西班牙专利ES2673224T9 Record material using phenol compound

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公开号:ES2673224T9
申请号:ES11821298.4T
申请日:2011-08-29
公开日:2018-07-13
发明作者:Hiroshi Sakai；Shuntaro Kinoshita；Tadahiro Kondo；Kazumi Jyujyo
申请人:Nippon Soda Co Ltd；
IPC主号:

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DESCRIPTION
Record material using phenol compound Technical field
The present invention relates to a method for producing a heat or pressure sensitive recording material that uses color development caused by a reaction between a color former and a color developer.
Background
Registration materials that use color development caused by a reaction between a color former and a color developer are widely used as thermal registration paper for fax / printer output / recording, or as sensitive copy paper. the pressure to simultaneously make a plurality of copies of documents, or the like, because registration processing can be performed with said registration materials without performing complicated processing such as developing and fixing processing in a short period of time using a comparative device simple. It is desired that said registration materials quickly reveal color, retain whiteness in a part without color development (hereinafter referred to as "background") and obtain a color revealed image with high strength and, from the point of view of stability of Long-term storage, in particular an excellent recording material is required in terms of resistance to backlight. Therefore, various efforts have been made to develop a color former, color developer, stabilizer and the like, but a sufficiently satisfactory recording material well balanced in dynamic sensitivity, storage property for a background and a background has not yet been found. Image and the like.
Although 2,4'-dihydroxydiphenylsulfone and 4-hydroxy-4'-isopropoxydiphenylsulfone are conventionally known as excellent recording materials in their storage properties for a background, the background light resistance achieved by them has not yet It is satisfactory.
The present inventors have already proposed an excellent record material in light resistance of a background and using a cinnamic acid amide compound as a color developer (see patent document 1), but the crystal obtained from this compound is colored in yellow and therefore not satisfactory enough, and therefore, a practical registration material has not yet been achieved.
Prior art documents
Patent documents
Patent document 1: publication of Japanese unexamined patent application No. 2003-305959 Patent document 2: published international application WO 2010/089982 A1
Patent documents 1 and 2 describe certain phenol compounds of formula (I) and registration materials comprising said phenol compounds.
Summary of the invention
Objective to be solved by the invention
An object of the present invention is to provide a recording material or a recording sheet that is capable of improving the above-mentioned disadvantages of conventional recording materials, is excellent not only in the whiteness of a background but also in the storage property for a background and an image and have excellent dynamic sensitivity.
Means to achieve the objective
The present inventors have discovered that an excellent recording material can be obtained in the storage property for a background and an image and that it also has an excellent dynamic sensitivity using, as a color developer, the amide-based compound of the cinnamic acid previously found in which an amide group and a hydroxyl group are prepared to be located in ortho positions, and have also found that the color of the crystal obtained, that is, a fatal defect, can be avoided in this way, resulting in the achievement of the present invention, relating to a developer of excellent color in the whiteness of a background.
Specifically, the present invention relates to:
(1) a method of producing a phenol compound represented by Formula (I):
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image 1
wherein R1 represents a hydroxyl group, a halogen atom, a C1-C6 alkyl group or a C-C6 alkoxy group, p represents 0 or an integer from 1 to 5, R2 and R3 each independently represent an atom of hydrogen or a C1-C6 alkyl group, R4 represents a hydrogen atom, a C1-C6 alkyl group, an optionally substituted phenyl group or an optionally substituted benzyl group; and a bond shown with a wavy line represents the E or Z form, or a mixture thereof, in which the phenol compound has a color space b * of 10 or less;
method comprising reacting a compound represented by formula (II) purified by reduction purification using a reducing agent:
image2
with a compound represented by the formula (III):
image3
in which R1 to R4 and p have the same meaning as defined in Formula (I) above, and in which X represents a hydroxyl group or a halogen atom, in the presence of a base, followed by crystallization,
(2) the method of producing a phenol compound according to (1), wherein the phenol compound represented by the formula (I) has a Hunter brightness of 75 or more,
(3) the method for producing a phenol compound according to (1) or (2), wherein the compound represented by formula (II) is a compound purified by reduction purification using at least one reducing agent selected from sulfite, thiosulfate, dithionite, hydrazine, metal halide salt and boron compound.
(4) the method of producing a phenol compound according to any one of (1) to (3), wherein the reductant is at least one selected from sodium sulphite, potassium sulphite, sodium thiosulfate, sodium thiosulfate potassium, sodium hydrosulfite and its hydrates, potassium hydrosulfite and its hydrates, tin dichloride and sodium borohydride,
(5) the method of producing a phenol compound according to any one of (1) to (4), wherein the base is at least one weak alkaline inorganic compound selected from sodium carbonate, sodium hydrogen carbonate, sodium carbonate potassium, potassium hydrogen carbonate, ammonium carbonate and ammonium hydrogen carbonate,
(6) the method of producing a phenol compound according to any one of (1) to (5), in which the crystallization is performed using a polar solvent as the crystallization solvent.
Brief description of the drawings
[Figure 1] Figure 1 is a diagram illustrating the results of the test examples for dynamic sensitivity.
Embodiment of the invention
(Phenol compound represented by Formula (I))
Next, a phenol compound represented by Formula (I) will be described.
In Formula (I), R1 represents a hydrogen atom; a halogen atom such as a fluorine atom, a
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chlorine atom, a bromine atom or an iodine atom; a linear, branched or cyclic C1-C6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl, cyclopropyl, cyclobutyl, 2-methylcyclo -propyl, cyclopropylmethyl, cyclopentyl or cyclohexyl; or a linear, branched or cyclic C1-C6 alkoxy group such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy, cyclopropoxy, cyclobutoxy, 2-methylcyclopropoxy, cyclopropylmetho cyclopentyloxy or cyclohexyloxy, and preferably represents a hydrogen atom.
R2 and R3 each independently represent a hydrogen atom; or a linear, branched or cyclic C1-C6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl, cyclopropyl, cyclobutyl, 2- methylcyclopropyl, cyclopropylmethyl, cyclopentyl or cyclohexyl, and each preferably represents a hydrogen atom.
R4 represents a hydrogen atom; a linear, branched or cyclic C1-C6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl, cyclopropyl, cyclobutyl, 2-methylcyclopropyl , cyclopropylmethyl, cyclopentyl or cyclohexyl; an optionally substituted phenyl group; or an optionally substituted benzyl group.
In this case, examples of a substituent for an "optionally substituted group" are a hydroxyl group; halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; C1-C6 alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, a isopentyl group, a neopentyl group, a t-pentyl group, an n-hexyl group, an isohexyl group, a 1-methylpentyl group and a 2-methylpentyl group; and C1-C6 alkoxy groups such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group and a t-butoxy group.
Incidentally, the compound represented by Formula (I) has geometric isomers as shown below, and depending on the reaction conditions and the purification method, in some cases only one isomer is obtained and in others a mixture of isomers is obtained. . All these isomers are encompassed within the scope of the present invention.
image4
A typical example of the compound represented by Formula (I) is N- (2-hydroxyphenyl) -cinnamoylamide.
(Production method for the phenol compound represented by Formula (I))
The compound represented by Formula (I) can be obtained by a reaction of a purified compound represented by Formula (II):
image5
[in which R4 has the same meaning as defined in Formula (I) mentioned above] with a compound represented by Formula (III):
image6
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[wherein R1 to R3 and p have the same meaning as defined in Formula (I) mentioned above, and X represents a hydroxyl group or a halogen atom] in an organic solvent in the presence of a base.
In this case, the examples of the halogen atom are the same as those defined with respect to R1 in the Formula (I) mentioned above.
The organic solvent is not particularly limited to the extent that it is inert to the compound represented by Formula (II) or Formula (III), and examples of the organic solvent are alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, nitriles such as acetonitrile, ethers such as tetrahydrofuran and dioxane, and amides such as N, N-dimethylformamide and N, N-dimethylacetamide. Alternatively, a solvent mixed with water can be used. Preferably, a solvent mixture of acetone-water is used.
