of the fluoran compound include 3 - diethylamino - 6 - methylfluoran, 3 - diethylamino - 6 - methyl - 7 - anilinofluoran, 3 - diethylamino - 6 - methyl - 7-(o,p - dimethylanilino)fluoran, 3 - diethylamino - 6 - methyl - 7 - chlorofluoran, 3 - diethylamino - 6 - methyl - 7-(m - trifluoromethylanilino)fluoran, 3 - diethylamino - 6 - methyl - 7-(o - chloroanilino)fluoran, 3 - diethylamino - 6 - methyl - 7-(p - chloroanilino)fluoran, 3 - diethylamino - 6 - methyl - 7-(o - fluoroanilino)fluoran, 3 - diethylamino - 6 - methyl - 7-(m - methylanilino)fluoran, 3 - diethylamino - 6 - methyl - 7 - n - octylanilinofluoran, 3 - diethylamino - 6 - methyl - 7 - n - octylaminofluoran, 3 - diethylamino - 6 - methyl - 7 - benzylaminofluoran, 3 - diethylamino - 6 - methyl - 7 - dibenzylaminofluoran, 3 - diethylamino - 6 - methyl - 7-(3 - methylphenylamino)fluoran, 3 - diethylamino - 6 - chloro - 7 - methylfluoran, 3 - diethylamino - 6 - chloro - 7 - anilinofluoran, 3 - diethylamino - 6 - chloro - 7 - p - methylanilinofluoran, 3 - diethylamino - 6 - ethoxyethyl - 7 - anilinofluoran, 3 - diethylamino - 7 - methylfluoran, 3 - diethylamino - 7 - octylaminofluoran, 3 - diethylamino - 7 - benzylaminofluoran, 3 - diethylamino - 7 - chlorofluoran, 3 - diethylamino - 7 - bromofluoran, 3 - diethylamino - 7 - phenoxyfluoran, 3 - diethylamino - 7 - phenylfluoran, 3 - diethylamino - 7-(m - trifluoromethylanilino)fluoran, 3 - diethylamino - 7-(o - chloroanilino)fluoran, 3 - diethylamino - 7-(p - chloroanilino)fluoran, 3 - diethylamino - 7-(o - fluoroanilino)fluoran, 3 - diethylamino - 7-(4 - nitroanilino)fluoran, 3 - diethylamino - 7-(3,4 - dichloroanilino)fluoran, 3 - diethylamino - benz[a]fluoran, 3 - diethylamino - benz[c]fluoran,3-Diethylamino-7,8-dibenzofluorane, 3-dibutylamino-6-methyl-fluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 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-7-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-fluoroanilino)fluorane, 3-di-n-pentylamino-6-methyl-7-anilinofluorane, 3-di-n-pentylamino-6-methyl-7-(p-chloroanilino)fluorane, 3-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, 3-(N-methyl-N-isoamylamino)-7-phenoxyfluorane, 3-(N-ethyl-N-cyclohexylamino)-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-hexylamino)-6-methyl-7-(p-chloroanilino)fluorane, 3-(N-ethyl-N-tolyl)amino-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-isoamylamino)-6-chloro-7-anilinofluorane3-(N-Ethyl-N-tetrahydrofurfurylamino)-6-methyl-7-anilinofluoran, 3-(N-ethyl-N-isobutylamino)-6-methyl-7-anilinofluoran, 3-(N-ethyl-N-ethoxypropylamino)-6-methyl-7-anilinofluoran, 3-(N-ethyl-N-tolyl)amino-6-methyl-7-phenethylaminofluoran, 3-(N-ethyl-N-n-hexylamino)-7-(o-chloroanilino)fluoran, 3-(N-ethyl-N-p-tolylamino)-7-(N-phenyl-N-methylamino)fluoran, 3-(N-methyl-N-isoamylamino)-7,8-benzofluoran, 3-cyclohexylamino-6-chlorofluoran, 3-pyrrolidino-6-chlorofluoran, 3-pyrrolidino-7-dibenzylaminofluoran, 2-(4-oxahexyl)-3-dimethylamino-6-methyl-7-anilinofluoran, 2-(4-oxahexyl)-3-diethylamino-6-methyl-7-anilinofluoran, 2-(4-oxahexyl)-3-dipropylamino-6-methyl-7-anilinofluoran, 2-methyl-6-p-(p-dimethylaminophenyl)aminoanilinofluoran, 2-methoxy-6-p-(p-dimethylaminophenyl)aminoanilinofluoran, 2-chloro-3-methyl-6-p-(p-phenylaminophenyl)aminoanilinofluoran, 2-chloro-6-p-(p-dimethylaminophenyl)aminoanilinofluoran, 2-nitro-6-p-(p-diethylaminophenyl)aminoanilinofluoran, 2-amino-6-p-(p-diethylaminophenyl)aminoanilinofluoran, 2-diethylamino-6-p-(p-diethylaminophenyl)aminoanilinofluoran, 2-phenyl-6-methyl-6-p-(p-phenylaminophenyl)aminoanilinofluoran, 2-benzyl-6-p-(p-phenylaminophenyl)aminoanilinofluoran, 2-hydroxy-6-p-(p-phenylaminophenyl)aminoanilinofluoran, 3-methyl-6-p-(p-dimethylaminophenyl)aminoanilinofluoran, 3-diethylamino-6-p-(p-diethylaminophenyl)aminoanilinofluoran,3-Diethylamino-6-p-(p-dibutylaminophenyl)aminoanilinofluoran, 2,4-dimethyl-6-[(4-dimethylamino)anilino]-fluorane, 3,6-dimethoxyfluorane, and the like can be mentioned.

[0259] Examples of the fluorene-based compound include 3,6,6'-tris(dimethylamino)spiro[fluorene-9,3'-phthalide], 3,6,6'-tris(diethylamino)spiro[fluorene-9,3'-phthalide], and the like.

[0260] Examples of the divinyl-based compound include 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, and the like.

[0261] Examples of the diphenylmethane-based compound include 4,4'-bisdimethylaminobenzhydrin benzyl ether, N-halophenyl leucoauramine, N-2,4,5-trichlorophenyl leucoauramine, and the like.

[0262] Examples of the thiazine-based compound include benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue, and the like.

[0263] Examples of the spiro-based compound include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3,3'-dichloro-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methylnaphtho-(3-methoxybenzene)-spiropyran, 3-propyl-spiro-dibenzopyran, and the like.

[0264] Among 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)-4-azaphthalide, 3-(1-ethyl-2-methylindol-3-yl)-3-(4-diethylamino-2-n-hexyloxyphenyl)-4-azaphthalide, 3-(1-ethyl-2-methylindol-3-yl)-3-(4-diethylamino)-2-methylphenyl-4-azaphthalide, 3-(2-methyl-1-n-octylindol-3-yl)-3-(4-diethylamino-2-ethoxyphenyl)-4-azaphthalide, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl-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)-5-dimethylaminophthalide, 3,3-bis(2-phenylindol-3-yl)-5-dimethylaminophthalide, 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-methylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-phenylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(1-methylpyrrol-2-yl)-6-dimethylaminophthalide, 3-(p-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3,6-bis(diethylamino)fluorane-γ-(3'-nitro)anilinolactam, 3,6-bis(diethylamino)fluorane-γ-(4'-nitro)anilinolactam, 1,1-bis-[2',2',2'',2''-tetrakis-(p-dimethylaminophenyl)-ethenyl]-2,2-dinitrilethane, 1,1-bis-[2',2',2'',2''-Tetrakis-(p-dimethylaminophenyl)-ethenyl]-2-β-naphthoyl ethane, 1,1-bis-[2',2',2'',2''-tetrakis-(p-dimethylaminophenyl)-ethenyl]-2,2-diacetyl ethane, bis-[2,2,2',2'-tetrakis-(p-dimethylaminophenyl)-ethenyl]-dimethyl methylmalonate, 2,2-bis{4-[6'-(N-cyclohexyl-N-methylamino)-3'-methylspiro[phthalide-3,9'-xanthene]-2'-ylamino]phenyl}propane and the like can be mentioned.,

