CN101003499B - Novel color former and recording material - Google Patents
Novel color former and recording material Download PDFInfo
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- CN101003499B CN101003499B CN2007100022320A CN200710002232A CN101003499B CN 101003499 B CN101003499 B CN 101003499B CN 2007100022320 A CN2007100022320 A CN 2007100022320A CN 200710002232 A CN200710002232 A CN 200710002232A CN 101003499 B CN101003499 B CN 101003499B
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- urea
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- propyl
- amino
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- 0 *c1ccccc1 Chemical compound *c1ccccc1 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N c1ccccc1 Chemical compound c1ccccc1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- LUCKOUJTCDCWOZ-UHFFFAOYSA-N COc(cc1)ccc1S(c(cc1)ccc1OC)(=N)=O Chemical compound COc(cc1)ccc1S(c(cc1)ccc1OC)(=N)=O LUCKOUJTCDCWOZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
A urea-urethane compound represented by the following formula; a process for producing the compound; a color developer comprising the urea-urethane compound; and a color former containing a colorless or light-colored leuco dye. (In the formula, R represents a residue of an aliphatic compound, etc.; and A1 and A2 each represents an optionally substituted residue of an aromatic compound, etc).
Description
The application is the dividing an application of patent application of the March 1 calendar year 2001 applying date, application number 01805811.6.
Technical field
The present invention relates to novel urea-urea hydride compounds.The invention still further relates to novel color former by using this urea-urea hydride compounds to obtain, and the recording materials by using this color former to obtain.
Color former of the present invention can be as the color former of the recording materials that use record energy such as heat, pressure, the invention particularly relates to the color former of the stability in storage that can give coloured part (source recording material surface) not and colour developing image improvement, and recording materials, especially thermal recording medium by using this color former to obtain.
Background technology
It is known using the various chemistry of records energy such as heat, the pressure system of adding lustre to.In the middle of these systems, very early with regard to known by usually by the two-pack system of adding lustre to that system forms of adding lustre to, this two-pack system of adding lustre to is made up of with the developer that can cause colour developing when contacting with dyestuff former colourless or light dyestuff former, and this system of adding lustre to is generally used for recording materials.For example, the pressure sensitive recording material of applying pressure record uses heat thermal recording medium that writes down and the photosensitive recording material that uses optical recording.
The pressure sensitive recording material uses with plane form usually, with stationery seemingly.Usually,, the gained emulsifying soln is become several microns, again emulsion is shaped to microcapsule and obtains the pressure sensitive recording material by dyestuff former being dissolved in the suitable solvent.To make microcapsule coating surface and developer coating surface toward each other by being stacked together up and down with the first layer paper (also being referred to as paper here) of microcapsule coated substrate acquisition with by the second layer paper (also being referred to as down paper here) that is coated with another base material acquisition with the developer layer that contains developer.When by writing, knock or similar fashion when bringing pressure to bear on the gained assembly, microcapsule are destroyed, discharge the content that comprises dyestuff former.Dyestuff former is transferred on the developer layer, contacts with developer, makes color reaction takes place, and has obtained visual record.
In recent years, comprise with the usually employing in various machine information devices such as facsimile recorder, printer, register etc. of the thermal photography method of heat energy record.The thermal recording medium that is used for the thermal photography method has the characteristic such as the high whiteness of many excellences, is similar to the outward appearance and the feel of common plane paper, and the excellent properties that is used to write down, for example, and high developing sensitivity.The thermal photography method is an ideal, and for example the device that uses in the method is little, does not need to safeguard and do not produce noise.Therefore, the use range of thermal photography method obtains increasing in multiple field, terminal, the label of the register that for example is used to measure, facsimile recorder, printer, computer and be used for the ticket vendor field of railway tickets etc.
In the thermal photography method, the main use by on base material, forming the recording materials of the layer acquisition that add lustre to that contains the two-pack color former, and the component of heat-sensitive composition is by being in contact with one another with the thermal treatment recording materials, this hotwork can be supplied with by thermal head (thermal head), brand, laser beam or analogue for record, thereby develops the color and record.Many compositions as color former are those compositions colourless or light by using, that obtain for electron stain precursor (especially leuco dye) and acid developer such as phenolic compound.By the example that uses the recording materials that dyestuff former obtains be by use crystal violet lactone and 4,4 '-temperature-sensitive paper (consulting U.S. patent 3539375 etc.) that the binding substances of isopropylidene diphenol (dihydroxyphenyl propane) obtains as the temperature-sensitive color former.
As dyestuff former that is used for above-mentioned each recording method and developer, main respectively the use given electron compound and is subjected to electron compound.This is because give electron compound and be subjected to electron compound for example to have the characteristic of following excellence: contacting with each other as the dyestuff former of giving electron compound with as the developer that is subjected to electron compound has obtained to have the image of highdensity almost instantaneous colour developing; Can obtain near the outward appearance of white and can obtain various tones as red, orange, yellow, green, blue, black etc.Yet the chemical-resistant of the colour developing image that is obtained is inferior, thus with plastic plate or rubber in the softening agent that contains, or during the chemical that contains in food or makeup contact, record content easily dissolved.Also have, the record stability in storage of colour developing image is so poor, and when making the time of lacking relatively under being exposed to sunlight, the record content is faded, and perhaps worse, the record content disappears.Therefore, comprise that the color former of dyestuff former and developer obviously is restricted on their purposes, and urgent hope makes improvements.
In recent years, be that the phenolic compound of representative is considered to be unsuitable for use with the dihydroxyphenyl propane, because they are likely the internal secretion interfering factors, therefore non-phenolic developer is preferred.
In order to satisfy this requirement, for example, JP-A-59-115887 and U.S. patent 4521793 disclose the recording materials of the binding substances that comprises the color former that contains aromatic isocyanate compound and imino-compound, as the recording materials with high shelf stability.These reference disclose various recording materials, wherein can two kinds of color formers be in contact with one another to react as heat, pressure, light or analogue by applying record.These reference have been described by suitable selection color former can generate shades of colour as red, orange, yellow, light brown, dun etc.Yet in the invention disclosed, the colour developing of black remains inadequate in these reference, and black be in the situation of present normally used recording materials press for.
JP-A-8-2111 and JP-A-8-2112 disclose the thermal recording medium with the layer that adds lustre to that contains colourless or light dyestuff former and carbamide compound, as the thermal recording medium by using non-phenolic developer to obtain.Yet the colorant density of these recording materials is low and have an inadequate shelf stability.
JP-A-5-116459 disclose have the temperature-sensitive that contains colourless or light dyestuff former and solsonylurea compounds add lustre to the layer thermal recording medium.Yet the whiteness of these recording materials is low and have an inadequate shelf stability.
Content of the present invention
The object of the invention provides novel urea-urea hydride compounds or urea-urea alkane composition, and when being used as developer in color former, this compound or compositions table reveal excellent performance.
The present invention also provides the novel color former and the recording materials of visual retention and colorant density excellence, especially thermal recording medium, it can be by obtaining with any color former that uses various ureas-urea hydride compounds or urea-urea alkane composition.
In addition, the present invention relates to by various additives being added to the novel color former that has further improved performance in urea-urea hydride compounds or urea-urea alkane composition and the dyestuff former, and the recording materials by using described color former to obtain.
The inventor has investigated the synthetic of all cpds that is used for color former in earnest, found that specific compound has wonderful performance characteristics, thereby has realized the present invention.In addition, the inventor finds that the associative list of specific compound and particular dye precursor reveals wonderful performance characteristics, thereby has finished the present invention.
That is of the present invention theing contents are as follows.
First aspect of the present invention relates to and is characterised in that the urea-urea hydride compounds of representing and having the molecular weight below 5,000 or 5,000 with following formula (c):
Wherein R is the aliphatic cpd residues, A
1And A
2Be the aromatic substance residue independently, the nitrogen-atoms of urea groups directly is bonded in aromatic ring A respectively
1And A
2Carbon atom on, and R, A
1And A
2Can have one or more substituting groups.
A second aspect of the present invention relates to the urea-urea hydride compounds that is characterised in that with following formula (d) expression:
Wherein R is the aliphatic cpd residues, and the hydrogen atom of each phenyl ring can be by the aromatic substance residue, aliphatic cpd residue, heterogeneous ring compound residue; hydroxyl, nitro, itrile group, formamyl; sulfamyl, carboxyl, nitroso-group; amino, oxygen amino, nitro amino; diazanyl, urea groups, isocyanate group; sulfydryl, sulfo group or halogen atom replace, and R can have one or more substituting groups.
A third aspect of the present invention relates to and is characterised in that with following formula (e) or (f) expression have at least one urea alkyl and at least one urea groups, sum no more than 10 also is no less than 3, and the urea-urea hydride compounds with the molecular weight below 5,000 or 5,000:
Wherein R is the aliphatic cpd residues, and Y is aromatic substance residue, heterogeneous ring compound residue or aliphatic cpd residue, α
1Be to be different from Y and to have divalent or aromatics, heterocycle or aliphatic cpd residue more than the divalent, n is the integer more than 2 or 2, and each residue can have one or more substituting groups; Or
Z wherein
1With Y be aromatic substance residue or heterogeneous ring compound residue independently, β
1Be to have divalent or the above aliphatic cpd residue of divalent, n is the integer more than 2 or 2, and each residue can have one or more substituting groups.