The base is not particularly limited, and examples of the base are organic bases such as pyridine and triethylamine, and weak alkaline inorganic compounds such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, ammonium carbonate and ammonium hydrogen carbonate. Preferably, sodium hydrogen carbonate is used.
In reaction with the compound represented by Formula (III), it can be dissolved in the solvent as a previous step or it can be used as is. In addition, it can be added intermittently little by little or added dropwise, but since the reaction is an exothermic reaction, it is not preferable to add the compound at once because heat is generated immediately.
The structure of the compound represented by Formula (I) can be attributed by NMR or the like and its purity can be calculated by liquid chromatography, gas chromatography or the like.
(Requirements to obtain the phenol compound represented by Formula (I) which has a high whiteness)
In the production of a compound represented by Formula (I) (hereinafter, the amide-based compound of cinnamic acid), even when it was confirmed by various analyzes that include gas chromatography that a compound represented by Formula (II ) (hereinafter, the 2-aminophenol compound) had a high purity, the amide-based compound of cinnamic acid in some cases was colored. In addition, an amide-based compound of the cinnamic acid produced using a 2-aminophenol compound that had been stored for a long period of time was also colored. In addition, an amide-based compound of cinnamic acid was colored when stored for a long period of time, although it was not colored immediately after production. The cause of such coloration was seriously studied, which resulted in the finding that there are three requirements to obtain an amide-based compound of uncolored cinnamic acid.
(First requirement)
The first requirement is to purify a 2-aminophenol compound. This purification can be performed specifically by a method described in "Purification method for the 2-aminophenol compound" described below.
(Second requirement)
By reacting a 2-aminophenol compound and any of the compounds represented by Formula (III) (hereinafter referred to as cinnamic acids), not only is an amide-based compound of cinnamic acid but also an HX byproduct. When X is a halogen compound, HX is an acidic substance. HX can form a salt together with an amino group of the 2-aminophenol compound. The amino group that has formed the salt is difficult to react with cinnamic acids. Therefore, it is necessary to trap the HX byproduct with an alkaline compound. Like this alkaline compound, the 2- aminophenol compound can be used. However, in this case, since the 2-aminophenol compound is necessary for the reaction in a molar amount of twice or more of the amide-based compound of the cinnamic acid, simply as a result, half or less of the compound is reacted. 2-aminophenol used, and therefore, the use of this compound for this purpose is economically inappropriate.
Therefore, the excessive amount of the 2-aminophenol compound can be replaced by a low cost alkaline inorganic compound. However, when a strong alkaline inorganic compound such as sodium hydroxide is used, the raw material compound discolors undesirably. Accordingly, the second requirement is to use a weak alkaline inorganic compound as an alkaline inorganic compound. Examples of the weak alkaline inorganic compound are sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, ammonium carbonate and ammonium hydrogen carbonate.
(Third requirement)
The third requirement is to use a polar solvent as a crystallization solvent, and in addition, wash the obtained crystal with a polar solvent, water or a solvent mixture of a polar solvent and water. As a process by way of
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specific example for crystallization, a polar solvent and water are added to an amide-based compound of the cinnamic acid prepared and dissolved by heating once, the resulting solution is cooled to separate the crystal and the crystal is sufficiently washed with water. Examples of the polar solvent are alcohols such as methanol and ethanol, ketones such as acetone and nitriles such as acetonitrile. Alternatively, the crystallization solvent may be a solvent mixture of a polar solvent and water. In addition, crystallization is preferably performed using water that has been acidified by a mineral acid such as hydrochloric acid. In addition, before the crystallization process, processing can be performed to add an organic solvent separable from water and water (or water that has been acidified by a mineral acid such as hydrochloric acid) and the separation of an aqueous layer. However, in the case of using a solvent mixture of a polar solvent and a non-polar solvent, a high proportion of the non-polar solvent is not preferable because the dye component or the component causing the coloration cannot be removed.
Between these first and third requirements, it is always necessary to satisfy the first requirement, but the second and third requirements must not always be met, but preferably they are satisfied. However, in the event that none of the requirements are met, an amide-based compound of the prepared cinnamic acid is colored or acquires color when stored for a long period of time, even when it is not colored immediately after production. Therefore, a compound represented by Formula (I) that does not color for a long period of time cannot be obtained until these requirements are met.
(Purification method for the 2-aminophenol compound)
A 2-aminophenol (o-aminophenol) compound used as the raw material for an amide-based compound of cinnamic acid can be purchased as a purified product or can be obtained by purifying a purchased unpurified product. The purification method is not particularly limited, but purification such as reduction purification, sublimation purification, recrystallization purification, silica gel separation purification or the like, elimination purification by adsorption with activated carbon or the like, or separation purification by separation of an organic solvent and water to obtain a purified 2-aminophenol compound.
The reductant used in purification is not particularly limited, and examples of the reductant are sulphites such as sodium sulphite and potassium sulphite, thiosulfates such as sodium thiosulfate and potassium thiosulfate, dithionites such as sodium hydrosulphite, potassium hydrosulphite and its hydrates, hydrazine, metal halide salts such as tin dichloride and boron compounds such as sodium borohydride.
In order to obtain an amide-based compound of cinnamic acid with high whiteness, it is preferable not only to use a purified 2-aminophenol compound as described above, but also to wash the prepared glass under acidic conditions after producing the compound. based on amide of cinnamic acid.
The acid to be used to achieve the acidic condition is not particularly limited, and acids such as hydrochloric acid, sulfuric acid or phosphoric acid can be used, among which hydrochloric acid is preferably used.
Examples of a method to achieve the acid condition are a method in which an acid is added after completion of the reaction, a method in which an acid is added before separating the crystal and a method in which an acid solvent is used. to wash the crystal, among which the method in which an acid is added after completion of the reaction is preferably used.
The amount of acid is not particularly limited and may be an amount sufficient to reach the acidic condition.
Purification to remove a colored substance can be performed, but not limited to, one or both of a method in which a 2-aminophenol compound used as a raw material is purified and a method in which a compound based on a cinnamic acid amide. By employing a method in which an unpurified 2- aminophenol is used as the raw material and the amide-based compound is purified from the resulting cinnamic acid, recrystallization purification alone is not sufficient and therefore it is necessary to employ a combination of a plurality of purification methods. Preferably, the 2-aminophenol compound is purified by reduction using a reductant and the crystal of the cinnamic acid amide-based compound is washed under acidic conditions.
(Measured values for whiteness and the like)
A color developer is applied on a substrate such as paper together with a color former and the like, and the resulting one is used as thermal recording paper. Thermal registration paper is required, as a product, to be whiter before color development. Therefore, the color developer is required to be whiter. In addition, the degree of white color can be measured with a spectrophotometer. A typical value measured for whiteness is indicated by Hunter's brightness (a W value). In addition, color spaces can be indicated based on JIS Z 8729 using the color system L * a * b * (such as L *, a * and b *).
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An excellent color developer is preferred in whiteness and in particular the color spaces a * and b *. Specifically, a Hunter brightness of 75 or more is sufficient and in practice 79 or more is preferable. In addition, a color space a * in a range of -5 or more and 0 or less is sufficient and in practice a range of -3 or more and 0 or less is preferable, and a color space b * is sufficient in a range of 0 or more and 10 or less and in practice a range of 0 or more and 8 or less is preferable.
Whiteness is indicated by Hunter's brightness (a value of W).
Hunter's brightness, the color spaces L *, a * and b * can be measured as follows:
A sample is filled in an accessory cell for dust measurement of a spectrophotometer (SD 5000 or SE 2000, manufactured by Nippon Denshoku Industries, Co., Ltd.) so that it does not transmit light, and the measurement is performed in a atmosphere at room temperature with a measuring diameter set to 28 mm.
(Registration material)
A recording material may be used to the extent that it comprises a color former and at least one phenol compound represented by Formula (I), and may be used, for example, as thermal registration material, sensitive copy material. Pressure and the like.