[0265] It is preferable that the leuco dye is contained in the thermosensitive color former in an amount of 1 to 20% by mass, more preferably 3 to 15% by mass, and even more preferably 5 to 10% by mass. When the amount of the leuco dye is less than 1% by mass, the coloring effect is hardly exhibited. When it exceeds 20% by mass, the dispersibility of the thermosensitive color former itself is poor, so that the cohesive force of the thermosensitive color developing layer film may not be obtained or poor adhesion to the plastic film substrate may occur., The content ratio of the color developer and the leuco dye contained in the thermosensitive color former is preferably color developer / leuco dye = 7 / 1 to 0.5 / 1, more preferably 5 / 1 to 1 / 1, and even more preferably 4 / 1 to 2 / 1. When the content ratio is within the above range, the thermosensitive color developability is excellent.,

[0266] It is preferable that the thermosensitive color former of the present invention contains an aqueous resin. As the aqueous resin, a conventionally known resin can be used as long as it can be dissolved or dispersed in an aqueous medium. The aqueous medium refers to one containing water or a hydrophilic solvent as a component. Among them, a water-soluble resin or an aqueous emulsion resin is more preferable.,

[0267] The water-soluble resin has ionic groups such as sulfonyl groups and carboxyl groups, and water-soluble substituents such as hydroxyl groups in the molecule, and is soluble in water. For example, water-soluble polyacrylamide, water-soluble acrylic resins, water-soluble polyester resins, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral and other polyvinyl alcohol-based resins, water-soluble nylon resins, water-soluble alkyd resins, water-soluble melamine resins, water-soluble urea resins, water-soluble phenolic resins, water-soluble epoxy resins, water-soluble polybutadiene resins, water-soluble urethane resins, water-soluble acrylic / styrene resins, water-soluble vinyl acetate / acrylic copolymer resins, water-soluble styrene / maleic acid copolymer resins, water-soluble fluorine resins, water-soluble polyisocyanate resins, polystyrene-based resins, polyvinyl pyrrolidone, polyethylene oxide, polyvinyl acetate, carboxymethyl cellulose, water-soluble polyether resins and their copolymers, and natural polymer compounds such as starch, gelatin, casein, gum arabic, chitosan, dextran and guar gum, etc. Among them, water-soluble acrylic resins and water-soluble polyester resins are more preferable. In particular, water-soluble polyester resins are even more preferable.

[0268] The aqueous emulsion resin refers to a state in which resin particles are dispersed in an aqueous medium or the like, and it does not matter whether the resin particles are solid or liquid. Examples of the resin particles include polyamides, polyimides, low-density polyethylene, high-density polyethylene, poly(meth)acrylate esters, polystyrenes and their derivatives such as polystyrene, polyvinyl chloride, phenolic resins, melamine resins, urea resins, epoxy resins, polybutadiene resins, polycarbonate, alkyd resins, fluorine resins, vinyl acetate resins, polyisocyanate resins, chlorinated polyolefin resins and their copolymers, etc. Among them, poly(meth)acrylate esters, polystyrenes and their derivatives such as polystyrene are more preferable. In particular, polystyrenes are even more preferable, and it is preferable to contain acidic monomer units such as acrylic acid units and methacrylic acid units.

[0269] The aqueous resin preferably contains 1 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass in the heat-sensitive color former. When the amount of the aqueous resin is less than 1% by mass, the dispersibility of the heat-sensitive color former itself is poor, so that the cohesive force of the heat-sensitive color developing layer film may not be obtained or poor adhesion to the plastic film substrate may occur. When it exceeds 50% by mass, there is a risk of a decrease in printing density and poor fluidity.

[0270] It is preferable that the heat-sensitive color former of the present invention contains alcohol. Examples of the alcohol include methanol, ethanol, propyl alcohol, isopropyl alcohol, normal propyl alcohol, 1-butanol, 2-butanol, isobutanol, tert-butanol, ethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,4-pentanediol, 2,5-hexanediol, 1,6-hexanediol, triethylene glycol, 1-methyl-1,3-butylene glycol, 2-methyl-1,3-butylene glycol, 2,4-diethyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, tripropylene glycol, 1,2-propylene glycol, 2-methyl-1,5-pentanediol, 2-methyl-1,4-pentanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,2,4-trimethyl-1,6-hexanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc. Among them, methanol, ethanol, propyl alcohol, isopropyl alcohol, normal propyl alcohol, and propylene glycol monomethyl ether are more preferable.

[0271] Preferably, the alcohol is contained in the heat-sensitive color former in an amount of 1 to 50% by mass, more preferably 2 to 40% by mass, and even more preferably 5 to 20% by mass. If the amount of the alcohol is less than 1% by mass, it may be difficult to dry and the high-speed printing suitability may be poor. If it exceeds 50% by mass, there may be a decrease in printing density and poor fluidity.

[0272] In the heat-sensitive color former of the present invention, a sensitizer can be used as needed, and a conventionally known sensitizer can be used. For example, fatty acid amides such as stearic acid amide, bisstearic acid amide, N-hydroxymethyl stearic acid amide, N-stearyl stearic acid amide, ethylene bisstearic acid amide, methylene bisstearic acid amide, methylol stearic acid amide, palmitic acid amide, p-toluenesulfonamide, stearic acid, fatty acid metal salts such as calcium, zinc or aluminum of behenic acid or palmitic acid, N-stearyl urea, benzyl-2-naphthyl ether, 4-benzylbiphenyl, 2,2'-bis(4-methoxyphenoxy)diethyl ether, α,α'-diphenoxyxylene, bis(4-methoxyphenyl)ether, p-benzylbiphenyl, diphenyl sulfone, benzyl benzyloxybenzoate, 2-benzyloxynaphthalene, 1,2-bis(p-tolyloxy)ethane, 1,2-bis(phenoxy)ethane, 1,2-bis(3-methylphenoxy)ethane, 1,3-bis(phenoxy)propane, dibenzyl oxalate, p-methylbenzyl oxalate, bis(4-methylbenzyl) oxalate ester, bis(4-chlorobenzyl) oxalate ester, diphenyl adipate, dimethyl terephthalate, dibenzyl terephthalate, phenyl benzenesulfonate, bis(4-allyloxyphenyl) sulfone, 1,2-diphenoxyethane, 4-acetylacetophenone, m-terphenyl, 1-hydroxy-2-naphthoic acid, acetacetic acid anilides, fatty acid anilides, etc. can be mentioned. Among them, 1,2-bis(3-methylphenoxy)ethane, 1,2-bis(p-tolyloxy)ethane, 1,2-bis(phenoxy)ethane are more preferable.

[0273] It is preferable that the heat-sensitive color former of the present invention contains water. The water is not particularly limited, and tap water, well water, distilled water, ion-exchanged water, pure water, etc. can be used. Among them, it is more preferable to use distilled water, ion-exchanged water, pure water.

[0274] The water content is the remainder of each of the above-described components.

[0275] In the heat-sensitive color former of the present invention, a colorant, an inorganic filler, an organic filler, an antifoaming agent, a leveling agent, an antiblocking agent, a pigment dispersant, an antistatic agent, a slip agent, a plasticizer, a tackifier, a curing agent, a silane coupling agent, a wax, etc. can also be contained as necessary. Any known and commonly used ones can be appropriately selected as long as the characteristics as a heat-sensitive color former are not impaired.

[0276] Examples of the colorant include inorganic or organic pigments such as amorphous silica, amorphous calcium silicate, heavy calcium carbonate, light calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium dioxide, zinc oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, colloidal silica, polystyrene powder, nylon powder, urea-formalin resin filler, styrene-methacrylic acid copolymer, styrene-butadiene copolymer, and hollow plastic pigment.

[0277] The method for manufacturing the heat-sensitive recording laminate of the present invention preferably includes a gravure printing step of forming a heat-sensitive color-forming layer provided by the heat-sensitive color former. The heat-sensitive color former can be used as it is in the gravure printing step, but may include a step of diluting with a diluting solvent using a Zahn cup #3 (manufactured by Reika Co., Ltd.) according to the coating conditions and coating effects, and can be adjusted to a desired viscosity for use. The viscosity in this case is preferably 10 to 40 seconds at 25°C. If it is less than 10 seconds, it is likely to swim, and if it is more than 40 seconds, the transferability during printing deteriorates.

[0278] The diluting solvent may be any one as long as it can be used to adjust the viscosity of the ink composition, and examples thereof include organic solvents and water. Commercially available products can also be used, and there are no particular restrictions. Examples of commercially available products include WA734 solvent (alcohol-based solvent), WA735 solvent (alcohol-based solvent), WA736 solvent (alcohol-based solvent), TA50 solvent (alcohol solvent), TA52 solvent (alcohol solvent) (all of the above are manufactured by Tokyo Ink Co., Ltd.), etc.

