Color developer and thermal recording material

Abstract

To provide a thermal recording material that achieves reduced environmental load by using isolated lignin and ensures excellent alcohol resistance in printed portions.SOLUTION: A thermal recording material comprises a developer represented by formula (1) and isolated lignin. (In formula (1), a, A, and L are as defined below. a is an integer selected from 1 to 5; A independently represents a fluoro group or a perfluoroalkyl group; L is any functional group represented by formula (2). In formula (2), R is an alkyl group having 1 to 4 carbon atoms. The symbol * indicates the bonding site to the sulfur atom in formula (1)).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a color developer and a heat-sensitive recording material. [Background technology]

[0002] Generally, colorless or pale-colored basic (electron-donating) leuco dyes (hereinafter referred to as "dyes") and an electron-accepting developer (hereinafter referred to as "developer") that reacts with the dye to produce color when heated. Thermal recording materials having a thermal recording layer mainly composed of a thermal recording agent (sometimes abbreviated as "thermal recording agent") are widely used. It has been put to use.

[0003] Many of the compounds used in these developers are 2,2-bis(4-hydroxyphenyl) ) propane (bisphenol A), bis(4-hydroxyphenyl) sulfone (bisphen On the other hand, phenol is a compound that mainly consists of a phenol structure, such as phenol S. Due to the toxicity and environmental risks caused by the skeleton, compounds that do not have a phenol structure are used as color developers. In addition, alcohol-based disinfectants are being used in medical settings and other places. In places where the temperature is high, a thermal recording medium with high alcohol resistance is required for the printed area.

[0004] For example, Patent Document 1 discloses a method for producing a dye using a compound having a specific sulfonylurea structure as a developer. The thermal recording medium used has good color development sensitivity, heat resistance, plasticizer resistance, humidity resistance, and water resistance. The durability of the printed area has been confirmed through various durability tests, including alcohol resistance, oil resistance, and grease resistance. It has been disclosed to be good. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2021 / 107037 Summary of the Invention [Problem to be solved by the invention]

[0006] According to the investigations of the present inventors, the compound having the sulfonylurea structure shown in Patent Document 1 was When a specific compound is used as a developer, the durability of the printed portion of the thermal recording material is good. However, a higher level of alcohol resistance is required. The object of the present invention is to reduce the environmental impact by using isolated lignin and to improve the alcohol resistance of the printed part. The object of the present invention is to provide a heat-sensitive recording material having excellent sealing properties. [Means for solving the problem]

[0007] As a result of extensive research, the present inventors have discovered that a thermal recording material containing a specific color developer and isolated lignin can be used. The present invention has been found to solve the above problems by providing the following: is.

[0008] [1] A heat-sensitive recording material comprising a color developer represented by the following formula (1) and isolated lignin: [ka] (In the above formula (1), a, A, and L are as follows: a is an integer selected from 1 to 5, Each A is independently a fluoro group or a perfluoroalkyl group, L is any functional group represented by the following formula (2). [ka] In the above formula (2), R is an alkyl group having 1 to 4 carbon atoms. * is the sulfur atom in formula (1) Binding sites are indicated.) [2] The color developer according to [1], wherein a in the formula (1) is 1 or 2. [3] The compound according to [1] or [2], wherein A is substituted at the m-position or p-position in the formula (1). Developer. [4] The color developer according to [3], wherein A is substituted at the m-position in the formula (1). [5] The color developer according to [3] or [4], wherein a in the formula (1) is 1. [6] In the formula (1), A is a fluoro group or a trifluoromethyl group [1] to [5]. 1. The developer according to any one of the preceding claims. [7] In the formula (1), L is a phenyl group, an o-toluyl group, a m-toluyl group, or a p-toluyl group. The color developer according to any one of [1] to [6], wherein the color developer is selected from the group consisting of aryl groups. [8] The isolated lignin is kraft lignin or enzymatically decomposed lignin, [1] to [ 7] The developer according to any one of the above items. [9] The thermosensitive recording material according to any one of [1] to [8], wherein the thermosensitive recording layer contains a sensitizer. .

[10] The weight ratio of the developer to the isolated lignin (developer / isolated lignin) is 40 / 60 to 9 The heat-sensitive recording material according to any one of [1] to [9], wherein the thermal conductivity is 0 / 10. [Effects of the Invention]

[0009] According to the present invention, a heat-sensitive recording material having excellent color development sensitivity and alcohol resistance in the printed area is provided. can be.

[0010] The present invention will be described in detail below, but the present invention is not limited to the following description. The present invention can be implemented in various modifications within the scope of the gist of the invention. In an invention, when using "~" to express numerical values ​​or physical properties, The latter value will be used as an inclusion.

[0011] [Thermal recording material] The heat-sensitive recording material of the present invention is a heat-sensitive recording material having a heat-sensitive recording layer, The thermal recording material contains a specific color developer and isolated lignin. The thermal recording layer of the thermal recording material may be any of a film, synthetic paper, card, etc. The film may be provided on a support, and may have a protective layer, an underlayer, or a barrier layer as required, as will be described later. Here, "on the support" means that the support has at least one layer. "Installed on a support" means that the surface of the support is on one side, and is usually on one side. At least a part of the layer may be present.

[0012] [Thermal recording layer] The thermosensitive recording material according to an embodiment of the present invention has a thermosensitive recording layer, The thermal recording layer contains a color developer and isolated lignin, as well as leuco Dyes, developers other than those mentioned above (hereinafter sometimes referred to as "other developers"), sensitizers The ink may contain stabilizers, binders, crosslinking agents, pigments, lubricants, and other additives.