A usage ratio of the compound represented by Formula (I) to the color former is generally 0.01 to 10 parts by mass, preferably 0.5 to 10 parts by mass and more preferably 1.0 to 5 parts by weight. mass based on 1 mass part of the color former.
(Other components of the registration material)
The recording material may comprise, if necessary, in addition to the color former and the compound represented by Formula (I), one or more of the known color developers, image stabilizers, sensitizers, fillers, dispersants, antioxidants, desensitizers , non-stick agents, anti-foam agents, light stabilizers, fluorescent brightening agents and the like. The content of each of these other components generally ranges from 0.1 to 15 parts by mass and preferably from 1 to 10 parts by mass based on 1 part by mass of the color former.
These agents can be included in a color developing layer, and when the recording material has a multilayer structure, they can be included in an arbitrary layer, for example, in a protective layer. Particularly when a coating layer or a primer layer is provided above and / or below the color developing layer, such layers may include an antioxidant, a light stabilizer or the like. In addition, if necessary, an antioxidant and a photo stabilizer can be included in said layer in a state encapsulated in a microcapsule.
Examples of the color former used in a recording material are leuco dyes such as fluorine-based, phthalate-based, lactam-based, triphenylmethane-based, phenocyanine-based and spiropyran-based dyes. The color former is not limited to these colorants, but any color former can be used to the extent that it reveals a color when it comes in contact with a color developer that is an acidic substance. In addition, it goes without saying that one of these color formers can be used individually to produce a color registration material revealed by the used color former, or a mixture of two or more of them can be used. For example, a mixture of three color primary colors of red, blue and green may be used or a black color former may be used to produce a recording material to reveal a true black color.
Examples of the fluoran-based color former are 3,3-bis (p-dimethylaminophenyl) -phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (with another name of lactone violet crystal), 3,3- bis (p-dimethylaminophenyl) -6- diethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) -6-chlorophthalamide, 3,3-bis (p-dibutylaminophenyl) -phthalide, 3-cyclohexylamino-6- chlorofluorane, 3-dimethylamino -5,7-dimethylfluorane, 3-N-methyl-N-isopropylamino-6-methyl-7-anilinofluorane, 3-N-methyl-N-isobutylamino-6-methyl-7-anilinofluorane, 3-N-methyl-N -isoamylamino-6-methyl-7-anilinofluoran, 3-diethylamino-7- chlorofluoran, 3-diethylamino-6,8-dimethylfluoran, 3-diethylamino-7-methylfluoran, 3-diethylamino-7,8-benzofluoran, 3- diethylamino -6-methyl-7-chlorofluoran, 3-dibutylamino-6-methyl-7-bromofluoran, 3- (Np-tolyl-N-ethylamino) -6-methyl-7- anilinofluoran, 3-pyrrolidino-6-methylamino-7 -anilinofluorane, 2- {N- (3'-trifluoromethylphenyl) amino} -6-diethylaminofluorane, 2- {3,6-bis (diethylamino) -9- (o-chloroanilino) xanthyl} ben zoic, 3-diethylamino-6-methyl-7- (m-trichloromethylanilino) fluoran, 3-diethylamino-7- (o-chloroanilino) fluoran, 3-dibutylamino-7- (o-chloroanilino) fluoran, 3-N-methyl -N-amylamino-6-methyl-7-anilinofluoran, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6- methyl-7-anilinofluorane, 3-diethylamino-6-methyl -7- (2 ', 4'-dimethylanilino) fluoran, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluoran, 3- (N, N-diethylamino) -7 - (N, N-dibenzylamino) fluoran, 3- (N-ethyl-N-isobutylamino) -6-methyl-7- anilinofluoran, 3- (N-ethyl-N-propylamino) -6-methyl-7-anilinofluorane, 3- (N-methyl-N-propylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isopentylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-toluidino ) -6-methyl-7-anilino-fluorano, 3-pyrrolidino-6- methyl-7-anilinofluorano, 3-piperidino-6-methyl-7-anilinofluorano, 3-dimethylamino-7- (m-trifluoromethylanilino) fluorano, 3 -
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dipentylamino-6-methyl-7-anilinofluoran, 3- (N-ethoxypropyl-N-ethylamino) -6-methyl-7-anilinofluoran, 3-dibutylamino-7- (o-fluoroanilino) fluoran, 3-diethylaminobenzo [a] fluoran , 3-diethylamino-5-methyl-7-benzylaminofluorane, 3-diethylamino-5- chlorofluoran, 3-diethylamino-6- (N, N'-dibenzylamino) fluoran, 3,6-dimethoxyfluorane, 2,4-dimethyl-6 - (4- dimethylaminophenyl) aminofluorane, 3-diethylamino-7- (m-trifluoromethylanilino) fluoran, 3-diethylamino-6-methyl-7-
octylaminofluorane, 3-diethylamino-6-methyl-7- (m-tolylamino) fluoran, 3-diethylamino-6-methyl-7- (2,4-xylamino) fluoran, 3- diethylamino-7- (o-fluoroanilino) fluoran , 3-diphenylamino-6-methyl-7-anilinofluoran,
Benzoyl leuco methylene blue, 6'-chloro-8'-methoxy-benzoindolino-spiropyran, 6'-bromo-3'-methoxy-benzoindolino-spiropyran, 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2'-Methoxy-5'-chlorophenyl) phthalide, 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2'-methoxy-5'-nitrophenyl) phthalide, 3- (2'-hydroxy- 4'-diethylaminophenyl) -3- (2'-methoxy-5'-methylphenyl) phthalamide, 3- (2'-methoxy-4'-dimethylaminophenyl) -3- (2'-hydroxy-4'-chloro-5 ' -methylphenyl) phthalide, 3-morphoreino-7- (N-propyl-trifluoromethylanilino) fluoran, 3- pyrrolidino-7-trifluoromethylanilinofluorane, 3-diethylamino-5-chloro-7- (N-benzyl-trifluoromethylanilino) fluoran, 3-pyrrolidino -7- (di-p-chlorophenyl) methylaminofluorane, 3-diethylamino-5-chloro-7- (a-phenylethylamino) fluoran, 3- (N-ethyl-p-toluidino) -7- (a-
phenylethylamino) fluoran, 3-diethylamino-7- (o-methoxycarbonylphenylamino) fluoran, 3-diethylamino-5-methyl-7- (a-
phenylethylamino) fluoran, 3-diethylamino-7-piperidinofluorane, 2-chloro-3- (N-methyltoluidino) -7- (pn-butylanilino) fluoran, 3- (N-methyl-N-isopropylamino) -6-methyl-7 -anilinofluorano, 3-dibutylamino-6-methyl-7-anilinofluorano, 3-dipentilamino-6-methyl- 7-anilinofluorano, 3,6-bis (dimethylamino) fluorenespiro (9,3 ') - 6'-dimethylaminophthalamide, 3- (N-benzyl-N-cyclohexylamino) -5,6- benzo-7-a-naphthylamino-4'-bromofluoran, 3-diethylamino-6-chloro-7-anilinofluorane, 3-N-ethyl-N- (2- ethoxypropyl) amino-6- methyl-7-anilinofluoran, 3-N-ethyl-N-tetrahydrofurfurylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-mesitidino- 4 ', 5'-benzofluoran, and 3- (N-ethyl-p-toluidino) -7- (methylphenylamino) fluoran.