[0279] The thickness of the heat-sensitive coloring layer is preferably 0.1 to 5 μm, and more preferably 0.2 to 3 μm. If the thickness of the heat-sensitive coloring layer is less than 0.1 μm, the coloring density after printing may be insufficient, and if it exceeds 5 μm, there is a risk of blocking.

[0280] The manufacturing method of the heat-sensitive recording laminate of the present invention preferably includes a coating step of forming an aqueous coating layer provided by an aqueous coating agent on the heat-sensitive coloring layer.

[0281] The aqueous coating agent preferably contains a water-soluble resin and water.

[0282] As the water-soluble resin used in the aqueous coating agent, the same water-soluble resin as the heat-sensitive coloring agent can be used. Among them, polyvinyl alcohols are more preferable. These water-soluble resins can be used alone or in admixture of two or more.

[0283] The water-soluble resin is preferably contained in the aqueous coating agent in an amount of 1 to 50% by mass, and more preferably 2 to 30% by mass. If the amount of the water-soluble resin is less than 1% by mass, the film-forming property of the aqueous coating layer is poor, and if it exceeds 50% by mass, the fluidity of the ink is poor and the manufacturing suitability is poor.

[0284] The water is not particularly limited, and tap water, well water, distilled water, ion-exchanged water, pure water, etc. can be used. Further, it may contain a solvent usually used in gravure ink. For example, aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane, alcohol solvents such as methanol, ethanol, isopropyl alcohol, normal propyl alcohol, 1-butanol, 2-butanol, isobutanol, and tert-butanol, ester solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, and tert-butyl acetate, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether, and esterified products thereof can be mentioned. As the esterified product, mainly acetylated ones are selected, and examples thereof include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Among them, from the viewpoints of printing suitability and versatility, toluene, ethyl acetate, n-propyl acetate, isopropyl alcohol, propylene glycol monomethyl ether, methyl ethyl ketone, etc. are more preferable. These can be used alone or in combination of two or more kinds.

[0285] In the aqueous coating agent, it is preferable that the water is in the range of 1 to 50% by mass. If it is less than 1% by mass, the wetting during printing deteriorates, and if it exceeds 50% by mass, the viscosity increases and the production suitability is inferior.

[0286] In the aqueous coating agent of the present invention, a colorant, an inorganic filler, an organic filler, an antifoaming agent, a leveling agent, an antiblocking agent, a pigment dispersant, an antistatic agent, a slip agent, a plasticizer, a tackifier, a curing agent, a silane coupling agent, a wax, etc. can also be contained as necessary. Any known and commonly used ones can be appropriately selected as long as the characteristics as an aqueous coating agent are not impaired.

[0287] The aqueous coating agent of the present invention can be used as it is in the gravure printing process, but depending on the coating conditions and coating effect, it may include a step of diluting with a diluting solvent using a Zahn cup #3 (manufactured by Reika Co., Ltd.) and can be used after adjusting to a desired viscosity. In this case, the viscosity is preferably 10 to 40 seconds at 25°C. If it is less than 10 seconds, it is likely to run, and if it is more than 40 seconds, the transferability during printing deteriorates.

[0288] Any diluting solvent can be used as long as it can adjust the viscosity of the aqueous coating agent, and examples include organic solvents and water, and commercially available products can also be used without particular limitation. Commercially available products include WA734 solvent (alcohol-based solvent), WA735 solvent (alcohol-based solvent), WA736 solvent (alcohol-based solvent), TA50 solvent (alcohol-based solvent), TA52 solvent (alcohol-based solvent) (all of the above are manufactured by Tokyo Ink Co., Ltd.), etc.

[0289] The thickness of the aqueous coating layer is preferably 0.01 to 2 μm, more preferably 0.05 to 1.4 μm, and even more preferably 0.1 to 1.2 μm. If the thickness of the aqueous coating layer is less than 0.01 μm, the film-forming property of the aqueous coating layer is inferior, and if it exceeds 2 μm, it is difficult to dry and there is a risk of inferior high-speed printing suitability.

[0290] The manufacturing method of the heat-sensitive recording laminate of the present invention preferably includes a coating step of forming an overcoat layer provided by an overcoat agent on the aqueous coating layer.

[0291] The overcoat agent preferably contains a thermoplastic resin, a polyisocyanate, and an organic solvent.

[0292] The thermoplastic resin is preferably an acrylic resin, a polyurethane resin, a vinyl chloride-vinyl acetate copolymer, or a fiber-based resin. Among them, an acrylic resin, a polyurethane resin, and a vinyl chloride-vinyl acetate copolymer are more preferable. These can be used alone or in combination of two or more.

[0293] The thermoplastic resin is preferably contained in the overcoat agent in an amount of 1 to 50% by mass, more preferably 2 to 45% by mass. If the amount of the thermoplastic resin is less than 1% by mass, the film-forming property of the overcoat layer is poor, and the protective effect on the heat-sensitive coloring layer is hardly exhibited. If it exceeds 50% by mass, there is a risk of blocking.

[0294] Examples of the polyisocyanate include alicyclic diisocyanates such as isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and methylcyclohexylene diisocyanate; aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, butane-1,4-diisocyanate, pentane-1,5-diisocyanate, and xylylene diisocyanate (XDI), and trimethylolpropane trimers thereof; aromatic diisocyanates such as tolylene diisocyanate (TDI), α,α,α',α'-tetramethylxylylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, and tetraalkyldiphenylmethane diisocyanate, and modified products thereof. Among these, alicyclic diisocyanates, aliphatic diisocyanates, and araliphatic diisocyanates are more preferred. These may be used alone or in admixture of two or more kinds.

[0295] The polyisocyanate is preferably contained in the overcoat agent in an amount of 1 to 50% by mass, more preferably 2 to 45% by mass. If the amount of the polyisocyanate is less than 1% by mass, it is difficult to obtain a crosslinking effect, and if it exceeds 50% by mass, there is a risk of blocking.

[0296] The content ratio of the thermoplastic resin and the polyisocyanate contained in the overcoat agent is preferably such that the solid content of the polyisocyanate is 100 / 1 to 100 / 50, more preferably 100 / 5 to 100 / 40, and even more preferably 100 / 15 to 100 / 35 with respect to 100 of the solid content of the thermoplastic resin contained in the overcoat agent. When the content ratio is within the above range, it is excellent in alcohol resistance, scratch resistance, water resistance, and oil resistance.

[0297] As the organic solvent, solvents usually used in gravure inks can be used. For example, aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane, alcohol solvents such as methanol, ethanol, isopropyl alcohol, normal propyl alcohol, 1-butanol, 2-butanol, isobutanol, and tert-butanol, ester solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, and tert-butyl acetate, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether, and their esterified products. As the esterified products, mainly acetylated ones are selected, such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Among them, from the viewpoints of printing suitability and versatility, toluene, ethyl acetate, n-propyl acetate, isopropyl alcohol, propylene glycol monomethyl ether, methyl ethyl ketone, etc. are more preferable. These can be used alone or in combination of two or more kinds.

[0298] In the overcoat agent, the organic solvent is preferably in the range of 45 to 90% by mass, more preferably in the range of 60 to 80% by mass. If it is less than 45% by mass, the solid content increases, the fluidity deteriorates, and the manufacturability of the overcoat agent is inferior. If it exceeds 90% by mass, the viscosity decreases, and there is a risk that a beautiful printing effect cannot be obtained.

[0299] In the overcoat agent of the present invention, if necessary, a colorant, an inorganic filler, an organic filler, an antifoaming agent, a leveling agent, a pigment dispersant, an antistatic agent, a slip agent, a plasticizer, a tackifier, a silane coupling agent, etc. can also be contained. Any known and commonly used ones can be appropriately selected as long as the characteristics as an overcoat agent are not impaired.

[0300] The overcoat agent of the present invention can be used as it is in the gravure printing process, but depending on the coating conditions and coating effect, it may include a step of diluting with a diluting solvent using a Zahn cup #3 (manufactured by Reika Co., Ltd.), and can be adjusted to a desired viscosity for use. In this case, the viscosity is preferably 10 to 40 seconds at 25°C. If it is less than 10 seconds, it is likely to swim, and if it is more than 40 seconds, the transferability during printing deteriorates.