The 4th aspect of the present invention relate to be characterised in that with following formula (g) or (h) expression urea-urea hydride compounds:
Wherein the hydrogen atom of each phenyl ring can be by the aromatic substance residue, aliphatic cpd residue, heterogeneous ring compound residue, hydroxyl; nitro, itrile group, formamyl; sulfamyl, carboxyl, nitroso-group; amino, oxygen amino, nitro amino; diazanyl, urea groups, isocyanate group; sulfydryl, sulfo group or halogen atom replace, β
1Be to have divalent or the above aliphatic cpd residue of divalent, n is the integer more than 2 or 2, and each residue can have one or more substituting groups; Or
Wherein R is the aliphatic cpd residue independently, and the hydrogen atom of each phenyl ring can be replaced by aromatic substance residue, aliphatic cpd residue or heterogeneous ring compound residue, and each residue can have one or more substituting groups, γ
1Be to be selected from-SO
2-,-O-,-(S)
n-,-(CH
2)
n-,-CO-,-CONH-,-NH-,-CH (COOR
1)-,-C (CF
3)
2-,-CR
2R
3-and with the group in any group of formula (a) expression:
Perhaps γ
1There is not R
1, R
2And R
3Respectively alkyl and n are 1 or 2 naturally.
The 5th aspect of the present invention relates to and is characterised in that the urea-urea alkane composition that contains urea-urea hydride compounds and thinner.
The 6th aspect of the present invention relates to urea-urea alkane composition according to a fifth aspect of the present invention, and wherein thinner is carbamide compound and/or urea hydride compounds.
The 7th aspect of the present invention relates to urea-urea alkane composition according to a fifth aspect of the present invention, and wherein thinner is the compound by the reaction of polyisocyanate compound and oxy-compound or aminocompound is obtained.
The 8th aspect of the present invention relates to the urea-urea alkane composition by the reaction of polyisocyanate compound and oxy-compound and aminocompound is obtained, it is characterized in that containing in the said composition in the molecular structure more than 50wt% or the 50wt% and contain at least one urea groups and at least one urea alkyl, sum is 2-10, and have 5, the urea of 000 or 5,000 following molecular weight-urea hydride compounds.
The 9th aspect of the present invention relates to urea-urea alkane composition according to an eighth aspect of the present invention, and wherein oxy-compound is a phenolic compound.
The of the present invention ten aspect relates to urea-urea alkane composition according to an eighth aspect of the present invention, and wherein oxy-compound is an alkylol cpd.
The 11 aspect of the present invention relates to according to each urea-urea alkane composition in the of the present invention the 8th to the tenth aspect, and wherein aminocompound is an aromatic amido compound.
The 12 aspect of the present invention relates to according to each urea-urea alkane composition in the 8th to the 11 aspect of the present invention, and wherein polyisocyanate compound is the aromatic polyisocyanate compound.
The 13 aspect of the present invention relates to production urea-urea alkane method for compositions, it is characterized in that making the reaction of polyisocyanate compound and oxy-compound, make that the ratio of hydroxyl equivalent number of the mole number of polyisocyanate compound and oxy-compound is 100/1 to 1/2, form one or more urea alkyl with some isocyanate group from polyisocyanate compound, add aminocompound then so that all the other isocyanic ester radical reactions of itself and polyisocyanate compound, to form one or more urea groups.
The 14 aspect of the present invention relates to production urea-urea alkane method for compositions, it is characterized in that making the reaction of polyisocyanate compound and aminocompound, make that the ratio of amino equivalent number of the mole number of polyisocyanate compound and aminocompound is 100/1 to 1/2, form one or more urea groups with some isocyanate group by polyisocyanate compound, add oxy-compound then so that all the other isocyanic ester radical reactions of itself and polyisocyanate compound, to form one or more urea alkyl.
The 15 aspect of the present invention relates to according to the of the present invention the 13 or urea-urea alkane the composition manufacturing method of the 14 aspect, the reaction that it is characterized in that forming the reaction of one or more urea alkyl continuously and form one or more urea groups.
The 16 aspect of the present invention relates to production urea-urea alkane method for compositions, this method comprises makes aminocompound and the polyisocyanates adducts reaction that obtains by polyisocyanate compound and oxy-compound reaction, make that the isocyanate group and the equivalence ratio of amino are 2/1 to 1/100, to form one or more urea groups, remove unreacted aminocompound then.
The 17 aspect of the present invention relates to production urea-urea alkane method for compositions, this method comprises that the polyisocyanates adducts that oxy-compound and reaction by polyisocyanate compound and aminocompound are obtained reacts, make that the equivalence ratio of isocyanate group and hydroxyl is 2/1 to 1/100, to form one or more urea alkyl, remove unreacted oxy-compound then.
The 18 aspect of the present invention relates to according to the present invention in the 13 to the 17 aspect each urea-urea alkane composition manufacturing method, the method is characterized in that without solvent to form the reaction of one or more urea alkyl and/or form the reaction of one or more urea groups, perhaps by using identical solvent to form the reaction of one or more urea alkyl and forming the reaction of one or more urea groups.
Nineteen of the present invention aspect relates to according to each urea-urea alkane composition manufacturing method in the 13 to the 18 aspect of the present invention, wherein forms the reaction of one or more urea alkyl and/or form the reaction of one or more urea groups under 0-300 ℃ temperature.
The 20 aspect of the present invention relate to according to the of the present invention the 13 in the nineteen aspect each urea-urea alkane composition manufacturing method, wherein in the presence of catalyzer, form the reaction of one or more urea alkyl and/or form the reaction of one or more urea groups.
The 21 aspect of the present invention relates to the color former that comprises the developer that contains urea-urea hydride compounds.
The 22 aspect of the present invention relates to and comprises the developer that contains urea-urea hydride compounds and the color former of colourless or light dyestuff former.
The 23 aspect of the present invention relates to the color former according to the 22 aspect of the present invention, and wherein colourless or light dyestuff former is a leuco dye.
The 24 aspect of the present invention relates to the color former according to the 21 to 23 aspect of the present invention, wherein said developer be according to of the present invention first to fourth aspect each urea-urea hydride compounds, according to the 5th to the 12 aspect of the present invention each urea-urea alkane composition or each the composition of production method acquisition by the 13 to the 20 aspect of the present invention.
The 25 aspect of the present invention relate to according to the of the present invention the 23 and the 24 aspect in each color former, it is characterized in that leuco dye is at least a leuco dye that is selected from triarylmethane type leuco dye, fluorane type leuco dye, fluorenes type leuco dye and the ditan type leuco dye.
The 26 aspect of the present invention relate to according to the of the present invention the 23 and the 24 aspect in each color former, it is characterized in that leuco dye is the compound with following formula (i) expression:
Y wherein
2And Y
3Be alkyl or alkoxyalkyl, Y
4Be hydrogen atom, alkyl or alkoxyl group, Y
5And Y
6Each be hydrogen atom, halogen atom, alkyl or alkoxyl group.
The 27 aspect of the present invention relates to according to each color former in the of the present invention the 23 and the 24 aspect, it is characterized in that leuco dye is the compound with following formula (j) expression:
R wherein
5And R
6Each be group by the expression of formula (k) or formula (l):
(R wherein
11-R
15Each be hydrogen atom, halogen atom, a 1-8 carbon atom alkyl, a 1-8 carbon atom alkoxyl group or-NR
16R
17, R wherein
16And R
17Each be the alkyl of 1-8 carbon atom), or
(R wherein
18And R
19Each is the alkyl or phenyl of hydrogen atom, a 1-8 carbon atom naturally), and R
7-R
10Each naturally alkyl, a 1-8 carbon atom of hydrogen atom, halogen atom, a 1-8 carbon atom alkoxyl group or-NR
20R
21, R wherein
20And R
21Each is the alkyl of 1-8 carbon atom naturally.
The 28 aspect of the present invention relates to according to each color former in the 21 to the 27 aspect of the present invention, and the fusing point that it is characterized in that urea-urea hydride compounds developer is not higher than 500 ℃ and be not less than 40 ℃.
The second nineteen aspect of the present invention relates to according to each color former in the 21 to the 27 aspect of the present invention, it is characterized in that urea-urea hydride compounds developer comprises to be selected from by following logical formula V or (VI) compound in the compound of expression:
Wherein the hydrogen atom of each phenyl ring can be replaced by aromatic substance residue, aliphatic cpd residue, heterogeneous ring compound residue, nitro, hydroxyl, carboxyl, nitroso-group, itrile group, formamyl, urea groups, isocyanate group, sulfydryl, sulfo group, sulfamyl or halogen atom; each residue can have one or more substituting groups, and γ is selected from-SO
2-,-O-,-(S)
n-,-(CH
2)
n-,-CO-,-CONH-and with the group in any group of formula (a) expression:
Perhaps γ does not exist, and n is 1 or 2; With
Wherein the hydrogen atom of each phenyl ring can be by aromatic substance residue, aliphatic cpd residue, heterogeneous ring compound residue, hydroxyl, nitro, itrile group, formamyl, sulfamyl, carboxyl, nitroso-group, amino, oxygen amino, nitro amino, diazanyl, urea groups, isocyanate group, sulfydryl, sulfo group or halogen atom displacement; each residue can have one or more substituting groups, and δ is selected from-SO
2-,-O-,-(S)
n-,-(CH
2)
n-,-CO-,-CONH-,-NH-,-CH (COOR
1)-,-C (CF
3)
2-and-CR
2R
3-in group or do not have R
1, R
2And R
3Each is alkyl naturally, and n is 1 or 2.
The 30 aspect of the present invention relates to according to each color former in the 21 to the 27 aspect of the present invention, it is characterized in that urea-urea hydride compounds developer comprises to be selected from by following structural formula (XX) and (XXI) compound in the compound of expression:
A hentriaconta-of the present invention aspect relates to according to each color former in the 21 to the 30 aspect of the present invention, but said composition further comprises the material of hot melt.
The 32 aspect of the present invention relates to the color former according to a hentriaconta-of the present invention aspect, but the material that it is characterized in that hot melt is to be selected from the betanaphthyl benzylic ether, to Benzyldiphenyl, 1,2-two (methylphenoxy) ethane, oxalic acid two-to methyl-benzyl ester, 1,2-hexichol oxygen ylmethyl benzene, at least a compound in meta-terphenyl and the stearylamide.