Among these color formers, 3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- cyclohexylamino-6-chlorofluoran, 3-diethylamino-7-chlorofluoran, 3-diethylamino-6,8-dimethylfluorane, 3- are preferred diethylamino-7- methylfluorane, 3-diethylamino-7,8-benzofluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-dibutylamino-5-methyl-7- bromofluoran, 3-diethylamino-7- (o-chloroanilino ) fluoran, 3-dibutylamino-7- (o-chloroanilino) fluoran, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluoran, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluoran, 3- (N, N-diethylamino) -7- (N, N-dibenzylamino) fluoran, 3- (N-ethyl-N-isobutylamino) -6-methyl-7-anilinofluorane, 3- (N-methyl-N-
propylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isopentylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-toluidino) -6-methyl-7-anilino -fluorane, 3- (N-ethoxypropyl-N-ethylamino) -6-methyl-7-anilinofluorane, 3-dibutylamino-7- (o-
fluoroanilino) fluorano, 3-diethylamino-7- (m-trifluoromethylanilino) fluorano, 3-diethylamino-6-methyl-7-octylaminofluorane, 3- diethylamino-6-methyl-7- (m-tolylamino) fluoran, 3-diethylamino- 7- (o-fluoroanilino) fluoran, 3-diphenylamino-6-methyl-7-
anilinofluoran, benzoyl leuco methylene blue, 3-dibutylamino-6-methyl-7-anilinofluoran, 3-N-ethyl-N-tetrahydrofurfurylamino-6-methyl-7-anilinofluoran and 3- (N-ethyl-p-toluidino) - 7- (methylphenylamino) fluoran.
Examples of a near-infrared absorbent dye are 3- [4- [4- (4-anilino) -anilino] anilino] -6-methyl-7- chlorofluoran, 3,3-bis [2- (4-dimethylaminophenyl) -2- (4-methoxyphenyl) vinyl] -4,5,6,7-tetrachlorophthalamide, and 3,6,6'-tris
(dimethylamino) spiro (fluorene-9,3'-phthalide).
The compound represented by Formula (I) can be suitably used as a color developer primarily for a thermal recording material, and the compound can be used alone or can be used in combination with a plurality of known color developers. In this case, a relationship between them is arbitrary.
Specific examples of other color developers are:
bisphenol compounds such as bisphenol A, 4,4'-sec-butylidenebisphenol, 4,4'-cyclohexylidenebisphenol, 2,2'-bis (4- hydroxyphenyl) -3,3'-dimethylbutane, 2,2'-dihydroxydiphenyl, pentamethylene -bis (4-hydroxybenzoate), 2,2-dimethyl-3,3-di (4- hydroxyphenyl) pentane, 2,2-di (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4 '- (1-phenylethylidene) bisphenol, 4,4'-ethylidenebisbisol, (hydroxyphenyl) methylphenol, 2,2'-bis (4-hydroxy -3-phenyl-phenyl) propane, 4,4 '- (1,3-phenylenediisopropylidene) bisphenol, 4,4' - (1,4-
phenylenedisopropylidene) bisphenol and 2, 2-bis (4-hydroxyphenol) butyl acetate; sulfur-containing bisphenol compounds, such as 4,4'-dihydroxy diphenylthioether, 1,7-di (4-hydroxyphenylthio) 3,5-dioxaheptane, 2,2'-bis (4- hydroxyphenylthio) diethyl ether and 4,4'-dihydroxy -3,3'-dimethyldiphenylthioether; esters of 4-hydroxybenzoic acid such as benzyl 4- hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, isopropyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, isobutyl 4-hydroxybenzoate, 4-hydroxybenzyl 4-hydroxybenzoate 4- methylbenzyl hydroxybenzoate and diphenylmethyl 4-hydroxybenzoate; metal salts of benzoic acid such as zinc benzoate and zinc 4-nitrobenzoate; Salicylic acids such as 4- [2- (4-methoxyphenyloxy) ethyloxy] salicylic acid; salts of salicylic acid metals such as zinc salicylate and zinc bis [4- (octyloxycarbonylamino) -2-hydroxybenzoate]; hydroxysulfones such as 4,4'-dihydroxydiphenylsulfone, 2,4'-dihydroxydiphenylsulfone, 4- hydroxy-4'-methyldiphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-4'-butoxyphenylsulfone, 4,4'-dihydroxy 3,3'dialyldiphenylsulfone, 3,4-dihydroxy-4'-methyldiphenylsulfone, 4,4'-dihydroxy-3,3 ', 5,5'-tetrabromodiphenylsulfone, 4-allyloxy-4'-hydroxy diphenylsulfone, 2- (4- hydroxyphenylsulfonyl) phenol, 4,4'-sulfonylbis [2- (2-propenyl)] phenol, 3 - [{4- (propoxy) phenyl} sulfonyl] phenol, 4 - [{4- (allyloxy) phenyl} sulfonyl] phenol , 4 - [{4- (benzyloxy) phenyl} sulfonyl] phenol and 2,4-bis (phenylsulfonyl) -5-methylphenol; salts of multivalent hydroxysulfone metals such as 4-phenylsulfonylphenoxy zinc, 4-phenylsulfonylphenoxy magnesium, 4-phenylsulfonylphenoxy aluminum and 4-phenylsulfonylphenoxy titanium; diesters of 4-hydroxyphthalic acid such as dimethyl 4-hydroxyphthalate, dicyclohexyl 4-hydroxyphthalate and diphenyl 4-hydroxyphthalate; esters of hydroxynaphthoic acid such as 2-hydroxy-6-carboxynaphthalene; trihalomethylsulfones such as
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tribromomethylphenylsulfone; sulfonylureas such as 4,4′-bis (p-toluenesulfonylaminocarbonylamino) diphenylmethane and N- (4-methylphenylsulfonyl) -N '- (3- (4-methylphenylsulfonyloxy) phenyl) urea; hydroxyacetophenone, p-phenylphenol, 4- benzyl hydroxyphenylacetate, p-benzylphenol, hydroquinonemonobenzyl ether, 2,4-dihydroxy-2'-methoxybenzanilide, tetracyanoquinodimethanes, N- (2-hydroxyphenyl) -2 - [(4-hydroxyphenyl) ] acetamide, N- (4-hydroxyphenyl) -2 - [(4-hydroxyphenyl) thio] acetamide, 4-hydroxybenzenesulfoanilide, 4'-hydroxy-4-methylbenzenesulfonanilide, 4,4'-bis (4-methyl-3-
phenoxycarbonyl) aminophenylureide)) diphenylsulfone, 3- (3-phenylureide) benzenesulfonanilide, octadecyl phosphate, dodecyl phosphate; and diphenylsulfone crosslinking compounds represented by the following formula, and a mixture thereof:
image7
(b represents an integer from 0 to 6)
Among these exemplified substances, the preferable examples are 4-hydroxy-4’-isopropoxydiphenylsulfone, diphenylsulfone crosslinking compounds and a mixture thereof.
Examples of the image stabilizer are diphenylsulfones containing epoxy groups such as 4-benzyloxy-4 '- (2- methylglycidyloxy) -diphenylsulfone and 4,4'-diglycidyloxydiphenylsulfone; 1,4-diglycidyloxybenzene, 4- [a- (hydroxymethyl) benzyloxy] -4'-hydroxydiphenylsulfone, a derivative of 2-propanol, a derivative of salicylic acid and a metal salt (especially zinc salts) of a derivative of oxynaphthoic acid , a 2,2-methylenebis (4,6-t-butylphenyl) phosphate metal salt, other water insoluble zinc compounds, hindered phenol compounds such as 2,2-bis (4'-hydroxy-3 ', 5 '- dibromophenyl) propane, 4,4'-sulfonylbis (2,6-dibromophenol), 4,4'-butylidene (6-t-butyl-3-methylphenol), 2,2'-methylene-bis (4- methyl) -5-t-butylphenol), 2,2'-methylene-bis (4-ethyl-6-t-butylphenol), 2,2'-di-t-butyl-5,5'-dimethyl-4,4 ' -sulfonyldiphenol, 1, 1,3-tris (2- methyl-4-hydroxy-5-cyclohexylphenyl) butane and 1, 1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, compounds Phenolic novolac and epoxy resins.
It is noted that the image stabilizer is preferably in a solid state at normal temperature, and a compound having a melting point of 60 ° C or more and dissolving minimally in water is particularly preferable.