[0301] The diluting solvent may be any as long as it can be used to adjust the viscosity of the ink composition, and examples include organic solvents, and commercially available products can also be used, with no particular limitation. Commercially available products include TS32 solvent (ester-based solvent), PU533 solvent (toluene-containing solvent), PU515 solvent (non-toluene solvent), SL9155 solvent (non-toluene solvent), CN104 solvent (non-toluene solvent), AC372 solvent (non-toluene solvent), PP575 solvent (toluene-containing solvent), SL9164 solvent (non-ketone solvent), SL9170 solvent (non-ketone solvent) (all of the above are manufactured by Tokyo Ink Co., Ltd.), etc.

[0302] The thickness of the overcoat layer is preferably 0.05 to 5 μm, more preferably 0.1 to 3 μm. If the thickness of the overcoat layer is less than 0.05 μm, the protective effect on the aqueous coat layer is insufficient. If it exceeds 5 μm, there is a risk of blocking.

[0303] The thermal recording laminate produced by the method for producing a thermal recording laminate of the present invention can be used to produce a printed matter by causing the thermal coloring layer to develop color using a thermal printer (for example, TH-M2 / PP, manufactured by Ookura Engineering Co., Ltd.). Regarding the color density, a heat sealer (manufactured by Tester Sangyo Co., Ltd.) or the like is used to cause the thermal recording laminate to develop color, and the L * a * b * It can be evaluated by the L value measured by the method defined in the color system (CIE1976). The lower the L value, the higher the blackness, and it can be judged as good. As the device for measuring the color density, a reflection densitometer, a spectral densitometer, a spectrophotometer, etc. can be used. For example, a portable spectral density / colorimeter eXact 2 (manufactured by X-Rite) can be mentioned.

[0304] The method for producing a thermal recording laminate of the present invention may include a coating step of forming an anchor coat layer provided by an anchor coating agent between the plastic film substrate and the thermal coloring layer.

[0305] For the anchor coating agent, a resin can be used. Examples of the resin include starches such as oxidized starch, esterified starch, and etherified starch; cellulose resins such as methyl cellulose, carboxymethyl cellulose, methoxy cellulose, hydroxyethyl cellulose, etc.; casein, gelatin, fully (or partially) saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, silicon-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, etc. (collectively referred to as polyvinyl alcohols); styrene-maleic anhydride copolymer latex, styrene-butadiene copolymer latex, vinyl acetate resin latex, urethane resin latex, acrylic resin latex, etc. These can be used alone or in combination of two or more.

[0306] The anchor coating agent can use the same organic solvents as the aqueous coating agent or the overcoat agent. Among them, from the viewpoints of printability and versatility, toluene, ethyl acetate, n-propyl acetate, isopropyl alcohol, propylene glycol monomethyl ether, methyl ethyl ketone, etc. can be mentioned. These can be used alone or in combination of two or more.

[0307] In the anchor coating agent of the present invention, if necessary, a colorant, an inorganic filler, an organic filler, an antifoaming agent, a leveling agent, an antiblocking agent, a pigment dispersant, an antistatic agent, a slip agent, a plasticizer, a tackifier, a system curing agent, a silane coupling agent, a wax, etc. can also be contained. Any well-known and commonly used ones can be appropriately selected as long as the characteristics as an anchor coating agent are not impaired. Commercially available products can also be used, and there is no particular limitation. Examples of commercially available products include LG-OX Anchor Agent D (manufactured by Tokyo Ink Co., Ltd.).

[0308] The anchor coat agent of the present invention can be used directly in the gravure printing process. However, depending on the coating conditions and coating effects, it may include a step of diluting with a diluting solvent using a Zahn cup #3 (manufactured by Reika Co., Ltd.) and can be adjusted to a desired viscosity for use. In this case, the viscosity is preferably 10 to 40 seconds at 25°C. If it is less than 10 seconds, it is likely to run, and if it is more than 40 seconds, the transferability during printing deteriorates.

[0309] The diluting solvent may be any as long as it can be used to adjust the viscosity of the anchor coat agent, and examples include organic solvents. Commercially available products can also be used, and there are no particular restrictions. Commercially available products include TS32 solvent (ester-based solvent), PU533 solvent (toluene-containing solvent), PU515 solvent (non-toluene solvent), SL9155 solvent (non-toluene solvent), CN104 solvent (non-toluene solvent), AC372 solvent (non-toluene solvent), PP575 solvent (toluene-containing solvent), SL9164 solvent (non-ketone solvent), SL9170 solvent (non-ketone solvent) (all of the above are manufactured by Tokyo Ink Co., Ltd.), etc.

[0310] The thickness of the anchor coat layer is preferably 0.05 to 3 μm, and more preferably 0.1 to 2 μm. If the thickness of the anchor coat layer is less than 0.05 μm, the coating amount is small, and there is a risk that the plastic film substrate cannot be covered. If it exceeds 3 μm, there is a risk of blocking.

[0311] As the step of preparing the plastic film substrate, it is preferable that the step is to prepare at least one selected from a plastic film or sheet and a laminate thereof. For example, polyester films such as polyethylene terephthalate (PET), polyethylene naphthalate, and polybutylene terephthalate, polyolefin films such as polyethylene, polypropylene, and ethylene-vinyl acetate, polystyrene films, alcohol-based films such as ethylene-vinyl alcohol and polyvinyl alcohol, polyamide films or barrier polyamide films with a barrier layer in the middle, polycarbonate films, polyacrylonitrile films, polyimide films, cellophane, moisture-proof cellophane, transparent vapor-deposited polyester films or transparent vapor-deposited polyamide films obtained by providing a vapor-deposited layer such as alumina or silica on a PET film or a polyamide film, various coating films coated with polyvinylidene chloride resin, polyvinyl alcohol resin, polyacrylic acid resin, etc., co-extruded films of PET and nylon, polylactic acid films, etc. These may be either stretched or unstretched, and it may also be a step of preparing one or more kinds laminated. An appropriate one can be selected in consideration of mechanical strength, dimensional stability, etc. Also, in order to improve the adhesion of the anchor coat layer and the laminate layer on the surface, corona treatment, low-temperature plasma treatment, flame treatment, solvent treatment, coating treatment, etc. can be applied, or those previously applied can be selected and prepared. Among them, it is preferable to prepare a PET film, a polypropylene film, a polyamide film, a coating film, a transparent vapor-deposited polyester film or a transparent vapor-deposited polyamide film, a co-extruded film, etc. The thickness of the plastic film substrate is not particularly limited as long as it does not interfere with printing suitability, winding suitability, etc., but is preferably 5 to 300 μm, and more preferably 6 to 250 μm.

[0312] Preferably, it is a gravure printing process for forming a thermosensitive color-developing layer provided by the thermosensitive color-developing agent on one side of the plastic film substrate. There are no particular restrictions on the coating process for forming an aqueous coating layer provided by the aqueous coating agent on the thermosensitive color-developing layer and the coating process for forming an overcoat layer provided by the overcoat agent on the aqueous coating layer, but a gravure printing process is more preferable. Furthermore, it is more preferable that the coating process for forming an anchor coat layer provided by an anchor coating agent is also a gravure printing process. Thus, it can be created by a gravure printing process using a multicolor gravure printing machine. Since it can be created by a gravure printing process, each layer can be formed over the entire surface, but it is also possible to easily form each layer partially.

[0313] The method for manufacturing the thermosensitive recording laminate of the present invention may include a laminating process or a coating process for forming a seal layer on the plastic film substrate on the side opposite to the thermosensitive color-developing layer.

[0314] Examples of the process for forming the seal layer include a laminating process such as bonding a laminate with heat-sealing properties or a known sealant film (dry lamination method, non-solvent lamination method, wet lamination method), resin coating by an extrusion lamination method (extrusion lamination method, co-extrusion lamination method, PE sandwich lamination method), heat bonding (heat lamination method), etc., and a coating process of a heat-sealing agent or a hot melt agent. Also included is a coating process of an adhesive or an adhesive agent.

[0315] The thickness of the seal layer is not particularly limited, but in the case of a sealant film, it is preferably 2 to 200 μm, in the case of resin coating by an extrusion lamination method, it is preferably 1 to 100 μm, in the case of coating with a heat-sealing agent, it is preferably 0.01 to 30 μm, and in the case of coating with a hot melt adhesive, it is preferably 1 to 50 μm.