[0013] [Developer] The color developer according to the first embodiment of the present invention is a color developer containing a compound represented by the following formula (1): do. [ka] (In the above formula (1), a, A, and L are as follows: a is an integer selected from 1 to 5, Each A is independently a fluoro group or a perfluoroalkyl group, L is any functional group represented by the following formula (2). [ka] In the above formula (2), R is an alkyl group having 1 to 4 carbon atoms. * is the sulfur atom in formula (1) The binding site of

[0014] The color developer according to the first aspect of the present invention has the remarkable effect of being excellent in color development sensitivity and storage stability. The reason why the above-mentioned color developer exhibits such excellent effects is believed to be as follows. That is, a fluoro group or a perfluoro group is used as a substituent for a sulfonylurea compound. By introducing an orthoalkyl group, the acidity and / or hydrogen bond donating ability of the NH moiety can be improved. This improves the sensitivity of the color development by making it easier to react with leuco dyes, and at the same time, stabilizes the color development state. This is thought to be because the storage stability is improved by converting the fluorine group or By having a perfluoroalkyl group, association and / or crystallinity are moderately suppressed. By doing so, amorphous stability can be effectively maintained without excessively lowering the energy required for melting. This is thought to be because the storage stability of the color-developed state, which is a metastable state, can be improved. Furthermore, by having a fluoro group or a perfluoroalkyl group as a substituent, leuco High color development is achieved by appropriately adjusting the molecular level compatibility with dyes and sensitizers. It is believed that sensitivity and storage stability can be achieved at the same time. The molecule has a hydrophilic portion due to the fluoro group or perfluoroalkyl group, and a hydrophobic portion due to the fluoro group or perfluoroalkyl group. By incorporating this, it is believed that storage stability can be improved under various storage conditions. Specifically, it is possible to improve resistance to moisture and water while also improving resistance to oil and grease. It is believed that resistance can be increased to a high level at the same time.

[0015] In the above formula (1), a is an integer selected from 1 to 5, preferably 3 or less, more preferably Preferably, a is 2 or less, and particularly preferably 1. When a is large, the hydrophobicity increases, and the water-soluble polymer The dispersibility of the polymer decreases, and the molecular weight increases, making it difficult for the molecules to move when melted. It is thought that the compatibility with leuco dyes and sensitizers is too low, resulting in a decrease in color development performance. . In the above formula (1), the perfluoroalkyl group in A has 1 to 12 carbon atoms. Preferably, the carbon number is 6 or less, more preferably 4 or less, and particularly preferably 1 carbon atom (trifluoromethyl). The perfluoroalkyl group with a large number of carbon atoms is too hydrophobic and cannot be dissolved in water. The dispersibility of the polymer decreases, and the molecular weight increases, making it difficult for the molecules to move when melted. It is believed that the color development performance deteriorates when the compatibility with the leuco dye and the sensitizer decreases too much. Each A is independently a fluoro group or a perfluoroalkyl group, but when a is 2 or more, In this case, all A's may be the same or different substituents, and all A's may be the same substituent. It is more preferable that A is a full-bodied copolymer because it provides appropriate hydrophobicity and compatibility. A fluoromethyl group or a trifluoromethyl group is preferred, and among these, high compatibility leads to high color development sensitivity. The trifluoromethyl group is particularly preferred due to its ease of realization.

[0016] The substitution position of the fluoro group or perfluoro group in A is not particularly limited, but The o- or m-position is preferred because it suppresses the formation of the hydroxyl group and provides suitable amorphous stability. and is spatially separated from adjacent NH moieties so as not to inhibit reactivity with leuco dyes. Therefore, the m-position or p-position is preferred. Therefore, the m-position is particularly preferred. When a is 2 or more, at least one A is at the m-position. It is preferable that there is.

[0017] L is any functional group represented by the above formula (2), i.e., a phenyl group and a monosubstituted phenyl group. The functional group is any one selected from the group consisting of a group. In the above formula (2), R is an alkyl group having 1 to 4 carbon atoms, and thermal motion is suppressed, resulting in storage stability. A methyl group or an ethyl group is preferred, and a methyl group is particularly preferred, since the properties of the methyl group are easily improved. I wish. The functional group represented by the above formula (2) is preferably a phenyl group, an o-tolyl group, an m-tolyl group, or a phenyl group. It is a p-tolyl group or a p-tolyl group.

[0018] In a particularly preferred embodiment of the color developer according to the first aspect of the present invention, in the above formula (1), a is 2 or less, A is a fluoro group or a perfluoro group having 4 or less carbon atoms, Alternatively, the substitution position of the perfluoro group is the m-position or the p-position, and in the above formula (2), R is methyl. The alkyl group is an alkyl group or an ethyl group.

[0019] Specific examples of the above formula (1) include, but are not limited to, the following: [ka] [ka]

[0020] The heat-sensitive recording material according to an embodiment of the present invention contains isolated lignin. It is lignin isolated by modifying it. Among the isolated lignins, the one that is handled industrially is The lignins used are called industrial lignins, and include lignosulfonic acid (salts) and kraft lignin. , soda lignin, soda-anthraquinone lignin, organosol lignin, explosive lignin lignin, sulfuric acid lignin, and lignin isolated by enzymatic decomposition (hereinafter referred to as "enzymatic decomposition") Among these, kraft lignin or enzymatically decomposed lignin is Enzymatically decomposed lignin is preferable in that it improves the alcohol resistance of the recorded portion. This is more preferable in that no sulfur remains due to the addition of sulfur and color development of the coating liquid can be suppressed.

[0021] Enzymatically decomposed lignin includes lignin derived from wood flour, lignin derived from bamboo, and lignin derived from straw. Examples include lignin derived from corn cobs and lignin derived from corn cobs.