Examples of the sensitizer are higher fatty acid amides such as stearic acid amide, stearic acid anilide and palmitic acid amide; amides such as benzamide, acetoacetanilide, acrylic thioacetanilide acid amide, ethylenebisamide, ortho-toluenesulfonamide and para-toluenesulfonamide; diesters of phthalic acid such as dimethyl phthalate, dibenzyl isophthalate, dimethyl isophthalate, dimethyl terephthalate, diethyl isophthalate, diphenyl isophthalate and dibenzyl terephthalate; diesters of oxalic acid such as dibenzyl oxalate, di (4-methylbenzyl) oxalate, di (4-chlorobenzyl) oxalate, a mixture of equal volume of benzyl oxalate and di (4-chlorobenzyl) oxalate, and a mixture of di (4-chlorobenzyl) oxalate and di (4-methylbenzyl) oxalate; bis (t-butylphenols) such as 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 4,4'-methylene-bis-2,6-di-t-butylphenol; 4,4'-dihydroxydiphenylsulfone diesters such as 4,4'-dimethoxydiphenylsulfone, 4,4'-diethoxydiphenylsulfone, 4,4'-dipropoxydiphenylsulfone, 4,4'-diisopropoxydiphenylsulfone, 4,4'-dibutoxydiphenylsulfone, 4,4' diisobutoxydiphenylsulfone, 4,4'-dipentyloxyidiphenylsulfone, 4,4'-dihexyloxydiphenylsulfone and 4,4'-diallyloxydiphenylsulfone; 2,4'-dihydroxydiphenylsulfone diesters such as 2,4'-dimethoxydiphenylsulfone, 2,4'-diethoxydiphenylsulfone, 2,4'-dipropoxydiphenylsulfone, 2,4'-diisopropoxyphenylsulfone, 2,4'-dibutoxydiphenylsulfone, 2,4'- diisobutoxydiphenylsulfone, 2,4'-dipentyloxydiphenylsulfone, 2,4'-dihexyloxydiphenylsulfone and 2,4'-diallyloxydiphenylsulfone;
1.2-bis (phenoxy) ethane, 1,2-bis (4-methylphenoxy) ethane, 1,2-bis (3-methylphenoxy) ethane, 1,2-bis (phenoxymethyl) benzene, 1,2-bis (4- methoxyphenylthio) ethane, 1,2-bis (4-methoxyphenoxy) propane, 1,3-phenoxy-2-propanol, 1,4-diphenylthio-2-butene, 1,4-diphenylthiobutane, 1,4-diphenoxy-2- butene, 1,5-bis (4-methoxyphenoxy) -3-oxapentane, 1,3-dibenzoyloxypropane, dibenzoyloxymethane, 4,4'-ethylenedioxy-bis-benzoic acid dibenzyl ester, bis- [2- (4-methoxyphenoxy) ) ethyl] ether, 2- naphthylbenzyl ether, 1,3-bis (2-vinyloxyethoxy) benzene, 1,4-diethoxynaphthalene, 1,4-dibenzyloxynaphthalene, 1,4-dimethoxynaphthalene, 1,4-bis (2-vinylxyethoxy) benzene, p- (2-vinyloxyethoxy) biphenyl, p-aryloxybiphenyl, p-propargiloxybiphenyl, p-benzyloxybenzyl alcohol, 4- (m-methylphenoxymethyl) biphenyl, 4-methylphenyl-biphenyl ether, di-p-naphthylphenylenediamine, 2,3-di-m-tolylbutane, 4-benzylbiphenyl, 4,4'-dimethylbiphenyl,
terphenyls such as m-terphenyl and p-terphenyl;
1,2-bis (3,4-dimethylphenyl) ethane, 2,3,5,6-tetramethyl-4'-methyldiphenylmethane, 4-acetylbiphenyl, dibenzoylmethane, triphenylmethane, phenyl 1-hydroxy-naphthoate, 1-hydroxy-2-naphthoate methyl, N-octadecylcarbamoyl-p-methoxycarbonylbenzene, benzyl benzyloxybenzoate, phenyl p-naphthoate, methyl p-nitrobenzoate, diphenylsulfone, carbonic acid derivatives such as diphenyl carbonate, guaiacol carbonate, di-p carbonate -tolyl and phenyl-a-naphthyl carbonate;
1,1-diphenylpropanol, 1,1-diphenylethanol, N-octadecylcarbamoylbenzene, dibenzyldisulfide, stearic acid and Amide AP-1 (a 7: 3 mixture of stearic acid amide and palmitic acid amide),
stearates such as aluminum stearate, calcium stearate and zinc stearate; zinc palmitate, behenic acid, zinc behenate, montanic acid wax and polyethylene wax.
Preferable examples are 2-naphthylbenzyl ether, m-terphenyl, 4-benzylbiphenyl, benzyl oxalate, di (4- chlorobenzyl) oxalate, a mixture of equal volume of benzyl oxalate and di (4-chlorobenzyl) oxalate, oxalate of di (4-
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methylbenzyl), a mixture of equal volume of di (4-dorobenzyl) oxalate and di (4-methylbenzyl) oxalate, phenyl 1-hydroxy-2-naphthoate, 1,2-bis (phenoxy) ethane, 1,2 -bis (3-methylphenoxy) ethane, 1,2-bis (phenoxymethyl) benzene, dimethyl terephthalate, stearic acid amide, Amide AP-1 (a 7: 3 mixture of stearic acid amide and palmitic acid amide), diphenylsulfone and 4-acetylbiphenyl.
More preferable examples are di (4-methylbenzyl) oxalate, 1,2-bis (3-methylphenoxy) ethane, 1,2-bis (phenoxymethyl) benzene, diphenylsulfone and 2-naphthylbenzyl ether.
Examples of the charge are silica, clay, kaolin, cooked kaolin, talc, satin white, aluminum hydroxide, calcium carbonate, magnesium carbonate, zinc oxide, titanium oxide, barium sulfate, magnesium silicate, aluminum silicate , a plastic pigment, diatomite, talc and aluminum hydroxide. Among these examples, cooked kaolin and calcium carbonate are suitably used. The charge is included in a content of 0.1 to 15 parts by mass and preferably 1 to 10 parts by mass based on 1 part by mass of the color former. In addition, a mixture of the charges described above can be used.
Examples of the dispersant are polyvinyl alcohol; polyvinyl alcohols of various degrees of saponification and degrees of polymerization such as acetoacetylated polyvinyl alcohol, carboxy-denatured polyvinyl alcohol, sulfonic acid denatured polyvinyl alcohol, amide denatured polyvinyl alcohol and butyral denatured polyvinyl alcohol; cellulose derivatives such as methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, ethyl cellulose, acetyl cellulose and hydroxymethyl cellulose; sodium polyacrylate, polyacrylic acid ester, polyacrylamide, starch, sulphosuccinic acid esters such as dioctyl sulfosuccinate, sodium dodecylbenzenesulfonate, lauryl alcohol sodium salt, sulfuric acid ester, a fatty acid salt, a styrene copolymer- maleic anhydride, a styrene-butadiene copolymer, polyvinyl chloride, polyvinyl acetate, polyacrylic acid ester, polyvinylbutyral, polyurethane, polystyrene and copolymers thereof, a polyamide resin, a silicone resin, a petroleum resin, a terpene resin, a ketone resin and a coumarone resin.
The dispersant can be dissolved in a solvent such as water, alcohol, ketone, ester or hydrocarbon for use, or it can be dispersed in water or another solvent in emulsion or paste state for use.
Examples of the antioxidant are 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-propylmethylenebis (3-methyl -6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4'-thiobis (2-t-butyl-5-methylphenol), 1,1,3- tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 4- {4- [1,1 - bis (4- hydroxyphenyl) ethyl] -a, a-dimethylbenzyl} phenol, 1,3,3-tris (2-methyl-4-hydroxy) -5-cyclohexylphenyl) butane, 2,2'-methylenebis (6-tert) - butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol), 1,3,5- tris [{4- (1,1-dimethylethyl) -3-hydroxy-2,6-dimethylphenyl} methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and 1 , 3,5-tris [{3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl} methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione .
Examples of the desensitizing agent are a higher fatty alcohol, polyethylene glycol and a guanidine derivative.
Examples of the non-stick agent are stearic acid, zinc stearate, calcium stearate, carnauba wax, paraffin wax and ester wax.