[0316] Examples of the sealant film include polyolefin films such as polyethylene, polypropylene, ethylene-vinyl acetate, and copolymers thereof, coextruded films and colored films thereof, polystyrene films, polyacrylonitrile films, ethylene-vinyl alcohol resin films, etc. It may be stretched or unstretched, and may be laminated with one type or two or more types.

[0317] When an adhesive is used in the laminating process such as the dry lamination method, non-solvent lamination method, wet lamination method, extrusion lamination method, etc., commercially available products may be used. For example, two-component or one-component urethane resin adhesives, acrylic, epoxy, polyester, polyethyleneimine, polybutadiene, aqueous urethane, isocyanate, organic titanium, starch-based water-soluble adhesives, and aqueous adhesives such as vinyl acetate emulsions can be mentioned. As the coating process of the adhesive for forming the sealant layer, a known coating process can be used. For example, a roll coater, reverse roll coater, gravure offset coater, gravure coater, microgravure coater, knife coater, bar coater, wire bar coater, die coater, dip coater, etc. can be used. The thickness of the adhesive is not particularly limited, but a range of about 0.001 to 10 μm is preferable, and a range of 0.01 to 5 μm is particularly preferable.

[0318] Examples of resins that can be used for the resin coating in the extrusion lamination process include polyethylene resins such as LDPE, LLDPE, and HDPE, polypropylene resin, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, acid-modified polyolefin resins obtained by modifying polyethylene or polypropylene with maleic acid or fumaric acid, polystyrene resin, thermoplastic resins such as polybutylene terephthalate resin, etc. These resins can be used alone or in combination of two or more types.

[0319] Examples of resins for heat sealants include, for example, thermoplastic resins such as vinylidene chloride, shellacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, nitrocellulose, cellulose acetate, cellulose acetyl propionate, cellulose acetyl butyrate, chlorinated rubber, cyclized rubber, polyamide resin, vinyl chloride-vinyl acetate copolymer, polyester resin, ketone resin, butyral resin, chlorinated polypropylene resin, chlorinated polyethylene resin, chlorinated ethylene vinyl acetate resin, ethylene vinyl acetate resin, (meth)acrylic resin, urethane resin, ethylene-vinyl alcohol resin, styrene maleic acid resin, casein, alkyd resin, etc. These can be used alone or in combination of two or more types. Examples include those in which these resins are dissolved in a solvent, or those dispersed in water such as acrylic emulsions, urethane emulsions, ethylene-vinyl alcohol emulsions, polyethylene emulsions, polypropylene emulsions, ethylene vinyl acetate emulsions, etc.

[0320] The method for manufacturing the thermosensitive recording laminate of the present invention may include a gravure printing step of forming a pattern layer on the plastic film substrate or on the plastic film substrate on the opposite side of the thermosensitive coloring layer. Further, it may include a gravure printing step of forming a colored ink layer. The order of the steps for forming the pattern layer and the colored ink layer is not limited. Also, it may be formed over the entire surface or on a part, and may be formed by halftone dots. The pattern layer is usually a layer formed using a color printing ink composition used for gravure printing, and is a layer on which patterns, characters, etc. are printed. Also, the colored ink layer is usually a layer formed using a white ink composition used for gravure printing, etc., and is a layer used for creating contrast with the pattern layer, etc. by solid or halftone dots to make it easier to see.

[0321] The package according to the embodiment of the present invention is preferably formed using the laminate, and may be a packaging bag, label, and lid material (collectively referred to as "package").

[0322] The configuration of the laminate to be the packaging bag may be a plastic film substrate / thermosensitive coloring layer / aqueous coat layer / overcoat layer, plastic film substrate / anchor coat layer / thermosensitive coloring layer / aqueous coat layer / overcoat layer, seal layer / DL / plastic film substrate / thermosensitive coloring layer / aqueous coat layer / overcoat layer, seal layer / DL / pattern layer / colored ink layer / plastic film substrate / thermosensitive coloring layer / aqueous coat layer / overcoat layer, seal layer / DL / pattern layer / plastic film substrate / colored ink layer / thermosensitive coloring layer / aqueous coat layer / overcoat layer, seal layer / DL / pattern layer / plastic film substrate / anchor coat layer / thermosensitive coloring layer / aqueous coat layer / overcoat layer, etc. The packaging bag may be in any well-known form such as a two-side seal, three-side seal, four-side seal, pillow seal, standing pouch, envelope sticker, gusset, and fusion seal.

[0323] As the label, it can also be formed by forming an adhesive layer or an adhesive layer on the plastic film base material on the other surface where the heat-sensitive coloring layer is formed, and further forming a release layer. The adhesive layer or the adhesive layer may be any material as long as it adheres to the plastic film base material and the release layer, such as a rubber-based adhesive material or an acrylic resin-based adhesive material, and the release layer can be easily peeled off. The release layer may be any of a polyethylene film, a polyester film, or paper (release paper). As the structure of the laminate to be the label, it may be an adhesive layer / plastic film base material / heat-sensitive coloring layer / aqueous coat layer / overcoat layer, a hot melt layer / plastic film base material / heat-sensitive coloring layer / aqueous coat layer / overcoat layer, an adhesive layer / pattern layer / colored ink layer / plastic film base material / heat-sensitive coloring layer / aqueous coat layer / overcoat layer, an adhesive layer / pattern layer / plastic film base material / colored ink layer / heat-sensitive coloring layer / aqueous coat layer / overcoat layer, an adhesive layer / pattern layer / plastic film base material / anchor coat layer / heat-sensitive coloring layer / aqueous coat layer / overcoat layer, etc.

[0324] As the lid material, it may be any of well-known forms such as a cover, a lid, or a cap. As the structure of the laminate to be the lid material, it may be a seal layer / DL / plastic film base material / heat-sensitive coloring layer / aqueous coat layer / overcoat layer, a seal layer / DL / pattern layer / colored ink layer / plastic film base material / heat-sensitive coloring layer / aqueous coat layer / overcoat layer, a seal layer / DL / pattern layer / plastic film base material / colored ink layer / heat-sensitive coloring layer / aqueous coat layer / overcoat layer, a seal layer / DL / pattern layer / plastic film base material / anchor coat layer / heat-sensitive coloring layer / aqueous coat layer / overcoat layer, etc.

[0325] Furthermore, it is preferable that the container becomes a sealed container by closely adhering to it. The close adhesion to the container may be carried out manually or by using a machine such as an automatic sealing device. These may be appropriately selected according to the type, form, size, quantity of food, the container to be sealed, equipment, environment, etc., and may be carried out by a method using heat sealing (thermocompression sealing), surface sealing, pasting or adhesion with an adhesive, etc. The container is more preferably a bottomed cylindrical container. In this case, it is preferable that the lid material covers the opening of the bottomed cylindrical container and is sealed, and it is more preferably sealed by heat sealing. Examples of the resin used for the container include thermoplastic resins such as polyethylene-based, polypropylene-based, polyethylene terephthalate, polyvinyl chloride, polystyrene, and polyacrylonitrile.

Examples

[0326] Examples and comparative examples are shown below to more specifically explain the present invention, but the present invention is not limited thereto. In the examples and comparative examples, "parts" represents parts by mass and "%" represents % by weight.

[0327] [Preparation of heat-sensitive color former] Production Example 1 (Preparation of developer dispersion) 30 parts of N,N'-di[3-(p-toluenesulfonyloxy)phenyl]urea, 30 parts of an aqueous resin (Hiros M-141, an aqueous acrylic emulsion resin, manufactured by Seiko PMC Co., Ltd.), 20 parts of methanol, and 20 parts of water were added, mixed and dispersed to prepare Agent A1. Similarly, according to the formulation in Table 1, Agent A2 to Agent A10 were prepared in the same manner as Agent A1.

[0328]

Table 1

[0329] Production Example 21 (Leuco dye dispersion) 30 parts of a leuco dye (3-dibutylamino-6-methyl-7-anilinofluoran, manufactured by Yamamoto Chemical Industry Co., Ltd.), 40 parts of an aqueous resin (Plascoat RZ-570, a water-soluble polyester resin, manufactured by Gohsei Chemical Industry Co., Ltd.), 15 parts of isopropyl alcohol, and 15 parts of water were added and stirred to prepare Agent B1. Similarly, according to the formulations in Table 2, Agent B2 to Agent B5 were prepared in the same manner as Agent B1.