[0022] The heat-sensitive recording material according to the embodiment of the present invention has excellent color development sensitivity and alcohol resistance in the printed area. The above-mentioned thermal recording material has the following excellent effects: The following reasons are presumed to be the cause. The colored state formed by the reaction of the developer and leuco dye is an amorphous state in which a reversible reaction also occurs. It is a metastable state and is easily inhibited by external factors. For example, contact with alcohol When the developer is dissolved in alcohol or crystallized, it bonds with the leuco dye. The part will be cut and discolored. Developers with sulfonylurea or urea groups to make them less soluble in alcohol Compounds with increased molecular weight by designing three or more benzene rings (for example, PF -201 and Nippon Soda's NKK-1304, etc.) improve alcohol resistance but reduce color sensitivity. It ends up happening. In order to demonstrate color development sensitivity, the use of a color developer having a sulfonylurea group or a urea group is also preferred. Known color developers designed with two or less Zene rings easily lose their color when they come into contact with alcohol. On the other hand, the polymer structure of isolated lignin reduces its affinity with alcohol, which is an external factor. This prevents the penetration of alcohol and stabilizes the bond between the leuco dye and the developer. Therefore, it is assumed that the color is difficult to erase. However, it is not possible to simply combine the above-mentioned known color developer designed to have two or less benzene rings with isolated lignin. Combining these leads to a significant decrease in color development sensitivity. The color developer represented by formula (1) having a fluoro group or a perfluoroalkyl group of this design is , the electron-withdrawing function activates the NH color-forming site and improves compatibility with leuco dyes. , and can fully demonstrate color development sensitivity compared to the above color developers, so it can be used in combination with isolated lignin. Therefore, the alcohol resistance can be improved without causing a decrease in sensitivity.

[0023] The isolated lignin may be used alone or in combination of two or more types. When using the developer, the weight ratio of the developer to the isolated lignin (developer / isolated lignin) is preferably Preferably, it is 40 / 60 to 90 / 10, and more preferably 50 / 50 to 70 / 30.

[0024] [Leuco dye] In this embodiment, the heat-sensitive recording layer preferably contains a leuco dye. It is usually basic, and any of the materials conventionally known in the field of pressure-sensitive or heat-sensitive recording paper can be used. Specific examples of leuco dyes include triphenylmethane-based leuco dyes and fluoran-based leuco dyes. Leuco dyes, fluorene-based leuco dyes, divinyl-based leuco dyes, etc. are preferred. Specific examples of colorless or pale-colored dyes (dye precursors) are shown below. The icosyl dye precursors may be used alone or in combination of two or more. The leuco dye is used in an amount of 10 to 200 parts by weight per 100 parts by weight of the developer of formula (1). It is preferably 15 to 150 parts by weight, and more preferably 20 to 10 0 parts by weight.

[0025] Triphenylmethane leuco dyes include 3,3-bis(p-dimethylaminophenyl) 3,3-(trimethyl)-6-dimethylaminophthalide [also known as crystal violet lactone]; Bis(p-dimethylaminophenyl)phthalide [also known as malachite green lactone], etc. Examples include:

[0026] Fluoran leuco dyes include 3-diethylamino-6-methylfluoran; Diethylamino-6-methyl-7-anilinofluoran;3-Diethylamino-6-methyl 3-Diethylamino-6-methyl- 7-Chlorofluoran; 3-Diethylamino-6-methyl-7-(m-trifluoromethyl) 3-Diethylamino-6-methyl-7-(o-chloroanilino)fluoran; ) Fluoran; 3-diethylamino-6-methyl-7-(p-chloroanilino)fluoran 3-Diethylamino-6-methyl-7-(o-fluoroanilino)fluoran Diethylamino-6-methyl-7-(m-methylanilino)fluoran;3-Diethylamino 3-Diethylamino-6-methyl-7-octylanilinofluoran -7-octylaminofluoran;3-diethylamino-6-methyl-7-benzylamine Fluoran; 3-Diethylamino-6-methyl-7-dibenzylaminofluoran; 3 -Diethylamino-6-chloro-7-methylfluoran;3-Diethylamino-6-chloro 3-Diethylamino-6-chloro-7-p-methylanilinofluoran; 3-Diethylamino-6-ethoxyethyl-7-anilinofluoran;3 -Diethylamino-7-methylfluoran; 3-Diethylamino-7-chlorofluoran ;3-Diethylamino-7-(m-trifluoromethylanilino)fluoran;3-Diethylamino 3-Diethylamino-7-(o-chloroanilino)fluoran; 3-Diethylamino-7-(p- 3-Diethylamino-7-(o-fluoroanilino)fluoran Fluoran;3-Diethylamino-benzo[a]fluoran;3-Diethylamino-benzo[ c] Fluoran; 3-dibutylamino-6-methyl-fluoran; 3-dibutylamino- 6-Methyl-7-anilinofluoran; 3-Dibutylamino-6-methyl-7-(o,p -dimethylanilino)fluoran;3-dibutylamino-6-methyl-7-(o-chloro Anilino)fluoran;3-Dibutylamino-6-methyl-7-(p-chloroanilino) Fluoran; 3-dibutylamino-6-methyl-7-(o-fluoroanilino)fluoran 3-Dibutylamino-6-methyl-7-(m-trifluoromethylanilino)fluoro Fluoran;3-Dibutylamino-6-methyl-chlorofluoran;3-Dibutylamino-6- Ethoxyethyl-7-anilinofluoran; 3-dibutylamino-6-chloro-7-anilinofluoran Linofluoran; 3-dibutylamino-6-methyl-7-p-methylanilinofluoran ;3-Dibutylamino-7-(o-chloroanilino)fluoran;3-Dibutylamino- 7-(o-Fluoroanilino)fluoran;3-Dipentylamino-6-methyl-7- Anilinofluoran; 3-dipentylamino-6-methyl-7-(p-chloroanilino ) Fluoran; 3-di-pentylamino-7-(m-trifluoromethylanilino)fluoran Fluoran;3-Dipentylamino-6-chloro-7-anilinofluoran;3-Dipentylamino 3-Pyrrolidino-6-methyl-7-(p-chloroanilino)fluoran; -Anilinofluoran; 3-piperidino-6-methyl-7-anilinofluoran; 3-( N-methyl-N-propylamino)-6-methyl-7-anilinofluoran;3-(N- Methyl-N-cyclohexylamino)-6-methyl-7-anilinofluoran;3-(N -ethyl-N-cyclohexylamino)-6-methyl-7-anilinofluoran;3-( N-ethyl-N-xylamino)-6-methyl-7-(p-chloroanilino)fluoran ;3-(N-ethyl-p-toluidino)-6-methyl-7-anilinofluoran;3-( N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluoran;3-(N -ethyl-N-isoamylamino)-6-chloro-7-anilinofluoran;3-(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-Cyclohexylamino-6-chlorofluoran;2-(4-oxahexyl)-3 -Dimethylamino-6-methyl-7-anilinofluoran;2-(4-oxahexyl) -3-Diethylamino-6-methyl-7-anilinofluoran;2-(4-oxahexyl 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 2-Benzyl 6-p-(p-phenylaminophenyl)aminoanilinofluoran -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 2,4-Diamino-6-p-(p-dibutylaminophenyl)aminoanilinofluoran Examples include methyl-6-[(4-dimethylamino)anilino]fluoran.