Examples of the antifoaming agent are anti-foaming agents based on denatured hydrocarbon and alcohol-based paraffin, based on fatty acid ester, oil based, silicone based, polyether based.
Examples of the light stabilizer are salicylic acid based UV absorbers such as phenyl salicylate, p-t-butylphenyl salicylate and p-octylphenyl salicylate; UV absorbers based on benzophenone, such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2 '-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone and bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane; benzotriazole-based UV absorbers such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ' , 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5' -di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole , 2- (2'-hydroxy-5 '- (1 ", 1", 3 ", 3" -tetramethylbutyl) phenyl) benzotriazole, 2- [2'-hydroxy-3'-
(3 ", 4", 5 ", 6" -tetrahydroftalimidomethyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-5'-t-octyl) phenyl) benzotriazole, 2- [2'-hydroxy-
3 ', 5'-bis (a, a-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (2'-hydroxy-3'-dodecyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 '- undecyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tridecyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy) 3'-tetradecyl-5'-methylphenyl) benzotriazole , 2- (2'-hydroxy-3'-pentadecyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-hexadecyl-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-4 '- (2 "-ethylhexyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-4' - (2" -ethylheptyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-4 '- (2 "-ethyloctyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-4 '- (2 "-propyloctyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-4' - (2" - propylheptyl) oxyphenyl] benzotriazole, 2- [2 '-hydroxy-4' - (2 "-propylhexyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-4 '- (1" -ethylhexyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-4' - ( 1 "-ethylheptyl) oxyphenylbenzotriazole, 2- [2'-hydroxy-4 '- (1'-ethyloctyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-4' - (1" -propyloctyl) oxyphenyl] benzotriazole, 2 - [2'-hydroxy-4 '- (1 "-propylheptyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-4 '- (1 "-propylhexyl) oxyphenyl] benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H -benzotriazol-2-
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il))] phenol and a condensate of polyethylene glycol and methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate; UV absorbers based on cyanoacrylate such as 2'-ethylhexyl-2-cyano-3,3-diphenyl acrylate and ethyl-2-cyano-3,3-diphenyl acrylate; UV absorbers based on hindered amines such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinic acid ester and 2- (3,5-di-t-butyl) bis (1,2,2,6,6-pentamethyl-4-piperidyl) malonic acid ester; and 1,8-dihydroxy-2-acetyl-3-methyl-6-methoxynaphthalene.
Examples of the fluorescent brightening agent are 4,4'-bis [2-anilino-4- (2-hydroxyethyl) amino-1,3,5-triazinyl-6- amino] stilbene-2,2'-disulfonic acid = salt disodium, 4,4'-bis [2-anilino-4-bis (hydroxyethyl) amino-1,3,5-triazinyl-6- amino] stilbene-2,2'-disulfonic acid = disodium salt, 4.4 acid '-bis [2-anilino-4-bis (hydroxypropyl) amino-1,3,5-triazinyl-6- amino] stilbene-2,2'-disulfonic acid = disodium salt, 4,4'-bis [2- methoxy-4- (2-hydroxyethyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2'-disulfonic acid = disodium salt, 4,4'-bis [2-methoxy-4- ( 2-hydroxypropyl) amino-1,3,5-triazinyl-6- amino] stilbene-2,2'-disulfonic acid = disodium salt, 4,4'-bis [2-m-sulfoanilino-4-bis (hydroxyethyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2'-disulfonic acid = disodium salt, 4- [2-p-sulfoanilino-4-bis (hydroxyethyl) amino-1,3,5- triazinyl-6- amino] -4 '- [2-m-sulfoanilino-4-bis (hydroxyethyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2'-disulfonic acid = tetrasodium salt, á 4,4'-bis [2-p-sulfoanilino-4-bis (hydroxyethyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2'-disulfonic acid = tetrasodium salt, 4.4 acid '-bis [2- (2,5-disulfoanilino) -4-phenoxyamino-1,3,5-triazinyl-6-amino] stilbene-2,2'-disulfonic acid = hexasodium salt, 4,4'-bis acid [2- (2,5-disulfoanilino) -4- (p-methoxycarbonylphenoxy) amino-1,3,5-triazinyl-6-amino] stilbene-2,2'-disulfonic acid = hexasodium salt, 4.4 'acid -bis [2- (p-sulfophenoxy) -4-bis (hydroxyethyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2'-disulfonic acid = hexasodium salt, 4,4'- acid bis [2- (2,5-disulfoanilino) -4-formalinylamino-1,3,5-triazinyl -6-amino] stilbene-2,2'-disulfonic acid = hexasodium salt and 4,4'-bis [2 - (2,5-disulfoanilino) -4-bis (hydroxyethyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2'-disulfonic acid = hexasodium salt.
(Method to produce record material)
When the present invention is applied to thermal registration paper, production can be carried out in the same manner as in a conventionally known method and, for example, thermal registration paper can be produced by dispersing particles of a compound described herein. and particles of a color former respectively in aqueous solutions of a water soluble binder, such as polyvinyl alcohol or cellulose, to give solutions in suspension, mix the solutions in suspension, apply the mixture thus obtained on a support such as paper and dry the resulting
When the present invention is applied to pressure sensitive copy paper, the pressure sensitive copy paper can be produced in the same manner as in a case where a known color developer or sensitizer is used. For example, a color former encapsulated in a microcapsule by a known method is dispersed using an appropriate dispersant, and the dispersion thus obtained is applied on paper to prepare a color developer sheet. In addition, a dispersion of a color developer is applied on paper to prepare a color developer sheet. The sheets thus prepared are combined with each other to produce pressure sensitive copy paper. The pressure-sensitive copy paper may be a unit consisting of upper paper having a coated bottom face and carrying a microcapsule containing an organic solvent solution of a color former and bottom paper having a coated top face and which carries a color developer (an acidic substance), or the so-called self-contained paper that has a face coated with the microcapsule and the color developer.
As the color developer used in the production or color developer included in a mixture for use in the production, one conventionally known can be used, and examples are inorganic acid substances such as acid clay, activated clay, attapulgite, bentonite, colloidal silica, silicate aluminum, magnesium silicate, zinc silicate, tin silicate, cooked kaolin and talc; aliphatic carboxylic acids such as oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid and stearic acid; aromatic carboxylic acids such as benzoic acid, pt-butylbenzoic acid, phthalic acid, gallic acid, salicylic acid, 3-isopropylsalicylic acid, 3- phenylsalicylic acid, 3-cyclohexylsalicylic acid, 3,5-di-t-butylsalicylic acid, 3 -methyl-5-benzyl salicylic acid, 3-phenyl-5- (2,2-dimethylbenzyl) salicylic acid, 3,5-di- (2-methylbenzyl) salicylic acid and 2-hydroxy-1-benzyl-3-naphthoic acid, and metal salts such as zinc, magnesium, aluminum and titanium of these aromatic carboxylic acids; color developers based on phenolic resin such as a p-phenylphenol-formalin resin and a p-butylphenolacetylene resin, and a mixture of said color developer based on phenolic resin and any of the metal salts of the aromatic carboxylic acids mentioned above .
The support used may be conventionally known paper, synthetic paper, a film, a plastic film, a foamed plastic film, a non-woven fabric or recycled paper such as used paper pulp. One of its mixtures can also be used as support.
In the case where paper is used as a support, a dispersion that includes a dispersion of a color former, a dispersion of a color developer and a dispersion of a charge, or alternatively, the dispersion can be applied directly to the paper Apply after coating the paper with a dispersion for a primer layer and dry the resulting. The dispersion is preferably applied after applying the dispersion for a primer layer because thus a greater dynamic sensitivity can be obtained.
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The dispersion for a primer layer is used to improve the smoothness on the surface of the support and is not particularly limited, and preferably includes a filler, a dispersant and water. Specifically, cooked kaolin or calcium carbonate is preferably used as filler, and preferably polyvinyl alcohol is used as dispersant.