The 33 aspect of the present invention relates to the color former according to a hentriaconta-of the present invention aspect, but wherein the material of hot melt is the material of representing with following structural formula (XVIII):
Wherein Y is-SO
2-,-(S)
n-,-O-,-CO-,-CH
2-,-CH (C
6H
5)-,-C (CH
3)
2-,-COCO-,-CO
3-,-COCH
2CO-,-COOCH
2-,-CONH-,-OCH
2-and-among the NH-any one; n is 1 or 2, and the hydrogen atom of each phenyl ring can be replaced by halogen atom, hydroxyl, nitro, nitroso-group, itrile group, isocyanate group, isothiocyanate group, sulfydryl, sulfamyl, sulfonic group, amino, aromatic substance residue, aliphatic cpd residue or heterogeneous ring compound residue.
The 34 aspect of the present invention relates to the color former according to the 33 aspect of the present invention, but wherein the material of hot melt is the material of representing with following structural formula (XIX):
Wherein the hydrogen atom of each phenyl ring can be by halogen atom, hydroxyl, nitro, nitroso-group, itrile group, isocyanate group, isothiocyanate group, sulfydryl, sulfamyl, sulfonic group, amino, aromatic substance residue, aliphatic cpd residue or the displacement of heterogeneous ring compound residue.
The 35 aspect of the present invention relates to according to each color former in the 21 to the 34 aspect of the present invention, and described composition further comprises isocyanate compound.
The 36 aspect of the present invention relates to according to each color former in the 21 to the 34 aspect of the present invention, and described composition further comprises isocyanate compound and imino-compound.
The 37 aspect of the present invention relates to according to each color former in the 21 to the 36 aspect of the present invention, and described composition further comprises aminocompound.
The 38 aspect of the present invention relates to according to each color former in the 21 to the 37 aspect of the present invention, and wherein developer further comprises acid developer.
The 3rd nineteen aspect of the present invention relates to the color former according to the 38 aspect of the present invention; it is characterized in that acid developer is to be selected from 2; two (4-the hydroxyphenyl)-propane of 2-; 4-isopropyl phenyl-4 '-the hydroxyphenyl sulfone; two (3-allyl group-4-hydroxyphenyl) sulfone; 2,4 '-dihydroxyl-sulfobenzide and 4,4 '-at least a developer in [oxygen two (vinyloxy grouies-to the phenylene alkylsulfonyl)] diphenol.
The 40 aspect of the present invention relates to according to each color former in the 21 to the 3rd nineteen aspect of the present invention, and described composition further comprises fluorescence dye.
The 41 aspect of the present invention relates to according to each color former in the 21 to the 40 aspect of the present invention, and described composition further comprises the shelf stability imparting agent.
The 42 aspect of the present invention relates to the recording materials of the layer that adds lustre to that comprises base material and form thereon, the described layer that adds lustre to comprise according in of the present invention first to the 4th aspect each urea-urea hydride compounds, according in the 5th to the 20 aspect of the present invention each urea-urea alkane composition or according to each the color former in the 21 to the 41 aspect of the present invention.
The 43 aspect of the present invention relates to the recording materials according to the 42 aspect of the present invention, it is characterized in that forming on the layer that adds lustre to the protective layer of the layer that adds lustre to.
The 44 aspect of the present invention relates to the recording materials according to the 43 aspect of the present invention, it is characterized in that protective layer comprises water-soluble polymers.
The 45 aspect of the present invention relate to according to the of the present invention the 43 and the 44 aspect in each recording materials, it is characterized in that protective layer comprises mineral dye and/or pigment dyestuff.
The 46 aspect of the present invention relates to according to each the recording materials in the 43 to the 45 aspect of the present invention, it is characterized in that protective layer comprises lubricant.
The 47 aspect of the present invention relates to the recording materials according to the 42 aspect of the present invention, it is characterized in that forming on base material the middle layer, and forms the layer that adds lustre on described middle layer.
The 48 aspect of the present invention relates to the recording materials according to the 47 aspect of the present invention, it is characterized in that the middle layer comprises water-soluble polymers.
The 4th nineteen aspect of the present invention relate to according to the of the present invention the 47 and the 48 aspect in each recording materials, it is characterized in that the middle layer comprises mineral dye and/or pigment dyestuff.
The 50 aspect of the present invention relates to the recording materials according to the 42 aspect of the present invention, it is characterized in that with base material on form on the opposite substrate surface of the face of the layer that adds lustre to and form back coating.
The 51 aspect of the present invention relates to the recording materials according to the 50 aspect of the present invention, it is characterized in that back coating comprises water-soluble polymers.
The 52 aspect of the present invention relate to according to the of the present invention the 50 and the 51 aspect in each recording materials, it is characterized in that back coating comprises mineral dye and/or pigment dyestuff.
The 53 aspect of the present invention relates to according to each recording materials in the 42 to the 52 aspect of the present invention, it is characterized in that using at least a compound that is selected from water-soluble polymers and the anion surfactant dispersion agent as urea-urea hydride compounds.
The 54 aspect of the present invention relates to according to each recording materials in the 42 to the 52 aspect of the present invention, it is characterized in that using at least a dispersion agent that is selected from the compound of poly-(vinyl alcohol), modification poly-(vinyl alcohol), methylcellulose gum, hydroxypropyl-methylcellulose gum, condensation sodium naphthalene sulfonate, poly carboxylic acid ammonium salt, water-soluble low molecular weight multipolymer and sulfo-succinic acid 2-ethylhexyl sodium as urea-urea hydride compounds.
The 55 aspect of the present invention relates to according to each recording materials in the 42 to the 54 aspect of the present invention, it is characterized in that using at least a dispersion agent that is selected from the compound of water-soluble polymers, nonionogenic tenside and anion surfactant as dyestuff former.
The 56 aspect of the present invention relates to according to each recording materials in the 42 to the 54 aspect of the present invention, it is characterized in that using at least a compound that is selected from methylcellulose gum, Vltra tears, cithrol, polyethylene oxide alkyl ethers sulfuric ester and the sulfo-succinic acid 2-ethylhexyl sodium dispersion agent as dyestuff former.
The 57 aspect of the present invention relates to according to each recording materials in the 42 to the 56 aspect of the present invention, and described material is a thermal recording medium.
The 58 aspect of the present invention relates to the thermal recording medium according to the 57 aspect of the present invention, it is characterized in that the mean particle size of urea-urea hydride compounds is not more than 5 μ m and is not less than 0.05 μ m.
The 5th nineteen aspect of the present invention relates to according to the of the present invention the 57 and the thermal recording medium of the 58 aspect, it is characterized in that the fluid temperature when grinding urea-urea hydride compounds is below 60 ℃ or 60 ℃.
The 60 aspect of the present invention relates to according to each thermal recording medium in the 57 to the 5th nineteen aspect of the present invention, it is characterized in that the pH when grinding urea-urea hydride compounds is 5-10.
The 61 aspect of the present invention relates to according to each thermal recording medium in the 57 to the 60 aspect of the present invention, but it is characterized in that using at least a compound that is selected from water-soluble polymers and the anion surfactant dispersion agent as the material of hot melt.
The 62 aspect of the present invention relates to according to each thermal recording medium in the 57 to the 60 aspect of the present invention, it is characterized in that using be selected from poly-(vinyl alcohol), modification poly-(vinyl alcohol) but, at least a compound in methylcellulose gum, Vltra tears, condensation sodium naphthalene sulfonate, poly carboxylic acid ammonium salt, water-soluble low molecular weight multipolymer and the sulfo-succinic acid 2-ethylhexyl sodium is as the dispersion agent of the material of hot melt.
The 63 aspect of the present invention relates to according to each thermal recording medium in the 57 to the 62 aspect of the present invention, but it is characterized in that the material of urea-urea hydride compounds and hot melt fine grinding together.
The 64 aspect of the present invention relates to according to each thermal recording medium in the 57 to the 63 aspect of the present invention, it is characterized in that the pH with the heat sensitive recording layer substrates coated surface of thermal recording medium is 3-9.
The 65 aspect of the present invention relates to the production method according to each thermal recording medium in the 57 to the 64 aspect of the present invention, it is characterized in that the pH that will be used to form the heat sensitive recording layer of thermal recording medium is that the temperature-sensitive coating fluid of 5-12 is coated on the base material.
The 66 aspect of the present invention relates to the recording materials according to the 42 aspect of the present invention, and described material is the heat-sensitive magnetic recording material.
The 67 aspect of the present invention relates to the heat-sensitive magnetic recording material according to the 66 aspect of the present invention, it is characterized in that formation comprises the heat sensitive recording layer of urea-urea hydride compounds developer on a face of base material, and on another face, form magnetic recording layer.
The 68 aspect of the present invention relates to use according to the of the present invention the 66 or the train ticket of the heat-sensitive magnetic recording material of the 67 aspect.
The 6th nineteen aspect of the present invention relates to use according to the of the present invention the 66 or the ticket of the heat-sensitive magnetic recording material of the 67 aspect.
The 70 aspect of the present invention relates to the recording materials according to the 42 aspect of the present invention, and described material is the label that is used for thermal photography.
The 71 aspect of the present invention relates to the label that is used for thermal photography according to the 70 aspect of the present invention, it is characterized in that formation comprises the heat sensitive recording layer of urea-urea hydride compounds developer on a face of base material, and on another side, form binder layer.
The 72 aspect of the present invention relates to the label that is used for thermal photography according to the 71 aspect of the present invention, it is characterized in that forming back coating between binder layer and base material.
The 73 aspect of the present invention relate to according to the of the present invention the 71 and the 72 aspect in each the label that is used for thermal photography, it is characterized in that between heat sensitive recording layer and base material, forming the middle layer.