[0027] Fluorene leuco dyes include 3,6,6'-tris(dimethylamino)spiro[ Fluorene-9,3'-phthalide];3,6,6'-tris(diethylamino)spiro[ fluorene-9,3'-phthalide], and the like.

[0028] Divinyl leuco dyes 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) ester] 3,3-bis[1,1-bis(4-thenyl]-4,5,6,7-tetrachlorophthalide; pyrrolidinophenyl)ethylene-2-yl]-4,5,6,7-tetrabromophthalide; 3,3-bis[1-(4-methoxyphenyl)-1-(4-pyrrolidinophenyl)ethylene] benzo-2-yl]-4,5,6,7-tetrachlorophthalide, and the like.

[0029] Other leuco dyes include 3-(4-diethylamino-2-ethoxyphenyl)- 3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide; 3-(4- Diethylamino-2-ethoxyphenyl)-3-(1-octyl-2-methylindole -3-yl)-4-azaphthalide;3-(4-cyclohexylethylamino-2-methoxy (1-phenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalyl 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide;3,6- Bis(diethylamino)fluoran-γ-(3'-nitro)anilinolactam;3,6- Bis(diethylamino)fluoran-γ-(4'-nitro)anilinolactam;1,1- Bis[2',2',2”,2”-tetrakis-(p-dimethylaminophenyl)-ethenyl 1,1-bis[2',2',2”,2”-tetrakis(2,2-dinitrileethane); -(p-dimethylaminophenyl)-ethenyl]-2-β-naphthoylethane;1,1- Bis[2',2',2”,2”-tetrakis(p-dimethylaminophenyl)ethenyl] -2,2-diacetylethane; bis[2,2,2',2'-tetrakis(p-dimethylacetone); [aminophenyl]ethenyl-methylmalonic acid dimethyl ester, etc.

[0030] [Other color developers] The thermosensitive recording layer may contain a color developer other than that represented by formula (1) within a range that does not impair the effects of the present invention. As other color developers, any of those known in the field of conventional pressure-sensitive or heat-sensitive recording paper may be used. Any of these can be used, and although there is no particular limitation, an electron-accepting developer is preferred. The other color developers may be used alone or in combination of two or more. When the color developer is used, the amount thereof to be used is preferably Preferably, 1 to 5,000 parts by weight, more preferably 5 to 1,000 parts by weight, and even more preferably , 10 to 500 parts by weight. By using other color developers, high color sensitivity is maintained, and heat resistance and humidity resistance are also achieved. The thermal recording material can be improved in image preservation properties such as durability and water resistance. As other color developers, any of those known in the field of conventional pressure-sensitive or heat-sensitive recording paper can be used. Other color developers include bisphenol compounds, urea compounds, and the like. Preferred are phenol compounds and novolak-type phenol compounds.

[0031] Bisphenol compounds include 4,4'-isopropylidenediphenol, 2,2 '-Bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)propane (hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxyphenyl)-4-methyl Pentane, 4,4'-dihydroxydiphenyl sulfide, di(4-hydroxy-3-methylphenyl) 2,2'-thiobis(3-tert-octylphenyl) sulfide, 2,2'-thiobis(3-tert-octylphenol) , 2,2'-thiobis(4-tert-octylphenol), 4,4'-dihydroxy Diphenyl sulfone, 2,4'-dihydroxydiphenyl sulfone, 4-hydroxy-4 '-Propoxydiphenyl sulfone, 4-hydroxy-4'-isopropoxydiphenyl Sulfone, 4-hydroxy-4'-allyloxydiphenyl sulfone, bis(3-allyl -4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-benzyloxy Phenyl sulfone, 3,4-dihydroxyphenyl-4'-methylphenyl sulfone, 2 ,4-bis(phenylsulfonyl)phenol, bisphenol A described in Patent No. 3913820 Phenol sulfone-bridged compounds, bisphenol sulfonates described in Patent No. 4004289 Examples include amine derivatives.

[0032] Urea compounds include 4,4'-bis(3-(phenoxycarbonylamino)methyl) diphenyl sulfone, N-(p- toluenesulfonyl)-N'-(3-p-toluenesulfonyloxyphenyl)urea, 4,4'-bis(3-tosylureido)difluoromethane as described in JP 2011-105638 A phenylmethane, N-[2-(3-phenylmethyl)methyl]methyl,

[0033] (Raido)phenyl]benzenesulfonamide, as described in JP 2017-165091 A N-[2-(acetoxy)phenyl]-N'-phenylurea, N-[3-(acetoxy)phenyl]-N'-phenylurea (iii)phenyl]-N'-phenylurea, N-[2-(benzoyloxy)phenyl]- N'-Phenylurea, N-[3-(benzoyloxy)phenyl]-N'-phenylurea Rare, N-(m-tolylaminocarbonyl) described in WO 2017 / 047572 -phenylalanine, N-(p-toluenesulfonyl)-phenylalanine, N-(phenylalanine N-(m-tolylaminocarbonyl)-valine, N-(m-tolylaminocarbonyl)-methionine, N-(m-tolylaminocarbonyl)-tyrosine, N-(m-tolylaminocarbonyl) -phenylglycine, N-(m-tolylaminocarbonyl)-valine, N-(m-tolyl Aminocarbonyl)-cysteine-S-benzyl, N-(m-tolylaminocarbonyl) -β-alanine, N-phenylaminothiocarbonyl-glycylglycine, N-(p-tolyl N-(p-phenylsulfonylaminocarbonyl)-phenylalanine-methyl ester (toluenesulfonyl)-β-alanine, N-(p-tolylaminocarbonyl)-methionine and amino acid derivatives such as N-(phenylaminocarbonyl)-methionine. do.