To form a layer of recording material on a support, a method can be employed in which a dispersion is applied which includes a dispersion of a color former, a dispersion of a color developer and a dispersion of a charge on a support and the resulting is dried, a method in which the dispersion is sprayed with a sprayer or the like and the resulting is dried, a method in which the support is immersed in the dispersion for a prescribed period of time and the resulting is dried, or similar. Furthermore, to apply the dispersion, a manual coating method, a pressure coating method, a roller coating method, an air knife coating method, a mixture coating method, a coating method can be used by blowing, a curtain coating method, a direct comma method, a direct engraving method, a reverse engraving method, a reverse roller coating method or the like.
Examples
The recording material will now be described in detail by way of examples, and it is noted that the present invention is not limited to the following examples.
[Example 1] (not according to the invention) Synthesis of N- (2-hydroxyphenyl) -cinnamoylamide
To a mixture of 75 ml of acetone, 25 ml of water and 4.6 g of sodium hydrogen carbonate, 6.0 g of purified 2-aminophenol (manufactured by Aldrich, purity: 99%) was added and the resulting mixture was cooled to 5 ° C. A solution of 8.6 g of cinnamoyl chloride in 10 ml of methylene chloride was added dropwise so as not to raise the temperature beyond 10 ° C. After the dropwise addition, a reaction was carried out at room temperature for 2 hours. After completing the reaction, the pH of the reaction solution thus obtained was acidified by adding 2.6 g of 35% hydrochloric acid, and then, the solvent was distilled off under reduced pressure. To the residue thus obtained 50 ml of methanol and 25 ml of water were added, and the resulting mixture was heated to 60 ° C once and cooled to 5 ° C. The crystal thus separated was filtered off, and the crystal was sufficiently washed with water until the filtrate was colorless. The resulting crystal was dried under reduced pressure, to obtain 11.1 g of the target compound as a white crystal (yield: 93% in terms of cinnamoyl chloride).
1H NMR (DMSO-de): 6.79 (dt, 1H), 6.88 (dd, 1H), 6.95 (dt, 1H), 7.16 (d, 1 h), 7.41 ( m, 3 H), 7.56 (d, 1 H), 7.63 (d, 2H), 7.92 (d, 1H), 9.47 (s, 1H), 9.96 (wide s, 1 HOUR).
Melting point: 160-163 ° C
[Example 2] Purification of 2-aminophenol by the purification method described in the unexamined Japanese patent application publication No. 6-239813 and synthesis of N- (2-hydroxyphenyl) -cinnamoylamide
A homogeneous solution was obtained by dispersing 6.0 g of 2-aminophenol of low purity (97%) in 20 ml of water and adding 5.7 g of 35% hydrochloric acid. 0.1 g of sodium hydrosulfite was added to the solution and dissolved in it, the resulting solution was cooled to 10 ° C, and 7.9 g of 28% sodium hydroxide was slowly added to neutralize the solution. . After the addition of 75 ml of acetone and 4.6 g of sodium hydrogen carbonate, the resulting solution was cooled to 5 ° C. A solution of 8.6 g of cinnamoyl chloride in 10 ml of methylene chloride was added dropwise, and after the temperature was raised to room temperature, a reaction was carried out for 2 hours. Next, a treatment similar to that of Example 1 was performed, to obtain 11.8 g of the target compound as a white crystal (yield: 99% in terms of cinnamoyl chloride). Melting point: 158-163 ° C
[Example 5] (not according to the invention)
In accordance with the procedure described in Example 1 of Japanese Unexamined Patent Application Publication No. 2003-305959, 10.0 g of purified 2-aminophenol (manufactured by Aldrich, purity: 99%) and 7 were used. , 7 g of cinnamoyl chloride to synthesize 8.38 g of N- (2-hydroxyphenyl) -cinnamoylamide (yield: 70.1% in terms of cinnamoyl chloride). The crystal thus obtained was white.
[Comparative Example 1]
Example 2 was practiced, except that no sodium hydrosulfite was added to synthesize N- (2-hydroxyphenyl) -cinnamoylamide. The title compound was obtained as a yellow crystal. The crystal thus obtained was recrystallized from n-hexane / ethyl acetate, but the crystal remained yellow.
[Comparative Example 2]
In accordance with the procedure described in Example 1 of the publication of the unexamined Japanese patent application No. 2003-305959, 5.0 g of unpurified 2-aminophenol (manufactured by Tokyo Chemical)
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Industry Co., Ltd., purity: 99.5%) and 3.8 g of cinnamoyl chloride to synthesize 2.3 g of N- (2-hydroxyphenyl) - cinnamoylamide (yield: 38% in terms of cinnamoyl chloride ). The crystal thus obtained was yellow. Melting point: 158-162 ° C
[Comparative Example 7]
In accordance with the procedure described in Example 1 of Japanese Unexamined Patent Application Publication No. 2003-305959, 5.0 g of 2-aminophenol was used, which was obtained by breaking the seal of unpurified 2-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd., purity: 99.5%) and its storage at room temperature for 1 year, and 3.8 g of cinnamoyl chloride to synthesize 8.71 g of N- (2- hydroxyphenyl) -cinnamoylamide (yield: 72.8% in terms of cinnamoyl chloride). The crystal thus obtained was yellow.
[Measurement example 1] Measurement of powder whiteness with the color difference meter
The compounds obtained in Examples 1, 2 and 5 and Comparative Examples 1, 2 and 7 were measured for Hunter brightness and color spaces L *, a * and b * by filling a sample of each compound in an accessory cell for powder measurement of a spectrum colorimeter (SD 5000, manufactured by Nippon Denshoku Industries, Co., Ltd.) so that it did not transmit light, and the measurement was performed in an atmosphere at room temperature with a measuring diameter set at 28 mm, And the results are shown in Table 1.
[Table 1]
Table 1 Results of the measurement of the color difference (powder)
Shine by Hunter L * a * b *
Example 1 89.83 93.45 -1.44 5.70
Example 2 91.20 95.11 -1.27 6.08
Example 5 85.00 89.50 0.38 7.22
Comparative Example 1 84.33 94.15 -4.06 13.82
Comparative Example 2 73.31 84.17 -0.70 20.79
Comparative Example 7 69.13 85.80 -2.94 30.42
It was found from the results shown in Table 1 that the value of b * is high and, therefore, the compound is yellow when 2-aminophenol is used for production without purification (Comparative Example 1), and that the b * value is high and, therefore, the compound is also yellow when using the production process of the unexamined Japanese patent application publication No. 2003-305959 (Comparative Example 2). In addition, the value of b * was found to be high and, therefore, the compound is yellow when unpurified 2-aminophenol is used in the production method of the present invention (Comparative Example 7). However, it was also found that in the case where purified 2-aminophenol (Examples 1,2 and 5) is used, the whiteness is excellent and the value of b * is low.
[Example 3] Production of thermal recording paper
Color former dispersion (Solution A) 3-di-n-butylamino-6-methyl-7-anilinofluorane 16 parts
Aqueous 10% polyvinyl alcohol solution 84 parts
Color developer dispersion (Solution B) Compound of Example 1 16 parts
Aqueous solution of 10% polyvinyl alcohol Filling dispersion (Solution C) 84 parts
calcium carbonate 27.8 parts
Aqueous 10% polyvinyl alcohol solution 26.2 parts
Water 71 parts
("part" represents mass parts)
First, the mixtures of the above-mentioned compositions of solutions A to C, respectively, were sufficiently ground with a sand mill to prepare the dispersion of the components of solutions A to C, and 1 part by mass of solution A, and 2 parts by mass of solution B and 4 parts by mass of solution C were mixed to obtain a coating liquid. The coating liquid was applied on white paper using a wire rod (manufactured by Webster, Wire bar No. 12) and dried, and the resulting was subjected to a calendering treatment, to produce thermal recording paper (in which the Dry mass content of the coating liquid was approximately 5.5 g / m2).
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[Example 6]
Thermal paper was produced in the same manner as described in Example 3, except that the compound of Example 1 was replaced with the compound of Example 5 in the color developer dispersion (solution B) of Example 3.