[0330]

Table 2

[0331] The materials used were as follows. JONCRYL PDX7741, an aqueous acrylic emulsion resin, manufactured by BASF JONCRYL PDX7779, an aqueous acrylic emulsion resin, manufactured by BASF JONCRYL PDX7326, an aqueous acrylic emulsion resin, manufactured by BASF JONCRYL HPD-96J, a water-soluble acrylic resin, manufactured by BASF JONCRYL HPD-196, a water-soluble acrylic resin, manufactured by BASF JONCRYL PDX7356, an aqueous acrylic emulsion resin, manufactured by BASF 1,3-bis-(3-[3-phenylureido]phenyloxysulfonyl)benzene, a developer N-[2-(3-phenylureido)phenyl]benzenesulfonamide, a developer N-p-toluenesulfonyl-N'-3-(p-toluenesulfonyloxy)phenylurea, a developer

[0332] Production Example 31 (Preparation of a heat-sensitive color former) Next, 70 parts of Agent A1 and 30 parts of Agent B1 were stirred to prepare heat-sensitive color former 1. Similarly, according to the formulations in Tables 3 to 4, heat-sensitive color formers 2 to 14 were prepared in the same manner as heat-sensitive color former 1.

[0333]

Table 3

[0334]

Table 4

[0335] Production Example 51 (Preparation of Aqueous Coating Agent) 30 parts of a 10% aqueous polyvinyl alcohol solution (manufactured by Nippon Vinyl Acetate Co., Ltd., Poval) was added with 20 parts of isopropyl alcohol and 50 parts of water, and stirred to prepare Aqueous Coating Agent 1.

[0336]

Table 5

[0337] [Preparation of Overcoat Agent] Production Example 81 40 parts of an acrylic resin solution (LG-OX Anchor Agent A, solid content 18%, manufactured by Tokyo Ink Co., Ltd.) and 10 parts of n-propyl acetate were stirred to prepare Coating Agent 1 of Production Example 61. Furthermore, 25 parts of trimethylolpropane trimer of xylylene diisocyanate and 25 parts of ethyl acetate were stirred to prepare Hardener 1 of Production Example 71. The Coating Agent 1 and the Hardener 1 were mixed at a ratio of Coating Agent 1:Hardener 1 = 100:8 immediately before the gravure printing described below to prepare Overcoat Agent 1 of Production Example 81. Similarly, according to the formulations in Table 6, Coating Agents 2 to 8 were prepared in the same manner as Coating Agent 1. Similarly, according to the formulations in Table 7, Hardener 2 was prepared in the same manner as Hardener 1. Similarly, according to the formulations in Table 8, Overcoat Agents 2 to 9 were prepared in the same manner as Overcoat Agent 1. Note that Overcoat Agent 7 is similar to Protective Liquid 1 of Comparative Example 4 in Patent Document 1. Overcoat Agent 8 is similar to the protective liquid of Example 6 in Patent Document 2. Overcoat Agent 9 is similar to Protective Liquid 1 of Example 21 in Patent Document 3.

[0338]

Table 6

[0339]

Table 7

[0340]

Table 8

[0341] The materials used were as follows. LG-FK R Medium A: Vinyl chloride-vinyl acetate copolymer solution, solid content 18%, manufactured by Tokyo Ink Co., Ltd. LAMREK R Medium: Urethane resin solution, solid content 15%, manufactured by Tokyo Ink Co., Ltd. ASN1004K: Acrylic resin emulsion, solid content 18%, manufactured by Mitsui Chemicals, Inc. NeoCryl A-1125: Acrylic resin emulsion, solid content 19.5%, manufactured by DSM Coating Resin Hexamethylene diisocyanate TMP trimer: Trimethylolpropane trimer of hexamethylene diisocyanate Hardener 3: Oxazoline group-containing polymer, Epocros WS-300, manufactured by Nippon Shokubai Co., Ltd.

[0342] [Production of laminate] [Example 1] Using a 5-color gravure printing press, on one side of a double-treated PET film (E-5202, abbreviation: double-treated PET, manufactured by Toyobo Co., Ltd.) with a thickness of 12 μm, thermosensitive color former 1 was printed with a film thickness of 2 μm in the first unit, aqueous coating agent 1 was printed with a film thickness of 1 μm in the second unit, and overcoating agent 1 was printed with a film thickness of 1 μm in the third unit, and then wound up to produce laminate 1. At this time, thermosensitive color former 1 was diluted with WA734 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), aqueous coating agent 1 was diluted with water, and overcoating agent 1 was diluted with SL9170 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), and the viscosity was adjusted to 17 seconds with a Zahn cup No. 3. Thus, a laminate 1 of both-treated PET / heat-sensitive color former 1 / aqueous coating agent 1 / overcoating agent 1 was obtained.

[0343] Similarly, as shown in Tables 9 to 10, laminates 2 to 27 (Examples 2 to 27) were obtained.

[0344] The plastic film substrates used were as follows. Aluminum-deposited PET film, Tetrite PC, thickness 12 μm, manufactured by Oike Industry Co., Ltd., abbreviation: Al-deposited PET (printed on the deposited surface) Transparent deposited PET film, Barilox 1011HG-CR, thickness 12 μm, manufactured by Toray Film Processing Co., Ltd., abbreviation: Transparent deposited PET (printed on the deposited surface) OPP film, OP U-2, thickness 20 μm, manufactured by Mitsui Chemicals Toagosei Co., Ltd., abbreviation: OPP Both-treated nylon film, ONMB, thickness 15 μm, manufactured by Unitika Ltd., abbreviation: Both-treated NY

[0345] <Example 28> Also, using a gravure printing machine, on one surface of a 12-μm-thick both-treated PET film (E-5202, manufactured by Toyobo Co., Ltd.), LG-OX anchor agent D (manufactured by Tokyo Ink Co., Ltd.) was printed to a film thickness of 1 μm with a first unit, wound up, and used as a plastic film substrate (abbreviation: PET anchor). At this time, LG-OX anchor agent D was diluted with SL9170 (a non-toluene-based solvent, manufactured by Tokyo Ink Co., Ltd.) and adjusted to a viscosity of 17 seconds with a Zahn cup No. 3. On the anchor agent-printed surface of this plastic film substrate (PET anchor), a heat-sensitive color former 1, an aqueous coating agent 1, and an overcoating agent 1 were printed in the same manner as in Example 1, wound up, and laminate 28 was obtained.

[0346]

Table 9

[0347]

Table 10

[0348] <Comparative Examples 1 - 5> A laminate 31 was obtained in the same manner as in Example 1, except that the aqueous coating agent was not printed (Comparative Example 1). Also, a laminate 32 was obtained in the same manner as in Example 1, except that the overcoating agent was not printed (Comparative Example 2). Laminates 33 - 35 were obtained in the same manner as in Comparative Example 1, except that the overcoating agent was replaced with overcoating agents 7 - 9. However, water was used as the diluting solvent. Note that laminate 33 is similar to Comparative Example 4 of Patent Document 1. Laminate 34 is similar to Example 6 of Patent Document 2. Laminate 35 is similar to Example 21 of Patent Document 3.

[0349]

Table 11

[0350] For the laminates, soil resistance, blocking, transparency, residual solvent, color density, adhesion, alcohol resistance, scratch resistance (before printing), head resistance, friction resistance, scratch resistance (after printing), water resistance, and oil resistance were evaluated and shown in Tables 9 - 11.

[0351] <Soil Resistance> For the laminates, the degree of blackening of the coating layer surface (heat - sensitive color - developing layer, aqueous coating layer, overcoating layer, hereinafter collectively referred to as the "coating layer") immediately after production was evaluated. It was a visual evaluation by 5 observers. Those in which the coating layer did not develop black color (less blackening) were judged as good. For soil resistance, ◎: all 5 observers judged no blackening; 〇: 3 observers judged no blackening; △: more than 3 observers judged slightly blackened (no practical problem); ×: all 5 observers judged black - colored. It was evaluated in 4 grades.