[0033] As the novolak type phenolic compound, there are mentioned the compounds described in WO 02 / 098674. Examples include phenol-formalin condensation products.

[0034] In addition to the compounds listed above, activated clay, attapulgite, colloidal silica, and silicate Inorganic acidic substances such as aluminum, hydroquinone monobenzyl ether, 4-hydroxybenzoic acid Benzyl carbonate, aminobenzenesulfonamide derivatives described in JP-A-8-59603 bis(4-hydroxyphenylthioethoxy)methane, 1,5-di(4-hydroxyphenylthioethoxy)methane (phenylthio)-3-oxapentane, bis(p-hydroxyphenyl)butyl acetate, Methyl bis(p-hydroxyphenyl)acetate, 1,1-bis(4-hydroxyphenyl)- 1-Phenylethane, 1,4-bis[α-methyl-α-(4'-hydroxyphenyl)ethane ethyl]benzene, 1,3-bis[α-methyl-α-(4'-hydroxyphenyl)ethyl ] Benzene, as described in International Publication No. 02 / 081229 and Japanese Patent Application Laid-Open No. 2002-301873 thiourea compounds such as N,N'-di-m-chlorophenylthiourea, p-chlorophenyl Benzoic acid, stearyl gallate, bis[4-(octyloxycarbonylamino)sulfonyl] Zinc licylate] dihydrate, 4-[2-(p-methoxyphenoxy)ethyloxy]salicylate acid, 4-[3-(p-tolylsulfonyl)propyloxy]salicylic acid, 5-[p-( Aromatic carboxylic acids such as 2-p-methoxyphenoxyethoxy)cumyl]salicylic acid, and The zinc, magnesium, aluminum, calcium, titanium, and manganese compounds of these aromatic carboxylic acids Salts with polyvalent metals such as zinc, tin, and nickel, as well as antipyri- zinc thiocyanate complexes, and complex zinc salts of terephthalaldehyde acid and other aromatic carboxylic acids. The higher fatty acid metal double salt and polyhydroxy aromatic compound described in JP-A-10-258577 are and metal chelate complexes of aromatic compounds.

[0035] Among the other developers mentioned above, 4,4'-dihydroxydiphenyl sulfone, 2,4' -Dihydroxydiphenyl sulfone, 4-hydroxy-4'-propoxydiphenyl sulfone 4-hydroxy-4'-isopropoxydiphenyl sulfone, 4-hydroxy-4 '-Allyloxydiphenyl sulfone, bis(3-allyl-4-hydroxyphenyl) sulfone sulfon, 4,4'-isopropylidenediphenol, 2,2'-bis(4-hydroxy- 3-methylphenyl)propane, diphenyl sulfone bridge described in Patent No. 3913820 Bridged compounds, diphenyl sulfone derivatives described in Patent No. 4004289, and WO 02 / 04444 phenol-formalin condensation products described in Patent Publication No. 2 / 098674, 4,4'-bis(3-(phenol (Phenoxycarbonylamino)methylphenylureido)diphenyl sulfone, Patent No. 46 N-(p-toluenesulfonyl)-N'-(3-p-toluenesulfonyl)- (phenyloxyphenyl)urea, 4,4'- Bis(3-tosylureido)diphenylmethane, as described in JP 2016-165835 A N-[2-(3-phenylureido)phenyl]benzenesulfonamide, International Publication N-(m-tolylaminocarbonyl)-phenylalanine as described in Patent Publication No. 2017 / 047572 N-(m-tolylaminocarbonyl)-methionine is preferred, and 4,4'-dihydro- 2,4'-dihydroxydiphenyl sulfone, 4-hydroxydiphenyl sulfone 4-hydroxy-4'-isopropoxydiphenyl sulfone, 4-hydroxy-4'-isopropoxydiphenyl sulfone Phenyl sulfone, 4-hydroxy-4'-allyloxydiphenyl sulfone, bis(3- (allyl-4-hydroxyphenyl) sulfone, bisphenyl ether described in Patent No. 3913820 Nol sulfone crosslinked compounds, bisphenol sulfones described in Patent No. 4004289 Derivatives, N-(p-toluenesulfonyl)-N'-(3 -p-toluenesulfonyloxyphenyl)urea, JP 2011-105638 A 4,4'-bis(3-tosylureido)diphenylmethane described in JP 2016-16 N-[2-(3-phenylureido)phenyl]benzenesulfonate as described in Patent Publication No. 5835 By using these compounds, the color development sensitivity of the thermal recording material can be maintained. While improving image preservation properties (heat resistance, plasticizer resistance, humidity resistance, water resistance, grease resistance), etc. It can be done.

[0036] [Sensitizer] In this embodiment, a known sensitizer may be used. There is no particular limitation on the sensitizer, but examples include For example, 1,2-di-(3-methylphenoxy)ethane, 2-benzyloxynaphthalene, Fatty acid amides having 10 to 21 carbon atoms (e.g., stearic acid amide, palmitic acid amide, etc.) ), ethylene bisamide, p-toluenesulfonamide, Montan acid wax, polyethylene Renwax, p-benzylbiphenyl, diphenyl sulfone, 4-biphenyl-p-tolyl aryl ether, m-terphenyl, 1,2-diphenoxyethane, dibenzyl oxalate, Di(p-chlorobenzyl) oxalate, Di(p-methylbenzyl) oxalate, Di(p-methylbenzyl) oxalate -p-Methylbenzyl ester, dibenzyl terephthalate, p-benzyloxybenzoic acid Benzyl, di-p-tolyl carbonate, phenyl-α-naphthyl carbonate, 1,4 -Diethoxynaphthalene, 1-hydroxy-2-naphthoic acid phenyl ester, o-hydroxy phenyl-bis-(phenyl ether), 4-(m-methylphenoxymethyl)biphenyl, 4,4'-Ethylenedioxy-bis-benzoic acid dibenzyl ester, dibenzoyloxy Methane, 1,2-di(3-methylphenoxy)ethylene, bis[2-(4-methoxy- phenyloxyethyl] ether, methyl p-nitrobenzoate, phenyl p-toluenesulfonate Among these, 1,2-di-(3-methylphenoxy) ) ethane, 1,2-diphenoxyethane, fatty acid amides having 10 to 21 carbon atoms (e.g., sucrose, stearic acid amide, palmitic acid amide, etc.), 2-benzyloxynaphthalene, diphenyl sulfone, p-toluenesulfonamide and oxalic acid-di-p-methylbenzyl ester The preferred color developing material is 1,2-di-(3-methylphenoxy) which exhibits high color development sensitivity even at low energy. These sensitizers may be used alone or in combination of two or more. When a sensitizer is used, the amount of the sensitizer used is the same as that of the developer according to the embodiment of the present invention. It is preferably 25 to 250 parts by weight, more preferably 50 to 100 parts by weight. 50 parts by weight.