The 74 aspect of the present invention relates to according to each the label that is used for thermal photography in the 71 to the 73 aspect of the present invention, it is characterized in that forming on heat sensitive recording layer protective layer.
The 75 aspect of the present invention relates to the recording materials according to the 42 aspect of the present invention, and described material is the polychrome thermal recording medium.
The 76 aspect of the present invention relates to the polychrome thermal recording medium according to the 75 aspect of the present invention, wherein form two-layer at least heat sensitive recording layer on a face of base material, described recording materials are characterised in that one deck at least of described heat sensitive recording layer comprises urea-urea hydride compounds developer.
The 77 aspect of the present invention relates to the polychrome thermal recording medium according to the 76 aspect of the present invention, it is characterized in that forming between heat sensitive recording layer the middle layer.
The 78 aspect of the present invention relates to the polychrome thermal recording medium, it is characterized in that comprising base material and the two-layer heat sensitive recording layer that is laminated on face of base material, described recording layer has different colour temps respectively and develops the color with different tones respectively, last heat sensitive recording layer can comprise the reagent that is used as developer and tonal rendering agent simultaneously, or comprise reversible developer, and heat sensitive recording layer comprises urea-urea hydride compounds developer down.
The 7th nineteen aspect of the present invention relates to the polychrome thermal recording medium according to the 78 aspect of the present invention, it is characterized in that in two-layer heat sensitive recording layer, the upper strata is can develop the color at low temperatures and the low temperature of the colour killing at high temperature layer that adds lustre to, and lower floor is the high temperature that can at high temperature the develop the color layer that adds lustre to.
The 80 aspect of the present invention relates to the goods that are used for laser labelling, it is characterized in that having in its surface the heat sensitive recording layer that comprises urea-urea hydride compounds developer.
The 81 aspect of the present invention relates to the goods that are used for laser labelling, it is characterized in that having in its surface the heat sensitive recording layer that comprises colourless or light dyestuff former, urea-urea alkane developer and recording sensitivity improving agent.
The 82 aspect of the present invention relate to according to the of the present invention the 80 and the 81 aspect in each goods that are used for laser labelling; it is characterized in that having the protective layer that comprises aqueous binders on heat sensitive recording layer, the second-order transition temperature of described binding agent is 20-80 ℃.
The 83 aspect of the present invention relates to the goods that are used for laser labelling according to the 81 aspect of the present invention, and wherein the recording sensitivity improving agent is at least a compound that is selected from aluminium hydroxide, white mica, wollastonite and the kaolin.
The 84 aspect of the present invention relates to according to each goods that are used for laser labelling in the 80 to the 83 aspect of the present invention, and described goods are any in label, wrapping material and the container.
The 85 aspect of the present invention relates to the production method of the goods that are used for laser labelling, it is characterized in that the marking composition that adds lustre to that will comprise urea-urea hydride compounds developer is applied on the base material base material drying that will so handle again.
The 86 aspect of the present invention relates to the method for producing the goods that are used for laser labelling, it is characterized in that the marking composition that adds lustre to that will comprise colourless or light dyestuff former, urea-urea hydride compounds developer and recording sensitivity improving agent is applied on the base material, the base material drying that will so handle again.
The 87 aspect of the present invention relates to the method for mark goods, it is characterized in that with laser beam irradiation according to each the heat sensitive recording layer of the goods that are used for laser labelling in the 80 to the 84 aspect of the present invention.
The 88 aspect of the present invention relates to the marking composition that adds lustre to, and it is characterized in that comprising urea-urea hydride compounds developer.
The 8th nineteen aspect of the present invention relates to the marking composition that adds lustre to, and it is characterized in that comprising colourless or light dyestuff former, urea-urea hydride compounds developer and recording sensitivity improving agent.Implement best mode of the present invention
Below will describe the present invention in detail.
Urea-urea the hydride compounds of of the present invention first to the 4th aspect has at least one urea groups and at least one urea alkyl separately.
In urea-urea hydride compounds aspect of the present invention first to the 4th, the aliphatic cpd residue is bonded on the end Sauerstoffatom of urea alkyl.Therefore, urea-urea hydride compounds can be as physics and chemical stability, and especially the compound of excellent heat stability obtains.And urea-urea hydride compounds can obtain by using relatively cheap raw material.
In addition, the initial alkylol cpd of aliphatic cpd residue that is bonded in the end Sauerstoffatom of urea alkyl can easily be removed, and also is like this even it keeps unreacted in the building-up reactions of urea-urea hydride compounds.Therefore, urea-urea hydride compounds can obtain with high purity.
The preferred form of urea groups end changes according to the molecular size of urea-urea hydride compounds.In the urea-urea hydride compounds of formula (c), each end of urea groups should be bonded on the aromatic substance residue.The aromatic substance residue is the aromatic ring shown in the formula (d) preferably.In the formula with relative macromole size (e) and urea (f)-urea hydride compounds, group in each end of urea groups is for example as follows: in formula (e), the group of each end can be any in aromatic substance residue, heterogeneous ring compound residue and the aliphatic cpd residue, in formula (f), the group of each end can be aromatic substance residue or heterogeneous ring compound residue.In formula (e) with (f) in the two, the group of each end of urea groups is the aromatic substance residue preferably.Urea groups and urea alkyl are adjacent to each other by at least one compound residue (this structure division hereinafter is referred to as urea-urea-alkyl structure part).Preferably, only there is a compound residue to be present between urea groups and the urea alkyl.In addition, this residue aromatic ring preferably.
Though the urea-urea hydride compounds of of the present invention first to the 4th aspect it be unclear that as the concrete mechanism that developer works, by inference, this function is owing to urea groups in urea-urea-alkyl structure part and the interaction between the urea alkyl.In formula (e) with (f), the number of urea-urea-alkyl structure part is two or more.On the other hand, under the certain situation in formula (c) or urea (d)-urea hydride compounds, the number of urea-urea-alkyl structure part is 1.In this case, be presumed as follows: in formula (c) or urea (d)-urea hydride compounds, the residue that is bonded in each end of urea groups is limited to most preferred residue, i.e. aromatic substance residue is so that can make this compound play the effect of developer to a certain extent; On the other hand, in formula (e) or (f), be bonded in the residue aromatic substance residue always of each end of urea alkyl.
The number that is present in the urea-urea-alkyl structure part in the molecule is 1-10, preferred 1-5, and more preferably 2-4 is enough.
Except urea-urea-alkyl structure part, urea-urea hydride compounds can have one or more other urea groups and urea alkyl in molecule.
The term " aliphatic series " that uses in the situation aspect of the present invention first to the 4th comprises term " alicyclic ".
The term " aliphatic cpd residue " that uses in the situation aspect of the present invention first to the 4th is meant the residue by the carbon atom keyed jointing of the part of the aliphatic hydrocrbon in the residue.Term used herein " aromatic substance residue " is meant the residue by the carbon atom keyed jointing of aromatic ring in the residue such as phenyl ring.Term used herein " heterogeneous ring compound residue " is meant by forming the residue of heterocyclic carbon atom keyed jointing in the residue.
The substituent preferred embodiment of aliphatic cpd residue, heterogeneous ring compound residue and aromatic substance residue is an alkyl, cycloalkyl, phenyl, amide group, alkoxyl group, nitro, itrile group, halogen atom, formyl radical, dialkyl amido, tosyl group and methane sulfonyl.
When consider will of the present invention first to the 4th aspect urea-urea hydride compounds when being used as developer or being used for thermal recording medium, be present in one or more aliphatic urea alkyl in the molecular structure of each urea-urea hydride compounds of of the present invention first to the 4th aspect and one or more urea groups total no more than 11 and be no less than 2, preferred no more than 11 and be no less than 3, more preferably no more than 11 and be no less than 4.The ratio of urea alkyl and urea groups preferably 1: 3 to 3: 1, more preferably 1: 2 to 2: 1, most preferably 1: 1.The molecular weight of urea-urea hydride compounds is below 5,000 or 5,000, below preferred 2,000 or 2,000.
In thermal recording medium, the preferred compound that uses with fusing point.The fusing point of the urea-urea hydride compounds of preferred of the present invention first to the 4th aspect is at 40 ℃ to 500 ℃, more preferably at 60 ℃ to 300 ℃, most preferably in 60 ℃ to 250 ℃ scope.
Synthetic method to each urea-urea hydride compounds of of the present invention first to the 4th aspect is not particularly limited.Wherein synthesize the method for urea-urea hydride compounds because easy but preferred by the reaction of isocyanate compound and alkylol cpd and amine compound.
To the preparation a first aspect of the present invention formula (c) urea-urea hydride compounds method without limits.The amine compound of the alkylol cpd that this compound for example can be by making following formula (m) and the isocyanate compound of following formula (n) and following formula (o) for example reacts according to reaction formula shown below (A ') or (B ') and obtains:
R-OH (m)
Wherein R can have one or more substituent aliphatic cpd residues;
OCN-A
1-NCO (n)
A wherein
1Be to have one or more substituent aromatic substance residues; With
A
2-NH
2 (o)
A wherein
2Be to have one or more substituent aromatic substance residues.
Method to the urea-urea hydride compounds of the formula (d) for preparing second aspect of the present invention is not particularly limited.The amine compound of the alkylol cpd that this compound for example can be by making formula (m) and the isocyanate compound of following formula (p) and following formula (q) for example reacts according to reaction formula shown below (C ') or (D ') and obtains:
Wherein the hydrogen atom of phenyl ring can be replaced by aromatic substance residue, aliphatic cpd residue, heterogeneous ring compound residue, hydroxyl, nitro, itrile group, formamyl, sulfamyl, carboxyl, nitroso-group, amino, oxygen amino, nitro amino, diazanyl, urea groups, isocyanate group, sulfydryl, sulfo group or halogen atom, and each residue can have one or more substituting groups; With
Wherein the hydrogen atom of phenyl ring can be replaced by aromatic substance residue, aliphatic cpd residue or heterogeneous ring compound residue, and each residue can have one or more substituting groups.