[0352] <Blocking> For the laminates, two pieces cut to a size of 3 cm × 3 cm immediately after production were prepared. These were overlapped with the coating layer surface and the plastic film substrate surface in contact, and pressed at 50 °C for 24 hours at 5 N / cm 2After applying the load, the delamination state and peel resistance were evaluated when the overlapping part of the coated layer surface and the plastic film substrate surface was peeled off. Those that peeled off without resistance and showed no delamination were judged to be good. For blocking, it was evaluated in two levels: ○: peeled off without resistance and no delamination; ×: large resistance during peeling and delamination was observed.

[0353] <Transparency> For the laminate, three pieces cut to a size of 2 cm × 3 cm immediately after production were prepared. Using HAZE GARD II (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the haze value of the coated layer surface was measured, and the average value was evaluated as the transparency. Those with a low haze value were judged to be good. For transparency, it was evaluated in three levels: ○: haze value less than 45; △: haze value 45 or more and less than 70; ×: haze value 70 or more.

[0354] <Residual solvent> For the laminate, after 24 hours at room temperature after production, it was cut into test pieces of 0.1 m 2 , placed in a vial, preheated at 80 °C for 30 minutes, and the headspace was analyzed by a gas chromatograph mass spectrometer (HS-20, detector: TCD type, manufactured by Shimadzu Corporation) to quantify the residual solvent. Those with less residual solvent were considered good. For the residual solvent, it was evaluated in three levels: ○: less than 5 mg / m 2 ; △ = 5 - 10 mg / m 2 ; × = 10 mg / m 2 or more.

[0355] <Color density> For the laminate, after storage in a 40 °C constant temperature bath for 24 hours after production, the L value when coloring was performed at 150 °C, printing pressure 2 kgf / cm 2 , printing pressure time 0.5 seconds using a heat sealer (manufactured by Tester Sangyo Co., Ltd.) was measured with a portable spectrocolorimeter eXact 2 (manufactured by X-Rite) and used as the color density. Those with a low L value (higher blackness) were judged to be good. For the color density, it was evaluated in three levels: ○: L value less than 20; △: L value 20 or more and less than 40; ×: L value 40 or more.

[0356] <Adhesion> For the laminate, after production, it was stored in a constant temperature bath at 40°C for 24 hours. Then, an adhesive tape (18 mm, manufactured by Nichiban Co., Ltd.) was attached to the coated surface and rapidly peeled off at a 90-degree angle. The peeling state of the coated surface was visually observed to evaluate the adhesion. Those with no peeling on the coated surface were judged to have good adhesion. The adhesion was evaluated in two levels: ○: no peeling at all, ×: peeling even slightly.

[0357] <Alcohol resistance> For the laminate, after production, it was stored in a constant temperature bath at 40°C for 24 hours. Then, the coated surface was rubbed with a cotton swab containing ethanol for disinfection (80% ethanol aqueous solution). The peeling state of the coated surface was visually observed to evaluate the alcohol resistance. Those with no peeling on the coated surface were judged to have good alcohol resistance. The alcohol resistance was evaluated in two levels: ○: no peeling at all, ×: peeling even slightly.

[0358] <Scratch resistance (before printing)> For the laminate, after production, it was stored in a constant temperature bath at 40°C for 24 hours. Then, the coated surface was rubbed 10 times with a metal spatula, and the peeling state of the coated layer was evaluated. It was a visual evaluation by 5 observers. Those with no peeling of the coated layer were judged to be good. The scratch resistance was evaluated in four levels: ◎: all 5 observers judged no peeling, 〇: 3 observers judged no peeling, △: more than 3 observers judged slightly peeling (no problem in practical use), ×: all 5 observers judged peeling.

[0359] <Head resistance> For the laminate, after production, it was stored in a constant temperature bath at 40°C for 24 hours. Then, using a thermal printer (TH-M2 / PP, manufactured by Ookura Engineering Co., Ltd.), a printed matter was produced by coloring with a pulse width of 1.4 msec. The rubbing condition at the heating part (head part) was evaluated by visually observing the printed part. Those with less rubbing at the printed part were judged to be good. It was evaluated in three levels: ○: no rubbing at the printed part, △: slightly rubbing can be seen, ×: obvious rubbing can be seen.

[0360] <Friction resistance> Under the same conditions as the <head resistance> evaluation, a dry cotton cloth (Kanakin No. 3) was used to apply a 400 g weight and rub it on the printed part of the printed matter obtained by printing the laminate, and the change in the printed part was visually observed to evaluate the abrasion resistance. Those with no change in the printed part were judged to be good. Regarding the abrasion resistance, ○: no change in the printed part even after rubbing 50 times or more, △: slightly scratched in the state of the printed part after rubbing 50 times (no problem in practical use), ×: the printed part disappears between 20 and less than 50 rubs, ××: the printed part disappears in less than 20 rubs, and it was evaluated in four levels.

[0361] <Scratch resistance (after printing)> Under the same conditions as the <head resistance> evaluation, the printed part of the printed matter obtained by printing the laminate was rubbed 10 times with a metal spatula, and the peeling state of the coating layer on the printed part was evaluated. It was a visual evaluation by 5 observers. Those with no peeling of the coating layer on the printed part were judged to be good. Regarding the scratch resistance, ◎: all 5 observers judged no peeling, 〇: 3 observers judged no peeling, △: 3 or more observers judged slightly peeling (no problem in practical use), ×: all 5 observers judged peeling, and it was evaluated in four levels.

[0362] <Water resistance> Under the same conditions as the <head resistance> evaluation, the printed part of the printed matter obtained by printing the laminate was rubbed with a cotton swab containing water, and the presence or absence of fading was visually observed and evaluated. Those with less fading in the printed part were judged to be good. Regarding the water resistance, ○: no fading in the printed part, △: slightly faded (no problem in practical use), ×: completely faded, and it was evaluated in three levels.

[0363] <Oil resistance> Under the same conditions as the <head resistance> evaluation, the printed part of the printed matter obtained by printing the laminate was rubbed with a cotton swab containing lubricating oil (New Haines - G, Nissei Co., Ltd.), and the presence or absence of fading was visually observed and evaluated. Those with less fading in the printed part were judged to be good. Regarding the oil resistance, ○: no fading in the printed part, △: slightly faded (no problem in practical use), ×: completely faded, and it was evaluated in three levels.

[0364] From Tables 9 to 11, it is clear that the laminates of Examples 1 to 28 have good soil stain resistance, blocking resistance, transparency, residual solvent, color density, adhesion, alcohol resistance, scratch resistance (before printing), head resistance, friction resistance, scratch resistance (after printing), water resistance, and oil resistance. On the other hand, it is clear that the laminate of Comparative Example 1 without an aqueous coat layer is inferior in soil stain resistance, color density, and alcohol resistance. It is clear that the laminate of Comparative Example 2 without an overcoat layer is inferior in scratch resistance, head resistance, friction resistance, and water resistance. It is clear that the laminate of Comparative Example 3 similar to Reference Document 1 is inferior in transparency, alcohol resistance, water resistance, and oil resistance. It is clear that the laminate of Comparative Example 4 similar to Reference Document 2 is inferior in alcohol resistance. It is clear that the laminate of Comparative Example 5 similar to Reference Document 3 is inferior in alcohol resistance and oil resistance.