[0037] [Stabilizer] In this embodiment, a known stabilizer may be used. There is no particular limitation on the stabilizer, but examples include: For example, hindered phenol compounds, ultraviolet absorbers (e.g., benzophenone compounds) Among these, hindered phenol compounds are preferred. The phenol-based compounds improve the image preservation properties (heat resistance, moisture resistance, water resistance, plasticizer resistance, etc.) of the recorded area. This is preferable in that it increases the The hindered phenol compound usually has 1 or more and 15 or less in one molecule, preferably is a compound having two or more and six or less hydroxyphenyl groups. The molecular weight of the alcohol-based compound is usually 200 or more and 2000 or less, preferably 250 or more and 1800 or less. 00 or less, more preferably 300 or more and 1500 or less. The melting point of the mixture is preferably 100°C or higher and 300°C or lower. Furthermore, at least one of the hydroxyphenyl groups contained in the hindered phenol compound In one molecule, if the position of the phenolic hydroxyl group is the 1st position, then the position Carbon atoms bonded to hydrogen atoms (i.e., no substituents at the 2nd or 6th positions) ) is preferred.

[0038] Specific examples of the hindered phenol compounds include those described in Japanese Patent Publication No. 39-4469 and tris(hydroxyphenyl)alkanes described in Japanese Patent Application Laid-Open No. 56-40629; 1,1,3-tris-substituted butane compounds. These are used in combination with two or more It may also be used. The hindered phenol compounds may be used alone or in combination of two or more. When a hindered phenol compound is used in a thermal recording material, the content The amount is preferably 1 to 100 parts by weight, more preferably 1 to 100 parts by weight, based on 100 parts by weight of the color developer of formula (1). Preferably, the content is 1 to 70 parts by weight, more preferably 1 to 50 parts by weight. If the content of the compound is less than the above range, the moisture resistance, water resistance, and heat resistance of the recorded area will decrease. There is a possibility that color development in the blank areas due to heating may not be suppressed. If the amount is greater than the range, the color development sensitivity may decrease and the plasticizer resistance of the recorded area may decrease. .

[0039] 〔binder〕 It is preferable to use a binder to form the heat-sensitive recording layer. Examples of suitable polyvinyl alcohols include fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, and acetylated polyvinyl alcohol, carboxy-modified polyvinyl alcohol, amide-modified soluble polyvinyl alcohol, sulfonic acid modified polyvinyl alcohol, butyral modified polyvinyl Polyvinyl alcohol, olefin-modified polyvinyl alcohol, nitrile-modified polyvinyl alcohol Pyrrolidone-modified polyvinyl alcohol, silicone-modified polyvinyl alcohol, Other modified polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, methyl cellulose, carboxymethyl cellulose, polystyrene, styrene-maleic anhydride Acid copolymers, styrene copolymers such as styrene-butadiene copolymers, ethyl cellulose and and cellulose derivatives such as acetyl cellulose, casein, gum arabic, oxidized starch, acetone Esterified starch, dialdehyde starch, esterified starch, polyvinyl chloride, polyvinyl acetate, poly acrylamide, polyacrylic ester, polyvinyl butyral, polyamide resin, Examples of the resin include silicone resin, petroleum resin, terpene resin, ketone resin, and coumarone resin. The amount of binder used is suitably about 5 to 25% by weight of the solid content of the heat-sensitive recording layer. The binder is generally used as a solution, emulsion, dispersion, paste, or a combination thereof. The solvent for the solution, emulsion or dispersion, or the medium for the paste, may be, for example, water. , alcohols, ketones, esters, hydrocarbons, etc.

[0040] [Crosslinking agent] Examples of crosslinking agents include glyoxal, methylolmelamine, and melamine formaldehyde. Dehyde resin, melamine urea resin, polyamine epichlorohydrin resin, polyamide epi Chlorhydrin resin, potassium persulfate, ammonium persulfate, sodium persulfate, ferric chloride, Examples include magnesium chloride, borax, boric acid, alum, and ammonium chloride. When a crosslinking agent is used, the amount thereof is preferably 100 parts by weight of the color developer of formula (1). is 0.5 to 500 parts by weight.

[0041] [Pigments] Examples of pigments include silica (excluding colloidal silica), calcium carbonate, and kaolin. Inorganic or inorganic materials such as cellulose, calcined kaolin, diatomaceous earth, talc, titanium oxide, and aluminum hydroxide When a pigment is used, the amount of the pigment used is 100% of the developer of formula (1). The amount is preferably 25 to 1000 parts by weight.

[0042] [Lubricant] Examples of lubricants include fatty acid metal salts such as zinc stearate and calcium stearate. When a lubricant is used, the amount of the lubricant used is The amount is preferably 0.5 to 500 parts by weight relative to 100 parts by weight of the color developer of formula (1).

[0043] [Other additives] Other additives include, for example, dispersants, antifoaming agents, fluorescent dyes, etc. When the additive is used, the amount thereof is preferably 100 parts by weight of the color developer of formula (1). The amount is preferably 0.5 to 500 parts by weight.