To the method for the urea-urea hydride compounds of the formula (e) for preparing the 3rd aspect of the present invention without limits.The amine compound of the alkylol cpd that this compound for example can be by making general formula (m) and the isocyanate compound of following general formula (r) and following general formula (s) for example reacts according to reaction formula shown below (E ') or (F ') and obtains:
OCN-Y-NCO (r)
Wherein Y is aromatic substance residue, heterogeneous ring compound residue or aliphatic cpd residue, and each residue can have one or more substituting groups; With
α
1 
(NH
2)
n (s)
α wherein
1Be to have divalent or above aromatics, aliphatic series or the heterogeneous ring compound residue of divalent, n is the integer more than 2 or 2, and each residue can have one or more substituting groups.
To the method for the urea-urea hydride compounds of the formula (f) for preparing the 3rd aspect of the present invention without limits.The alkylol cpd of the amine compound that this compound for example can be by making following general formula (t) and the isocyanate compound of general formula (r) and following general formula (u) for example reacts according to reaction formula shown below (G ') or (H ') and obtains:
Z
1-NH
2 (t)
Z wherein
1Be aromatic substance residue or heterogeneous ring compound residue, and each residue can have one or more substituting groups; With
β
1 
OH]n (u)
β wherein
1Be to have divalent or the above aliphatic cpd residue of divalent, and can have one or more substituting groups, n is the integer more than 2 or 2.
To the method for the urea-urea hydride compounds of the formula (g) for preparing the 4th aspect of the present invention without limits.The amine compound of the alkylol cpd that this compound for example can be by making formula (u) and the isocyanate compound of formula (p) and formula (q) for example reacts according to reaction formula shown below (I ') or (J ') and obtains:
Method to the urea-urea hydride compounds of the formula (h) for preparing the 4th aspect of the present invention has no particular limits.The alkylol cpd of the amine compound that this compound for example can be by making following formula (XVII) and the isocyanate compound of formula (p) and general formula (m) for example reacts according to reaction formula shown below (K ') or (L ') and obtains:
Wherein the hydrogen atom of each phenyl ring can be replaced by aromatic substance residue, aliphatic cpd residue, heterogeneous ring compound residue, nitro, hydroxyl, carboxyl, nitroso-group, itrile group, formamyl, urea groups, isocyanate group, sulfydryl, sulfo group, sulfamyl or halogen atom; each residue can have one or more substituting groups, γ
1Be to be selected from-SO
2-,-O-,-(S)
n-,-(CH
2)
n-,-CO-,-CONH-,-NH-,-CH (COOR
1)-,-C (CF
3)
2-,-CR
2R
3-and with the group in any group of formula (a) expression:
Perhaps γ
1There is not R
1, R
2And R
3Each is alkyl naturally, and n is 1 or 2.
The compound of formula (m)-(u) that can be used in the urea-urea hydride compounds of synthetic following formula (c)-(h) will be in following detailed description.
As the alkylol cpd of general formula (m), can use any alkylol cpd, as long as it has the one or more OH groups on the one or more carbon atoms that are bonded in aliphatic cpd respectively.The example of alkylol cpd is at solvent handbook (Solvent Handbook), KodanshaScientific Co., Ltd., the 9th impression (1989), the alcohol of describing in 327-420 page or leaf and the 772-817 page or leaf.Alkylol cpd for example comprises fatty alcohol such as methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, cyclopentanol, tertiary amyl alcohol, 2-amylalcohol, primary isoamyl alcohol, hexanol, 3-hexanol, hexalin, hexahydrobenzyl alcohol, 4-methyl-2-amylalcohol, enanthol, iso-heptanol, octanol (octanol), 2-ethyl-1-hexanol, octanol (capryl alcohol), nonyl alcohol, isononyl alcohol, decyl alcohol, hendecanol, dodecanol, tridecyl alcohol, tetradecanol, cetyl alcohol, Stearyl alcohol, isooctadecanol etc.; Unsaturated aliphatic is pure as vinyl carbinol, methallyl alcohol, crotyl alcohol, propargyl alcohol etc.; Fatty alcohol with keyed jointing aromatic substance residue thereon, as benzylalcohol, styryl carbinol etc.; Fatty alcohol with keyed jointing heterogeneous ring compound residue thereon, as the 2-piconol, 3-piconol, 4-piconol, furfuryl alcohol etc.; Halogenation fatty alcohol such as ethylene chlorhydrin, 1-chloro-3-hydroxy propane etc.; Glycol ether is as glycol monomethyl methyl ether, ethylene glycol monomethyl ether, the glycol monomethyl propyl ether, glycol monomethyl isopropyl ether, ethylene glycol monobutyl ether, the glycol monomethyl isobutyl ether, ethylene glycol mono hexyl ether, glycol monomethyl phenyl ether, the diglycol monotertiary methyl ether, carbiphene, diglycol monotertiary propyl ether, the diglycol monotertiary isopropyl ether, diglycol monotertiary butyl ether, diglycol monotertiary isobutyl ether, the diglycol monotertiary hexyl ether, diglycol monotertiary phenyl ether, propylene glycol monomethyl ether, propylene glycol list ethyl ether, propylene glycol list propyl ether, propylene glycol monoisopropyl ether, the propylene glycol single-butyl ether, propylene glycol list isobutyl ether, propylene glycol list phenyl ether, DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol list propyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol single-butyl ether, dipropylene glycol list isobutyl ether, dipropylene glycol list phenyl ether etc.; Glycol such as ethylene glycol, glycol ether, triglycol, 1, ammediol, 1,2-propylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, hexylene glycol, 1,9-nonanediol, neopentyl glycol, methyl pentanediol etc.; Aliphatic polyol such as glycerine, Viscotrol C, TriMethylolPropane(TMP), trimethylolethane, hexanetriol, tetramethylolmethane, Alpha-Methyl glucosides, sorbyl alcohol, sucrose etc.; Polyvalent alcohol such as polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, adipic acid ester deutero-polyvalent alcohol, epoxy group(ing) modified polyalcohol, polyester ether polylol, polycarbonate polyol, polycaprolactone glycol, the amine modified polyalcohol, one or both or the multiple mixture (glycerine and propylene glycol) that join polyhydroxy-alcohol by the mixture (for example oxyethane and propylene oxide) with a kind of oxyalkylene or two or more oxyalkylenes are gone up the polyether glycol that obtains, the acryl polyvalent alcohol, fluoridize polyvalent alcohol, polybutadiene polyol, poly-hydroxy polyvalent alcohol, Viscotrol C deutero-polyvalent alcohol, polymer polyatomic alcohol, halogen-containing polyvalent alcohol, phosphorated polyvalent alcohol etc.; With alkanolamine such as N, N-dialkyl group-thanomin, N, N-dialkyl group Yi Bingchunan, N-alkyl diethanolamine, N-alkyl diisopropanolamine (DIPA), trolamine, tri-isopropanolamine, N, N, N ', N '-four (2-hydroxyethyl) quadrol, N, N, N ', N ' ,-four (2-hydroxypropyl) quadrol etc.
In the above-mentioned alkylol cpd that exemplifies, preferably have the monohydroxy-alcohol of an OH base, more preferably have the fatty alcohol and the glycol ether of 10 or 10 following carbon atoms.
Isocyanate compound to formula (n) is not particularly limited, as long as it is to have the aromatic isocyanate that is bonded in the two or more isocyanate group on the carbon atom respectively.Isocyanate compound for example comprises phenylene vulcabond, metaphenylene vulcabond, adjacent phenylene vulcabond, 2,5-dimethoxy benzene-1,4-vulcabond, 2,4 toluene diisocyanate, 2, the 6-tolylene diisocyanate, diphenylmethanediisocyanate, o-tolidine vulcabond, diphenyl ether vulcabond, 1, the 5-naphthalene diisocyanate, dianisidine vulcabond, 3,3 '-dimethyl-4,4 '-diphenylmethanediisocyanate, triphenylmethane triisocyanate, three (4-phenyl isocyanate) thiophosphatephosphorothioate, 4,4 ', 4 " three isocyanatos-2,5-dimethoxytrityl amine and 4; 4 ', 4 " three isocyanatos-triphenylamine.As the isocyanate compound of formula (n), can also use vulcabond dimer such as N, N '-(4,4 '-dimethyl-3,3 '-phenylbenzene two isocyanatos)-urea diketone (Desmodule TT, trade(brand)name), toluene diisocyanate dimer; With diisocyanate trimer as 4,4 ', 4 " trimethylammonium-3,3 ', 3 " three isocyanatos-2,4,6-triphenyl cyanurates.Can also use tolylene diisocyanate, the water adduction isocyanic ester of diphenylmethanediisocyanate etc., as 1, two (3-isocyanato-4-aminomethyl phenyl) ureas of 3-; The trimethylolpropane adduct of polyvalent alcohol adducts such as tolylene diisocyanate (Desmodule L and Coronate L, trade(brand)name); And amine adduct.Can also use the compound with two or more isocyanate group (content of these reference is quoted for reference here) of the row of the isocyanate compound described in the specification sheets of the specification sheets that belongs to JP-A-10-76757 and JP-A-10-95171 and isocyanic ester addition compound.