Claims

1. On one surface of a plastic film substrate, a heat-sensitive coloring layer composed of a leuco dye, at least one developer selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), and a compound represented by the following general formula (4), an aqueous resin, an alcohol, and water, On the heat-sensitive coloring layer, an aqueous coating layer composed of an aqueous coating agent containing a water-soluble resin and water, On the aqueous coating layer, a heat-sensitive recording laminate characterized by having an overcoat layer composed of an overcoat agent containing a thermoplastic resin, a polyisocyanate, and an organic solvent. 【Chemical Formula 1】 (R １ is a linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms substituted with a halogen atom, or an unsubstituted or aryl group having 6 to 12 carbon atoms substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom, and they may be the same or different, R ２ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and they may be the same or different, Z １ is a sulfonyloxy group, a sulfonyl group or a sulfonamide group.) 【Chemical 2】 (R ３ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkyloxyalkyl group having 3 to 12 carbon atoms, a polyoxyalkylene alkyl group having 3 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkylsulfanyl group having 1 to 12 carbon atoms, an aralkylsulfanyl group having 7 to 12 carbon atoms, an arylsulfanyl group having 6 to 14 carbon atoms, an alkylsulfonyl group having 1 to 12 carbon atoms, an aralkylsulfonyl group having 7 to 12 carbon atoms, an arylsulfonyl group having 6 to 15 carbon atoms, an aralkylsulfonylamino group having 7 to 12 carbon atoms, an arylsulfonylamino group having 6 to 15 carbon atoms, an acyl group having 2 to 10 carbon atoms, an acylamino group having 2 to 10 carbon atoms, an (acyl having 2 to 10 carbon atoms) oxycarbonylamino group, an (alkyl having 1 to 12 carbon atoms) oxycarbonylamino group, an aralkyloxycarbonylamino group, an (aralkyl having 7 to 12 carbon atoms) oxycarbonylamino group, or an (aryl having 6 to 15 carbon atoms) oxycarbonylamino group, and two adjacent R ３ may be bonded to each other to form an aromatic ring or a non-aromatic ring together with the carbon atoms to which they are respectively bonded, and R ４ , R ５ are a hydrogen atom or a methyl group, a, b, c are independently integers of 0 to 4, a + c is an integer of 0 to 5, n is 0 or 1, Y is a divalent organic group, and Z ２ is a sulfonyloxy group or a sulfonyl group.) 【Chemical Formula 3】 (R ６ is a linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms substituted with a halogen atom, or an unsubstituted or aryl group having 6 to 12 carbon atoms substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom, R ７ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, l and m are 0 or 1, and Z ３ is a sulfonyloxy group, a sulfonyl group or a sulfonamide group.) 【Chemical Formula 4】 (R ８ is a linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms substituted with a halogen atom, or an unsubstituted or aryl group having 6 to 12 carbon atoms substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom, and they may be the same or different, R ９ is a methyl group, d is an integer of 0 to 4, Z ４ and Z ５ are a sulfonyloxy group, a sulfonyl group or a sulfonamide group, and they may be the same or different.)

2. On one surface of a plastic film substrate, a heat-sensitive coloring layer composed of a leuco dye, a compound represented by the following general formula (5), an aqueous resin, an alcohol, and water, On the heat-sensitive coloring layer, an aqueous coating layer composed of an aqueous coating agent containing a water-soluble resin and water, On the aqueous coating layer, a heat-sensitive recording laminate characterized by having an overcoat layer composed of an overcoat agent containing a thermoplastic resin, a polyisocyanate, and an organic solvent. 【Chemical Formula 5】 (R １０ is a linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms substituted with a halogen atom, or an unsubstituted or aryl group having 6 to 12 carbon atoms substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom, and they may be the same or different from each other.)

3. The heat-sensitive recording laminate according to claim 1 or 2, wherein the aqueous resin is a water-soluble resin or an aqueous emulsion resin.

4. The heat-sensitive recording laminate according to claim 1 or 2, wherein the thermoplastic resin is an acrylic resin, a polyurethane resin, a vinyl chloride-vinyl acetate copolymer, or a fiber-based resin.

5. The heat-sensitive recording laminate according to claim 3, wherein the thermoplastic resin is an acrylic resin, a polyurethane resin, a vinyl chloride-vinyl acetate copolymer, or a fiber-based resin.

6. An overcoat set for use in the heat-sensitive recording laminate according to any one of claims 1 or 2, A coating agent A containing a thermoplastic resin and an organic solvent, A curing agent B containing a polyisocyanate and an organic solvent, characterized by comprising an overcoat set.

7. An overcoat set for use in the heat-sensitive recording laminate according to claim 3, A coating agent A containing a thermoplastic resin and an organic solvent, A curing agent B containing a polyisocyanate and an organic solvent, characterized by comprising an overcoat set.

8. A step of preparing a plastic film substrate, A gravure printing step of forming a heat-sensitive coloring layer provided with a leuco dye, a developer, an aqueous resin, an alcohol, and a heat-sensitive coloring agent containing water on one side of the plastic film substrate; A coating step of forming an aqueous coating layer provided with an aqueous coating agent containing a water-soluble resin and water on the heat-sensitive coloring layer; In a method for manufacturing a heat-sensitive recording laminate including a coating step of forming an overcoat layer provided with an overcoat agent containing a thermoplastic resin, a polyisocyanate, and an organic solvent on the aqueous coating layer, The method for manufacturing a heat-sensitive recording laminate is characterized in that the developer is at least one of a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), and a compound represented by the following general formula (4). 【Chemical Formula 6】 (R １ is a linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms substituted with a halogen atom, or an unsubstituted or aryl group having 6 to 12 carbon atoms substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom, and they may be the same or different from each other. R ２ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and they may be the same or different from each other. Z １ is a sulfonyloxy group, a sulfonyl group or a sulfonamide group.) [Chemical Formula 7] (R ３ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkyloxyalkyl group having 3 to 12 carbon atoms, a polyoxyalkylene alkyl group having 3 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkylsulfanyl group having 1 to 12 carbon atoms, an aralkylsulfanyl group having 7 to 12 carbon atoms, an arylsulfanyl group having 6 to 14 carbon atoms, an alkylsulfonyl group having 1 to 12 carbon atoms, an aralkylsulfonyl group having 7 to 12 carbon atoms, an arylsulfonyl group having 6 to 15 carbon atoms, an aralkylsulfonylamino group having 7 to 12 carbon atoms, an arylsulfonylamino group having 6 to 15 carbon atoms, an acyl group having 2 to 10 carbon atoms, an acylamino group having 2 to 10 carbon atoms, an (acyl having 2 to 10 carbon atoms)oxycarbonylamino group, an (alkyl having 1 to 12 carbon atoms)oxycarbonylamino group, an aralkyloxycarbonylamino group, an (aralkyl having 7 to 12 carbon atoms)oxycarbonylamino group, or an (aryl having 6 to 15 carbon atoms)oxycarbonylamino group, and two adjacent R ３ may be bonded to each other to form an aromatic ring or a non-aromatic ring together with the carbon atoms to which they are respectively bonded, R ４ , R ５ is a hydrogen atom or a methyl group, a, b, c are independently integers from 0 to 4, a + c is an integer from 0 to 5, n is 0 or 1, Y is a divalent organic group, Z ２ is a sulfonyloxy group or a sulfonyl group.) 【Chemical 8】 (R ６ is a linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms substituted with a halogen atom, or an unsubstituted or aryl group having 6 to 12 carbon atoms substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom, R ７ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, l and m are 0 or 1, and Z ３ is a sulfonyloxy group, a sulfonyl group or a sulfonamide group.) 【Chemical Formula 9】 (R ８ is a linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms substituted with a halogen atom, or an unsubstituted or aryl group having 6 to 12 carbon atoms substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom, and they may be the same or different, R ９ is a methyl group, d is an integer of 0 to 4, Z ４ and Z ５ are a sulfonyloxy group, a sulfonyl group or a sulfonamide group, and they may be the same or different.)

9. A step of preparing a plastic film substrate; A gravure printing step of forming a heat-sensitive coloring layer provided with a leuco dye, a developer, an aqueous resin, an alcohol, and a heat-sensitive coloring agent containing water on one side of the plastic film substrate; A coating step of forming an aqueous coating layer provided with an aqueous coating agent containing a water-soluble resin and water on the heat-sensitive coloring layer; In a method for manufacturing a heat-sensitive recording laminate including a coating step of forming an overcoat layer provided with an overcoat agent containing a thermoplastic resin, a polyisocyanate, and an organic solvent on the aqueous coating layer, The method for manufacturing a heat-sensitive recording laminate is characterized in that the developer is a compound represented by the following general formula (5). 【Chemical 10】 (R １０ is a linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms substituted with a halogen atom, or an unsubstituted or aryl group having 6 to 12 carbon atoms substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom, and they may be the same or different from each other.)

10. The method for manufacturing a heat-sensitive recording laminate according to claim 8 or 9, wherein the aqueous resin is a water-soluble resin or an aqueous emulsion resin.

11. The method for manufacturing a heat-sensitive recording laminate according to claim 8 or 9, wherein the thermoplastic resin is an acrylic resin, a polyurethane resin, a vinyl chloride-vinyl acetate copolymer, or a fiber-based resin.

12. The method for manufacturing a heat-sensitive recording laminate according to claim 10, wherein the thermoplastic resin is an acrylic resin, a polyurethane resin, a vinyl chloride-vinyl acetate copolymer, or a fiber-based resin.

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