[0044] [Support] There are no particular restrictions on the shape, structure, size, material, etc. of the support used in the thermal recording material. The shape of the support may be a sheet, a roll, or the like. The support may have a single layer structure or a laminated structure. The size of the support can be appropriately selected depending on the intended use of the thermal recording material. The support material may be, for example, a plastic film, synthetic paper, wood-free paper, or recycled paper pulp. Paper, recycled paper, one-sided glossy paper, greaseproof paper, coated paper, art paper, cast coated paper, lightly coated paper, resin Examples include laminated paper and release paper. In addition, composite sheets that combine these are used as supports. It may also be used as such. The thickness of the support is not particularly limited and can be appropriately selected depending on the purpose. The thickness is preferably 2,000 μm or less, and more preferably 50 to 1,000 μm.

[0045] [Protective layer] In the thermal recording material, a protective layer may be provided on the thermal recording layer. If a protective layer is provided on the thermal recording material to improve the image preservability, the color development sensitivity decreases. However, since the color developer used in the thermal recording material has good color development sensitivity, Even if a protective layer is provided on the thermal paper, the color development sensitivity required for thermal paper can be maintained. The types and amounts of various components used in the recording are determined according to the required performance and recording suitability. However, it is not limited to the above.

[0046] [Underlayer, back layer, middle layer] In thermal recording materials, in order to further increase color sensitivity, An under layer composed of the following may be provided between the support and the thermosensitive recording layer. In order to correct the curl of the recording material, a sheet is attached to the side of the support opposite to the side on which the thermal recording layer is present. As an embodiment of each layer in the heat-sensitive recording material of the present invention, a protective layer may be provided. The example of the embodiment is a laminated structure in the order of / thermosensitive recording layer / under layer / support / back layer. This is not limited to: Furthermore, the thermal recording layer is provided between the support and the underlayer, between the underlayer and the thermal recording layer, and between the thermal recording layer and the underlayer. An intermediate layer is formed between the recording layer and the protective layer and / or between the support and the back layer. Good too.

[0047] [Method of manufacturing the thermal recording material] The thermal recording material contains a basic leuco dye, a developer, a sensitizer, and other ingredients as needed. A coating solution containing the sensitizer, other color developers, stabilizers, etc. is applied to at least one side of the support. The thermosensitive recording layer can be formed by coating and drying at least a part of the substrate. This coating liquid can be applied according to well-known conventional techniques. There is no particular limitation on the coating means. For example, air knife coater, rod blade coater, bent blade coater Equipped with various coaters such as bevel blade coater, roll coater, curtain coater, etc. An off-machine coater or an on-machine coater may be used.

[0048] The coating liquid for forming the thermosensitive recording layer contains, for example, a color developer and a sensitizer, and optionally Leuco dyes, other sensitizers, other color developers, stabilizers, etc. are mixed and then mixed in a ball mill, atr Grinding machines such as a sand grinder or suitable emulsifying equipment into particles of several microns or less After the particles are pulverized to a diameter of 100 mm, a binder or the like can be added to form the powder. The solvent used in the coating liquid may be water, alcohol, or the like. It is usually 20 to 40% by weight. The coating amount of the thermal recording layer can be appropriately selected depending on the composition and the application of the thermal recording material. However, the dry weight is usually 1 to 20 g / m 2 , preferably 2 to 12 g / m 2 is in the range .

[0049] Also, the protective layer, the underlayer, the back layer, and the intermediate layer can also be formed by applying and drying a coating solution containing the same constituent components as those of the above-described heat-sensitive recording layer. Further, the heat-sensitive recording material having each layer formed thereon may be subjected to a treatment known in the art (for example, smoothing treatment by supercalendering or the like).

[0050] [Uses of the Heat-Sensitive Recording Material] The heat-sensitive recording material of the present embodiment can be suitably used for applications such as paper, film, IC cards, friction ball pens, etc.

Examples

[0051] Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the following examples and comparative examples, paper provided with an underlayer on one surface of a support was used, and a heat-sensitive recording layer (heat-sensitive coloring layer) was formed on the underlayer. In the following examples and comparative examples, "parts" and "% " indicate "parts by weight" and "weight % ", respectively, unless otherwise specified.

[0052] [Coating Solution for the Heat-Sensitive Recording Layer] The following Liquid A to Liquid F were each prepared. In Liquid A, Liquid B, and Liquid C, wet grinding was performed with a Ready Mill (RMB-02 ) manufactured by Imex Co., Ltd. until the average particle diameter of each component became 0.5 μm. Here, the average particle diameter is the average diameter in the volume-based distribution, and was measured with a laser diffraction / scattering type particle size distribution measuring device (Microtrac MT3000 II) manufactured by Nikkiso Co., Ltd.

[0053] [Example 1] [Liquid A] · 4-Methyl-N-[[[3-(trifluoromethyl)phenyl]amino]carbonyl] benzenesulfonamide (synthesis example of Patent Document 1 (International Publication No. 2021 / 107037)) Based on Example 2, it was synthesized by the same operation. Hereinafter, it is referred to as "Compound 1". : 28.0 parts · Kraft lignin (derived from softwood): 12.0 parts · Polyvinyl alcohol (10% aqueous solution): 50.0 parts · Water: 10.0 parts <Liquid B> · 3-Dibutylamino-6-methyl-7-anilinofluoran (manufactured by Yamamoto Chemical Co., Ltd., trade name "ODB-2"): 36.5 parts · Polyvinyl alcohol (10% aqueous solution): 60.0 parts · Water: 3.5 parts <Liquid C> · Stearamide (manufactured by Mitsubishi Chemical Corporation, trade name "AP-1") : 40.0 parts · Polyvinyl alcohol (10% aqueous solution): 50.0 parts · Water: 10.0 parts <Liquid D> · 60% calcium carbonate dispersion (manufactured by Okutama Kogyo Co., Ltd., trade name "Tamapal TP- 123CS") <Liquid E> · 36% zinc stearate dispersion (manufactured by Chukyo Yushi Co., Ltd., trade name "Hydrin Z-8-36" ) <Liquid F> · 10% polyvinyl alcohol aqueous solution (manufactured by Nippon Gosei Co., Ltd., trade name "Gosenol NH-1 8" of 10% aqueous solution)