In the above isocyanate compound that exemplifies, the aromatic isocyanate with the isocyanate group that is bonded in phenyl ring is preferred.More preferably to phenylene vulcabond, metaphenylene vulcabond, adjacent phenylene vulcabond, 2,4 toluene diisocyanate, 2, the 6-tolylene diisocyanate, diphenylmethanediisocyanate, o-tolidine vulcabond, the diphenyl ether vulcabond, l,5 naphthylene diisocyanate, the triphenyl methane vulcabond, N, N '-(4,4 '-dimethyl-3,3 '-phenylbenzene two isocyanatos) urea diketone (Desmodule TT, 4,4 trade(brand)name), ', 4 " trimethylammonium-3; 3 ', 3 " three isocyanatos-2,4,6-triphenyl cyanurate, 1, the trimethylolpropane adduct (Desmodule L and Coronate L, trade(brand)name) of two (3-isocyanato-4-methyl-phenyl) ureas of 3-and tolylene diisocyanate.The particularly preferred example of the isocyanate compound of formula (n) is a tolylene diisocyanate.In the middle of tolylene diisocyanate, 2,4 toluene diisocyanate is preferred.Except 2,4 toluene diisocyanate, sell 2,4 toluene diisocyanate and 2 on the market usually, the mixture of 6-tolylene diisocyanate can low price obtain, and also can be used as the isocyanate compound of formula (n).
As the amine compound of general formula (o), for example can mention aromatic amine, as aniline; Ortho Toluidine, meta-aminotoluene, para-totuidine; o-anisidine, P-anisidine, p-phenetidine; N, N-dimethyl-P-pHENYLENE dI AMINE, N; N-diethyl-P-pHENYLENE dI AMINE, 2, the 4-dimethoxyaniline; 2,5-dimethoxyaniline, 3; the 4-dimethoxyaniline, p-aminoacetanilide, para-amino benzoic acid; Ortho-Aminophenol, Metha Amino Phenon, p-aminophenol; 2,3-xylidene(s), 2; the 4-xylidene(s), 3, the 4-xylidene(s); 2,6-xylidene(s), 4-aminobenzonitrile; anthranilic acid, p-cresol is fixed, and 2; the 5-dichlorphenamide bulk powder, 2, the 6-dichlorphenamide bulk powder; 3,4-dichlorphenamide bulk powder, 3; the 5-dichlorphenamide bulk powder, 2,4; the 5-trichloroaniline, Alpha-Naphthyl amine, amino anthracene; o ethyl aniline, Ortho-Chloro aniline, m-chloro aniline; p-Chlorobenzoic acid amide, methylphenylamine, N-ethylaniline; N propyl aniline, N-butylaniline, N; the N-aceto-acetyl aniline, bromination trimethylphenyl ammonium, 4; 4 '-diamino-3,3 '-diethyl-ditan, 4; 4 '-the diaminobenzene formylaniline, 3, the 5-diaminochlorobenzene; diamino-diphenyl ether, 3,3 '-two chloro-4; 4 '-diaminodiphenyl-methane, 3,3 '-dimethyl-4; 4 '-diaminodiphenyl-methane, tolidine alkali, adjacent phenylenediamine; m-phenylenediamine, P-pHENYLENE dI AMINE, 2-chloro-P-pHENYLENE dI AMINE; dianisidine, methyl p-aminobenzoate, parathesin; the para-amino benzoic acid n-propyl, para-amino benzoic acid isopropyl ester, planoform; the para-amino benzoic acid dodecyl ester, para-amino benzoic acid benzyl ester, adjacent aminobenzophenone; the m-aminophenyl ethyl ketone, para-aminoacetophenone, m-aminophenyl methane amide; anthranilamide, Para Amino Benzamide is to amino-N-methyl-benzamide; 3-amino-4-methyl benzamide, 3-amino-4-methoxy benzamide, 3-amino-4-chlorobenzamide; right-(N-phenyl amino formyl radical) aniline, right-[N-(4-chloro-phenyl-)-formamyl] aniline, right-[N-(4-aminophenyl) formamyl]-aniline; 2-methoxyl group-5-(N-phenyl amino formyl radical) aniline, 2-methoxyl group-5-[N-(2 '-methyl-3 '-chloro-phenyl-) formamyl]-aniline, 2-methoxyl group-5-[N-(2 '-chloro-phenyl-) formamyl]-aniline; 5-acetylaminohydroxyphenylarsonic acid 2-anisidine, 4-acetylaminohydroxyphenylarsonic acid aniline, 4-(N-methyl-N-kharophen) aniline; 2,5-diethoxy-4-(N-benzoyl-amido) aniline, 2; 5-dimethoxy-4 '-(N-benzoyl-amido) aniline, 2-methoxyl group-4-(N-benzoyl-amido)-5-monomethylaniline, 4-sulfamyl aniline; 3-sulfamyl aniline, 2-(N-ethyl-N-phenyl amino alkylsulfonyl) aniline, 4-dimethylamino alkylsulfonyl aniline; 4-diethylamino alkylsulfonyl aniline, Sulphathiazole, 4-ADP base sulfone; 2-chloro-5-N-phenyl sulfamoyl base aniline, 2-methoxyl group-5-N, N-diethyl-sulfamyl aniline; 2,5-dimethoxy-4 '-N-phenyl sulfamoyl base aniline, 2-methoxyl group-5-benzyl alkylsulfonyl aniline; 2-phenoxy group alkylsulfonyl aniline, 2-(2 '-chlorophenoxy) alkylsulfonyl aniline, 3-Phenylsulfamoyl base-4-monomethylaniline; two [4-(m-aminophenyl oxygen base) phenyl] sulfone, two [4-(p-aminophenyl oxygen base) phenyl] sulfone, two [3-methyl-4-(p-aminophenyl oxygen base) phenyl] sulfone; 3,3 '-dimethoxy-4 ', 4 '-benzidine; 3,3 '-dimethyl-4,4 '-benzidine; 2,2 '-two chloro-4,4 '-diamino-5; 5 '-dimethoxy-biphenyl, 2,2 '; 5,5 '-tetrachloro-4,4 '-benzidine; the o-tolidine sulfone, 2,4 '-benzidine; 2,2 '-benzidine, 4; 4 '-benzidine, 2,2 '-two chloro-4; 4 '-benzidine, 3,3 '-two chloro-4; 4 '-benzidine, 2,2 '-dimethyl-4; 4 '-benzidine, 4,4 '-thiobis aniline; 2,2 '-the dithio dianiline, 4; 4 '-the dithio dianiline, 4,4 '-diamino-diphenyl ether; 3,3 '-diamino-diphenyl ether, 3; 4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl-methane; 3,4 '-diaminodiphenyl-methane, two (3-amino-4-chloro-phenyl-) sulfone; two (3, the 4-diamino-phenyl) sulfone, 4; 4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone; 3,4 '-diamino diphenyl sulfone, 3; 3 '-diaminodiphenyl-methane, 4,4-diamino-diphenylamine; 4,4 '-ethylenebis aniline, 4; 4 '-diamino-2,2 '-the dimethyl dibenzyl, 3; 3 '-diaminobenzophenone, 4,4 '-diaminobenzophenone; 1, two (4-amino-benzene oxygen) benzene of 4-, 1; two (4-amino-benzene oxygen) benzene of 3-, 1, two (3-amino-phenoxy group) benzene of 3-; 9, two (4-aminophenyl) fluorenes of 9-, 2; two (the 4-amino-benzene oxygen phenyl) propane of 2-, 4,4 '-two (4-amino-phenoxy group) biphenyl; 3,3 ', 4; 4 '-the tetramino diphenyl ether, 3,3 '; 4,4 '-the tetramino sulfobenzide, 3; 3 ' 4,4 '-the tetramino benzophenone, the 3-aminobenzonitrile; the 4-phenoxybenzamine, 3-phenoxybenzamine, 4; 4 '-the methylene-bis Ortho Toluidine, 4,4 '-(to the phenylene isopropylidene)-two-(2; the 6-xylidene(s)), adjacent chloro-p-Nitroaniline, adjacent nitro-p-Chlorobenzoic acid amide; 2,6-two chloro-4-N-methyl-p-nitroanilines, 5-chloro-2-N-methyl-p-nitroaniline; 2-amino-4-chlorophenol, o-Nitraniline, m-nitraniline; p-Nitroaniline, 2-methyl-4-N-methyl-p-nitroaniline, nitro-para-totuidine; 2-amino-5-nitrobenzonitrile, N-methyl p-aminophenol sulfate, 2; the 4-diaminophenol, N-(beta-hydroxyethyl)-Ortho-Aminophenol-sulfuric ester, Sulphanilic Acid; m-sulfanilic acid, 4B acid, C acid; 2B acid, to fluoro-aniline, adjacent fluoroaniline; 3-chloro-4-fluoroaniline, 2,4 difluorobenzene amine; 2,3, the 4-trifluoromethyl aniline; mamino-trifluoromethyl benzene, a toluylene diamine, 2-aminothiophenol; 2-amino-3-bromo-5-nitrobenzonitrile; diphenylamine, to amino-diphenyl-amine, the octyl group diphenylamine; 2-methyl-4-methoxyl group diphenylamine; N, N-phenylbenzene-P-pHENYLENE dI AMINE, dianisidine; 3; 3 '-dichlorobenzidine, 4,4 '-diaminostilbene-2; 2 '-disulfonic acid; the benzyl ethylaniline, 1, the 8-naphthylene diamine; sodium naphthionate; 2-amino-1-naphthalene sulfonic aicd, H acid, J acid; phenyl J acid; 1,4-diamino-anthraquinone, 1; 4-diamino-2,3-dichloroanthraquinone etc.
The aromatic isocyanate compound of formula (p) comprises 2,4 toluene diisocyanate, 2, and the 6-tolylene diisocyanate, the metaphenylene vulcabond, to phenylene vulcabond, adjacent phenylene vulcabond etc.Wherein, tolylene diisocyanate is preferred, and 2,4 toluene diisocyanate is preferred.