[Comparative Example 3]
Thermal paper was produced in the same manner as described in Example 3, except that the compound of Example 1 was replaced by 4-hydroxy-4'-isopropoxydiphenylsulfone in the color developer dispersion (solution B) of Example 3.
[Comparative Example 4]
Thermal paper was produced in the same manner as described in Example 3, except that the compound of Example 1 was replaced by the following compound:
image8
in the color developer dispersion (solution B) of Example 3. [Comparative Example 5]
Thermal paper was produced in the same manner as described in Example 3, except that the compound of Example 1 was replaced by the following compound:
image9
in the color developer dispersion (solution B) of Example 3.
[Comparative Example 8]
Thermal paper was produced in the same manner as described in Example 3, except that the compound of Example 1 was replaced with the compound of Comparative Example 7 in the color developer dispersion (solution B) of Example 3.
[Example 4]
The thermal recording paper was produced in the same manner as described in Example 3, except that the white paper of Example 3 was replaced by white paper, which was obtained by applying a dispersion to a primer layer having the following composition in dry mass content of approximately 8 g / m2 and drying the resulting:
Dispersion for the primer layer
Calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., Unibur-70) 27.8 parts Aqueous solution of 10% polyvinyl alcohol 26.2 parts
Water 71 parts
[Comparative Example 6]
Thermal paper was produced in the same manner as described in Example 4 using the dispersion described in Example 3 except that the compound of Example 1 was replaced by 4-hydroxy-4'-isopropoxy diphenylsulfone in the color developer dispersion ( solution B) of Example 3.
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[Test example 1] (Dynamic sensitivity)
A portion of each recording paper produced in Examples 3 and 4 and comparative examples 3 to 6 was cut to undergo a dynamic sensitivity test by using a thermal paper color developing sensitivity tester (trade name: TH -PMH, manufactured by Ohkura Electric Co., Ltd.), in which the color was revealed under a printing voltage of 17 V at pulse widths of 0.2, 0.35, 0.5, 0.65, 0.8, 0.95, 1.1, 1.25, 1.4, 1.6 and 1.8 ms, and the print densities thus obtained were measured using a Macbeth reflection densitometer (trade name: RD- 19I, manufactured by Gretag-Macbeth AG).
The results are shown together in Figure 1. In addition, Table 2 below shows the values obtained in the color development at pulse widths of 1.1 and 1.25 ms as representative values. From these results it follows that the thermal recording paper of Example 3 shows a color developing sensitivity equivalent to 4-hydroxy-4'-isopropoxydiphenylsulfone and that an aromatic compound on one side of the aminophenol can achieve greater dynamic sensitivity when it replaces an amino group and a phenol ortho group instead of in position for.
[Table 2]
Table 2 Dynamic sensitivity
Pulse width
1.1 ms 1.25 ms
Example 3 0.80 1.02
Example 4 1.20 1.30
Comparative Example 3 0.93 1.14
Comparative Example 4 0.42 0.62
Comparative Example 5 0.43 0.60
Comparative Example 6 1.13 1.30
It was found from Table 2 that thermal recording paper has a dynamic sensitivity equivalent to that of a commercially available color developer by comparing between Example 3 and Comparative Example 3 and between Example 4 and Example comparative 6. In addition, it was found that thermal recording paper can be further improved in terms of dynamic sensitivity when a color developing layer is applied after applying a primer layer.
[Measurement example 2] (Measurement results of thermal paper color difference)
The ISO whiteness of each recording paper produced in Examples 3 and 6 and Comparative Example 8 was measured using a spectrophotometer (FP 10, manufactured by Nippon Denshoku Industries, Co., Ltd), and the color spaces L *, a * and b * of the recording paper were measured using a spectrophotometer (Spectroeye LT, manufactured by X-rite Inc.). The results are shown in Table 3.
[Table 3]
Table 3 Results of color difference measurement (thermal paper)
ISO whiteness L * a * b *
Example 3 80.24 94.56 -0.45 1.39
Example 6 65.30 92.30 -1.87 9.75
Comparative Example 8 59.77 91.89 -3.29 14.44
As a result of the evaluation of the color difference performed on the thermal paper actually produced as indicated above (Table 3), it was found that the ISO whiteness and the color spaces a * and b * were poor when 2-aminophenol was not used. purified (Comparative Example 8).
In addition, when purified 2-aminophenol is used, in the case where the production method of the present invention (note 1) was used for production (Example 3), ISO whiteness and color spaces a * and b * they are superior compared to the case where the known production method was used (note 2) (Example 6).
Note 1: The production method of the present invention is a method in which 2-aminophenol and cinnamoyl chloride are used in equimolar amounts, sodium hydrogen carbonate is used as the alkaline compound for the reaction, the crystal is separated from a solvent mixture of methanol and water, and the crystal is washed with water. Note 2: The known production method is a method in which 2-aminophenol and cinnamoyl chloride are used in a 2: 1 molar ratio for the reaction, and the crystal is separated from a solvent mixture of toluene / methyl isobutyl ketone .
(Conclusion)
To produce an excellent color developer in the whiteness of a background, it is always necessary to satisfy the first requirement, and furthermore, the second requirement and the third requirement are preferably satisfied. In accordance with the production method of the present invention, an amide-based phenol compound of the cinnamic acid can be obtained for the first time which is free of coloration of its crystal and is also free of coloration when used in production of thermal paper.
Industrial applicability
10
According to the present invention, when a cinnamic acid amide-based phenol compound is used as a color developer, an unprecedented recording material can be obtained that is excellent in background whiteness, has good color development benefits and it has a great storage property for both a background and an image, and particularly, a recording material that is excellent in the whiteness of a background 15 and in practice is extremely excellent in the color development capabilities.

权利要求:
Claims (6)
[1]
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1. A method of producing a phenol compound represented by Formula (I):
image 1
wherein R1 represents a hydroxyl group, a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, p represents 0 or an integer from 1 to 5, R2 and R3 each independently represent an atom of hydrogen or a C1-C6 alkyl group, R4 represents a hydrogen atom, a C1-C6 alkyl group, an optionally substituted phenyl group or an optionally substituted benzyl group; and a bond shown with a wavy line represents the E or Z form, or a mixture thereof, wherein the phenol compound has a color space b * of 10 or less; method comprising reacting a compound represented by formula (II) purified by reduction purification using a reducing agent:
image2
with a compound represented by the formula (III):
image3
in which R1 to R4 and p have the same meaning as defined in Formula (I) above, and in which X represents a hydroxyl group or a halogen atom, in the presence of a base, followed by crystallization.
[2]
2. The method of producing a phenol compound according to claim 1, wherein the phenol compound represented by the formula (I) has a Hunter brightness of 75 or more.
[3]
3. The method of producing a phenol compound according to claim 1 or claim 2, wherein the compound represented by formula (II) is a compound purified by reduction purification, using at least one reducing agent selected from sulphite, thiosulfate , dithionite, hydrazine, metal halide salt and boron compound.
[4]
4. The method of producing a phenol compound according to any one of claims 1 to 3, wherein the reducer is at least one selected from sodium sulphite, potassium sulphite, sodium thiosulfate, potassium thiosulfate, sodium hydrosulphite and its hydrates, potassium hydrosulfite and its hydrates, tin dichloride and sodium borohydride.
[5]
5. The method of producing a phenol compound according to any one of claims 1 to 4, wherein the base is at least one weak alkaline inorganic compound, selected from sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate , ammonium carbonate and ammonium hydrogen carbonate.
[6]
6. The method of producing a phenol compound according to any one of claims 1 to 5, wherein crystallization is performed using a polar solvent as a crystallization solvent.

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WO2010089982A1|2009-02-03|2010-08-12|日本曹達株式会社|Rewritable recording material|JP5713505B2|2009-09-29|2015-05-07|日本曹達株式会社|Recording materials using phenolic compounds|

法律状态:

优先权:

申请号 | 申请日 | 专利标题

JP2010195363|2010-09-01|

PCT/JP2011/004782|WO2012029276A1|2010-09-01|2011-08-29|Recording material using phenol compound|

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