[0054] Each liquid was mixed in the following ratio to prepare a coating solution for the thermosensitive recording layer. Liquid A: 18.89 parts Liquid B: 10.00 parts Liquid C: 9.44 parts Liquid D: 17.87 parts Liquid E: 6.00 parts Liquid F: 19.62 parts Next, an underlayer was provided on one side of the high-quality paper as the support, and on top of the underlayer, a heat-sensitive recording layer with a dry weight of 3 g / m 2 was applied and dried (using a forced-air dryer at 60°C for 2 minutes) to form a heat-sensitive recording layer. Then, the support with the underlayer and the heat-sensitive recording layer formed thereon was processed with a super calender to achieve a smoothness of 500 - 1000 seconds to obtain a heat-sensitive recording material. This was further smoothed with a super calender under a pressure of 1 kgf / cm to obtain a heat-sensitive recording material. [[Example 2]] 2 The following proportions of each liquid were mixed to prepare a coating liquid for the heat-sensitive recording layer.

[0055] Liquid A: 18.89 parts Liquid B: 10.00 parts Liquid D: 17.87 parts Liquid E: 6.00 parts Liquid F: 19.62 parts Next, an underlayer was provided on one side of the high-quality paper as the support, and on top of the underlayer, a heat-sensitive recording layer with a dry weight of 3 g / m was applied and dried (using a forced-air dryer at 60°C for 2 minutes) to form a heat-sensitive recording layer. Then, the support with the underlayer and the heat-sensitive recording layer formed thereon was processed with a super calender to achieve a smoothness of 500 - 1000 seconds to obtain a heat-sensitive recording material. This was further smoothed with a super calender under a pressure of 1 kgf / cm 2 to obtain a heat-sensitive recording material. [[Example 3]] 2

[0056] For Example 3 The proportion of Liquid A <Liquid A> · Compound 1: 20.0 parts · Kraft lignin (derived from softwood): 20.0 parts​​​​​ · Polyvinyl alcohol (10% aqueous solution): 50.0 parts · Water: 10.0 parts A heat-sensitive recording material was produced in the same manner as in Example 2, except that it was changed to the above.

[0057] [Example 4] A heat-sensitive recording material was produced in the same manner as in Example 2, except that kraft lignin (derived from softwood) in Solution A was changed to enzymatically decomposed lignin (derived from corn cobs).

[0058] [Comparative Example 1] The proportion of Solution A was <Solution A> · Compound 1: 40.0 parts · Polyvinyl alcohol (10% aqueous solution): 50.0 parts · Water: 10.0 parts A heat-sensitive recording material was produced in the same manner as in Example 1, except that it was changed to the above.

[0059] [Comparative Example 2] The proportion of Solution A was <Solution A> · Compound 1: 40.0 parts · Polyvinyl alcohol (10% aqueous solution): 50.0 parts · Water: 10.0 parts A heat-sensitive recording material was produced in the same manner as in Example 2, except that it was changed to the above.

[0060] [Color Development Sensitivity Test] Printing of a tone pattern was performed using a thermal printer (TH-M2 / PS) manufactured by Okura Electric Co., Ltd., and the image density at an applied energy of 0.36 mJ / dot was measured with a spectrophotometer · Colorimeter (eXact) manufactured by X-Rite. The results are shown in Table 1. In this test, the higher the value of the image density, the better the color development sensitivity.

[0061] [Alcohol Resistance] ​​​An Okura Electric thermal printer (TH-M2 / PS) was used to measure the applied energy of 0.3 A thermal recording material printed with a checkerboard pattern at 6 mJ / dot was immersed in 25% ethanol water for 20 minutes. After leaving it at room temperature for 24 hours, the image density was measured using an X-Rite spectrodensitometer. The image retention rate after the test is shown in Table 1.

[0062] [Table 1] As is clear from the results in Table 1, Example 1 has a higher alcohol resistance than Comparative Example 1. The high image density was maintained even after the test.

[0063] [Table 2] Furthermore, as is clear from the results in Table 2, Examples 2 to 4 have a higher image quality in the printed area than Comparative Example 2. The image density has increased and the color sensitivity has improved. In addition, the image has high alcohol resistance even after the test. From the above, it can be seen that the developer described in the present application and the isolated lignin as an additive can effectively It can be seen that the use of , provides excellent alcohol resistance in durability tests.

[0064] As described above, the present invention provides a heat-sensitive recording material having excellent alcohol resistance. can.

Claims

1. A heat-sensitive recording material comprising a color developer represented by the following formula (1) and isolated lignin: 【Chemistry 1】 (In the above formula (1), a, A, and L are as follows: a is an integer selected from 1 to 5; Each A is independently a fluoro group or a perfluoroalkyl group; L is any functional group represented by the following formula (2). 【Chemistry 2】 In the above formula (2), R is an alkyl group having 1 to 4 carbon atoms. * indicates the bonding site with the sulfur atom in formula (1).

2. 2. The heat-sensitive recording material according to claim 1, wherein a is 1 or 2 in formula (1).

3. 3. The heat-sensitive recording material according to claim 1, wherein in formula (1), A is substituted at the m-position or p-position.

4. 4. The heat-sensitive recording material according to claim 3, wherein in formula (1), A is substituted at the m-position.

5. 5. The heat-sensitive recording material according to claim 3, wherein a is 1 in formula (1).

6. 6. The heat-sensitive recording material according to claim 1, wherein A in formula (1) is a fluoro group or a trifluoromethyl group.

7. 7. The heat-sensitive recording material according to claim 1, wherein in formula (1), L is selected from the group consisting of a phenyl group, an o-toluyl group, an m-toluyl group, and a p-toluyl group.

8. 8. The heat-sensitive recording material according to claim 1, wherein the isolated lignin is kraft lignin or enzymatically decomposed lignin.

9. The heat-sensitive recording material according to any one of claims 1 to 8, wherein the heat-sensitive recording material contains a sensitizer.

10. 10. The heat-sensitive recording material according to claim 1, wherein the weight ratio of the developer to the isolated lignin (developer / isolated lignin) is 40 / 60 to 90 / 10.

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