Aromatic amine compound to formula (q) is not particularly limited, as long as it has the one or more amino on the one or more carbon atoms that directly are bonded in phenyl ring respectively.In addition, the hydrogen atom of phenyl ring can use aromatic substance residue, aliphatic cpd residue, heterogeneous ring compound residue, hydroxyl, nitro, itrile group, formamyl, sulfamyl, carboxyl, nitroso-group, oxygen amino, nitro amino, diazanyl, urea groups, isocyanate group, sulfydryl, sulfo group or halogen atom to replace.The aromatic amine compound of formula (q) comprises for example aromatic monoamine such as aniline, Ortho Toluidine, meta-aminotoluene, para-totuidine, o-anisidine, P-anisidine, p-phenetidine, 2, the 4-dimethoxyaniline, 2,5-dimethoxyaniline, 3, the 4-dimethoxyaniline, to amino-Acetanilide, the aniline of carboxyl substituted is (for example, para-amino benzoic acid), aniline (for example, the Ortho-Aminophenol of hydroxyl replacement, Metha Amino Phenon, p-aminophenol and 2-amino-4-chlorophenol), 2, the 3-xylidene(s), toluene 24 diamine, 3,4-xylidene(s), 2, the 6-xylidene(s), the aniline (for example, 4-aminobenzonitrile) that nitrile replaces, anthranilic acid, p-cresol is fixed, and the aniline that halogen replaces is (for example, 2,5-dichlorphenamide bulk powder, 2, the 6-dichlorphenamide bulk powder, 3, the 4-dichlorphenamide bulk powder, 3,5-dichlorphenamide bulk powder, 2,4, the 5-trichloroaniline, Ortho-Chloro aniline, m-chloro aniline and p-Chlorobenzoic acid amide), Alpha-Naphthyl amine, amino anthracene, o ethyl aniline, methyl p-aminobenzoate, parathesin, the para-amino benzoic acid n-propyl, para-amino benzoic acid isopropyl ester, planoform, the para-amino benzoic acid dodecyl ester, para-amino benzoic acid benzyl ester, adjacent aminobenzophenone, m-aminophenyl ethyl ketone, para-aminoacetophenone, the m-aminophenyl methane amide, anthranilamide, Para Amino Benzamide, to amino-N-methyl-benzamide, 3-amino-4-methyl benzamide, 3-amino-4-methoxy benzamide, 3-amino-4-chlorobenzamide, formamyl aniline is (for example right-(N-phenyl amino formyl radical) aniline, right-[N-(4-chloro-phenyl-) formamyl] aniline, right-[N-(4-aminophenyl)-formamyl] aniline, 2-methoxyl group-5-(N-phenyl amino formyl radical)-aniline, 2-methoxyl group-5-[N-(2 '-methyl-3 '-chloro-phenyl-)-formamyl] aniline and 2-methoxyl group-5-[N-(2 '-chloro-phenyl-)-formamyl] aniline), 5-acetylamino-2-anisidine, 4-acetylaminoaniline, 2-methoxyl group-4-(N-benzoyl-amido)-5-monomethylaniline, sulfamyl aniline (4-sulfamyl-aniline for example, 3-sulfamyl aniline, 2-chloro-5-N-phenyl-sulfamyl aniline, 2-methoxyl group-5-N, N-diethyl amino alkylsulfonyl-aniline and 2,5-dimethoxy-4 '-N-phenyl sulfamoyl base aniline), 2-(N-ethyl-N-phenyl amino alkylsulfonyl) aniline, 4-dimethyl-amino-sulfonyl aniline, 4-diethylamino alkylsulfonyl aniline, Sulphathiazole, 4-ADP base sulfone, 2-methoxyl group-5-benzyl alkylsulfonyl aniline, 2-phenoxy group alkylsulfonyl aniline, 2-(2 '-chlorophenoxy) alkylsulfonyl aniline, 3-Phenylsulfamoyl base-4-monomethylaniline, aniline (for example adjacent chloro-p-Nitroaniline that nitro replaces, ortho-nitro-parachloroaniline, 2,6-two chloro-4-N-methyl-p-nitroanilines, 5-chloro-2-N-methyl-p-nitroaniline, o-Nitraniline, m-nitraniline, p-Nitroaniline, 2-methyl-4-N-methyl-p-nitroaniline, between nitro-para-totuidine and 2-amino-5-nitrobenzonitrile), Sulphanilic Acid, m-sulfanilic acid, 4B acid, C acid, 2B acid, para-fluoroaniline, adjacent fluoroaniline, 3-chloro-4-fluoroaniline, 2,4 difluorobenzene amine, 2,3, the 4-trifluoromethyl aniline, mamino-trifluoromethyl benzene, 2-amino-3-bromo-5-nitrobenzonitrile etc.; Have one or more substituent aromatic monoamine such as the carboxyl of comprising, nitroso-group, oxygen amino, nitro amino, diazanyl, urea groups, isocyanate group, sulfydryl, sulfo group; With aromatic diamine as 4,4 '-diamino-3,3 '-the diethyl ditan, 4,4 '-the diaminobenzene formylaniline, 3, the 5-diaminochlorobenzene, diamino-diphenyl ether, 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane, 3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane, tolidine alkali, dianisidine, two [4-(m-aminophenyl oxygen base) phenyl] sulfone, two [4-(p-aminophenyl oxygen base) phenyl] sulfone, two [3-methyl-4-(p-aminophenyl oxygen base) phenyl] sulfone, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, Ortho Toluidine sulfone, 2,4 '-benzidine, 2,2 '-benzidine, 4,4 '-benzidine, 2,2 '-two chloro-4,4 '-benzidine, 3,3 '-two chloro-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-thiobis aniline, 2,2 '-the dithio dianiline, 4,4 '-the dithio dianiline, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, two (3-amino-4-chloro-phenyl-) sulfone, two (3, the 4-diamino-phenyl) sulfone, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 3,4 '-diamino diphenyl sulfone, 3,3 '-diamino-ditan, 4,4 '-diamino-diphenyl amine, 4,4 '-ethylenebis aniline, 4,4 '-diamino-2,2 '-the dimethyl dibenzyl, 3,3 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-phenoxy group) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 3-, 9, two (4-aminophenyl) fluorenes of 9-, 2, two (the 4-amino-benzene oxygen phenyl) propane of 2-, 4,4 '-two (4-amino-benzene oxygen) biphenyl, dianisidine, 3,3 '-dichlorobenzidine etc.Wherein, aromatic monoamine is preferred the use, and aniline and anils most preferably use.
Isocyanate compound to formula (r) is not particularly limited, as long as it has the two or more isocyanate group that are bonded in respectively on the carbon atom.This compound for example comprises phenylene vulcabond, metaphenylene vulcabond, adjacent phenylene vulcabond, 2,5-dimethoxy benzene-1,4-vulcabond, 2,4 toluene diisocyanate, 2, the 6-tolylene diisocyanate, diphenylmethanediisocyanate, o-tolidine vulcabond, the diphenyl ether vulcabond, l,5 naphthylene diisocyanate, the dianisidine vulcabond, 9-ethyl-carbazole-3,6-vulcabond, 3,3 '-dimethyl-4,4 '-diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, three (4-phenyl isocyanate) thiophosphatephosphorothioate, 4,4 ', 4 " three isocyanatos-2; 5-dimethoxytrityl amine, 4,4 '; 4 "-three isocyanato triphenylamines, between eylylene diisocyanate, lysinediisocyanate, dimer acid diisocyanate, isopropylidene is two-4-cyclohexyl-isocyanic ester, dicyclohexyl methane diisocyanate and methylcyclohexane diisocyanate.
As the isocyanate compound of formula (r), can also use vulcabond dimer such as N, N '-(4,4 '-dimethyl-3,3 '-phenylbenzene two isocyanatos)-urea diketone (Desmodule TT, trade(brand)name), toluene diisocyanate dimer; With diisocyanate trimer as 4,4 ', 4 " trimethylammonium-3,3 ', 3 " three isocyanatos-2,4,6-triphenyl cyanurates.Can also use tolylene diisocyanate, the water adduction isocyanic ester of diphenylmethanediisocyanate etc., as 1, two (3-isocyanato-4-aminomethyl phenyl) ureas of 3-; The trimethylolpropane adduct of polyvalent alcohol adducts such as tolylene diisocyanate (Desmodule L and Coronate L, trade(brand)name); And amine adduct.Can also use the compound with two or more isocyanate group (content of these reference is quoted for reference here) of the row of the isocyanate compound described in the specification sheets of the specification sheets that belongs to JP-A-10-76757 and JP-A-10-95171 and isocyanic ester addition compound.
In the above isocyanate compound that exemplifies, the aromatic isocyanate that has the isocyanate group that is bonded in phenyl ring is preferred.More preferably to phenylene vulcabond, metaphenylene vulcabond, adjacent phenylene vulcabond, 2,4 toluene diisocyanate, 2, the 6-tolylene diisocyanate, diphenylmethanediisocyanate, o-tolidine vulcabond, the diphenyl ether vulcabond, l,5 naphthylene diisocyanate, triphenylmethane triisocyanate, N, N '-(4,4 '-dimethyl-3,3 '-phenylbenzene two isocyanatos) urea diketone (Desmodule TT, 4,4 trade(brand)name), ', 4 " trimethylammonium-3; 3 ', 3 " three isocyanatos-2,4,6-triphenyl cyanurate, 1, the trimethylolpropane adduct (Desmodule L and Coronate L, trade(brand)name) of two (3-isocyanato-4-aminomethyl phenyl) ureas of 3-and tolylene diisocyanate.The particularly preferred example of the isocyanate compound of formula (r) is a tolylene diisocyanate.In the middle of tolylene diisocyanate, 2,4 toluene diisocyanate is preferred.Except 2,4 toluene diisocyanate, 2,4 toluene diisocyanate and 2, the mixture of 6-tolylene diisocyanate are generally on sale on market, can obtain at a low price, and also can be used as the isocyanate compound of formula (r).
The amine compound of mutual-through type (s) is not particularly limited, as long as it has two or more amino.This compound for example comprise aromatic amine as 4,4 '-diamino-3,3 '-the diethyl ditan, 4,4 '-the diaminobenzene formylaniline, 3, the 5-diaminochlorobenzene, diamino-diphenyl ether, 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane, 3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane, tolidine alkali, dianisidine, two [4-(m-aminophenyl oxygen base) phenyl] sulfone, two [4-(p-aminophenyl oxygen base) phenyl] sulfone, two [3-methyl-4-(p-aminophenyl oxygen base) phenyl] sulfone, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, o-tolidine sulfone, 2,4 '-benzidine, 2,2 '-benzidine, 4,4 '-benzidine, 2,2 '-two chloro-4,4 '-benzidine, 3,3 '-two chloro-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-thiobis aniline, 2,2 '-the dithio dianiline, 4,4 '-the dithio dianiline, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, two (3-amino-4-chloro-phenyl-) sulfone, two (3, the 4-diamino-phenyl) sulfone, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 3,4 '-diamino diphenyl sulfone, 3,3 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl amine, 4,4 '-ethylenebis aniline, 4,4 '-diamino-2,2 '-the dimethyl dibenzyl, 3,3 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-phenoxy group) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 3-, 9, two (4-aminophenyl) fluorenes of 9-, 2, two (the 4-amino-benzene oxygen phenyl) propane of 2-, 4,4 '-two (4-amino-benzene oxygen) biphenyl, dianisidine, 3,3 '-dichlorobenzidine, tolidine alkali, adjacent phenylenediamine, m-phenylenediamine, P-pHENYLENE dI AMINE etc.; Heterogeneous ring compound amine such as guanamines, acetylguanamine, 2,4-diamino-6-[2 '-methylimidazolyl-(1)] ethyl-S-triazine, 2,3-diamino-pyridine, 2,5-diamino-pyridine, 2,3,5-triamino pyridine, two (aminopropyl) piperazine etc.; With aliphatic amine such as methane diamines, 1,1, the 3-diaminopropanes, 1,4-diaminobutane, 1,3-diamino-2-hydroxy propane, ethylene diamine, diethylenetriamine, Triethylenetetramine (TETA), tetren, N-methyl-3,3 '-imino-two (propyl group amine), hexamethylene-diamine, two (amino methyl) hexanaphthene, isophorone diamine, isopropylidene two (aminocyclohexane), 4,4-diamino-dicyclohexyl methyl hydride, m-xylylene amine etc.In the above amine compound that exemplifies, aromatic amine is preferred, and having at least two amino is particularly preferred with the anils of following formula (VIII) expression also:
R wherein
1, R
2, R
3And R
4Be hydrogen atom, halogen atom, alkyl, alkoxyl group or amino independently, X
1And X
2Independently be group amino or that represent with following formula (b):
Y
1Be-SO
2-,-O-,-(S)
n-,-(CH
2)
n-,-CO-,-CONH-,-NH-,-CH (COOR
1)-,-C (CF
3)
2-,-CR
2R
3-and with in any one group of formula (a) expression any one:
Or there is not R
1, R
2And R
3Each is alkyl naturally, and n is 1 or 2.
The amine compound of general formula (t) comprises aromatic amine such as aniline, Ortho Toluidine, meta-aminotoluene, para-totuidine, o-anisidine, P-anisidine, p-phenetidine, N, N-dimethyl-right-phenylenediamine, N, N-diethyl-P-pHENYLENE dI AMINE, 2, the 4-dimethoxyaniline, 2, the 5-dimethoxyaniline, 3, the 4-dimethoxyaniline is to amino-Acetanilide, para-amino benzoic acid, Ortho-Aminophenol, Metha Amino Phenon, p-aminophenol, 2, the 3-xylidene(s), toluene 24 diamine, 3, the 4-xylidene(s), 2, the 6-xylidene(s), the 4-aminobenzonitrile, anthranilic acid, p-cresol is fixed, 2,5-dichlorphenamide bulk powder, 2, the 6-dichlorphenamide bulk powder, 3, the 4-dichlorphenamide bulk powder, 3,5-dichlorphenamide bulk powder, 2,4,5-trichloroaniline, alpha-naphthylamine, amino anthracene, o ethyl aniline, Ortho-Chloro aniline, m-chloro aniline, p-Chlorobenzoic acid amide, methylphenylamine, N-ethylaniline, N propyl aniline, N-butylaniline, N, N-diglycidylaniline, N, N-diglycidyl-Ortho Toluidine, etheric acid aniline, bromination trimethylphenyl ammonium, 4,4 '-diamino-3,3 '-the diethyl ditan, 4,4 '-the diaminobenzene formylaniline, 3, the 5-diaminochlorobenzene, diamino-diphenyl ether, 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane, 3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane, tolidine alkali, adjacent phenylenediamine, m-phenylenediamine, P-pHENYLENE dI AMINE, 2-chloro-P-pHENYLENE dI AMINE, dianisidine, methyl p-aminobenzoate, parathesin, para-amino benzoic acid n-propyl, para-amino benzoic acid isopropyl ester, planoform, para-amino benzoic acid dodecyl ester, para-amino benzoic acid benzyl ester, adjacent aminobenzophenone, m-aminophenyl ethyl ketone, para-aminoacetophenone, the m-aminophenyl methane amide, anthranilamide, Para Amino Benzamide, right-amino-N-methylbenzene Shen acid amides, 3-amino-4-methyl benzamide, 3-amino-4-methoxy benzamide, 3-amino-4-chlorobenzamide, right-(N-phenyl amino formyl radical) aniline, right-[N-(4-chloro-phenyl-) formamyl] aniline, to [N-(4-aminophenyl)-formamyl] aniline, 2-methoxyl group-5-(N-phenyl amino formyl radical)-aniline, 2-methoxyl group-5-[N-(2 '-methyl-3 '-chloro-phenyl-) formamyl] aniline, 2-methoxyl group-5-[N-(2 '-chloro-phenyl-)-formamyl] aniline, 5-acetylamino-2-anisidine, 4-acetylaminoaniline, 4-(N-methyl-N-kharophen) aniline, 2,5-diethoxy-4-(N-benzoyl-amido) aniline, 2,5-dimethoxy-4 '-(N-benzoyl-amido) aniline, 2-methoxyl group-4-(N-benzoyl-amino)-5-monomethylaniline, 4-sulfamyl aniline, 3-sulfamyl aniline, 2-(N-ethyl-N-phenyl amino alkylsulfonyl)-aniline, 4-dimethylamino alkylsulfonyl aniline, 4-diethylin alkylsulfonyl aniline, Sulphathiazole, 4-ADP base sulfone, 2-chloro-5-N-phenyl sulfamoyl base aniline, 2-methoxyl group-5-N, N-diethyl amino alkylsulfonyl aniline, 2,5-dimethoxy-4 '-N-phenyl sulfamoyl base aniline, 2-methoxyl group-5-benzyl alkylsulfonyl aniline, 2-phenoxy group alkylsulfonyl aniline, 2-(2 '-the chloro-phenoxy group) alkylsulfonyl aniline, 3-phenylsulfamoyl-4-monomethylaniline, two [4-(m-aminophenyl oxygen base) phenyl] sulfone, two [4-(p-aminophenyl oxygen base) phenyl] sulfone, two [3-methyl-4-(p-aminophenyl oxygen base) phenyl] sulfone, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, o-tolidine sulfone, 2,4 '-benzidine, 2,2 '-benzidine, 4,4 '-benzidine, 2,2 '-two chloro-4,4 '-benzidine, 3,3 '-two chloro-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-thiobis aniline, 2,2 '-the dithio dianiline, 4,4 '-the dithio dianiline, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, two (3-amino-4-chloro-phenyl-) sulfone, two (3, the 4-diamino-phenyl) sulfone, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 3,4 '-diamino diphenyl sulfone, 3,3 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl amine, 4,4 '-ethylenebis aniline, 4,4 '-diamino-2,2 '-the dimethyl dibenzyl, 3,3 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-phenoxy group) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 3-, 9, two (4-aminophenyl) fluorenes of 9-, 2, two (the 4-amino-benzene oxygen phenyl) propane of 2-, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 3,3 ', 4,4 '-the tetramino diphenyl ether, 3,3 ', 4,4 '-the tetramino sulfobenzide, 3,3 ', 4,4 '-the tetramino benzophenone, 3-aminobenzonitrile, 4-phenoxybenzamine, the 3-phenoxybenzamine, 4,4 '-methylene-bis-Ortho Toluidine, 4,4 '-(to the phenylene isopropylidene)-two-(2, the 6-xylidene(s)), adjacent chloro-p-Nitroaniline, adjacent nitro-p-Chlorobenzoic acid amide, 2,6-two chloro-4-N-methyl-p-nitroanilines, 5-chloro-2-N-methyl-p-nitroaniline, 2-amino-4-chlorophenol, o-Nitraniline, m-nitraniline, p-Nitroaniline, 2-methyl-4-N-methyl-p-nitroaniline, nitro-para-totuidine, 2-amino-5-nitrobenzonitrile, N-methyl p-aminophenol sulfate, 2, the 4-diaminophenol, N-(beta-hydroxyethyl)-Ortho-Aminophenol sulfuric ester, Sulphanilic Acid, m-sulfanilic acid, 4B acid, C acid, 2B acid, para-fluoroaniline, adjacent fluoroaniline, 3-chloro-4-fluoroaniline, 2,4 difluorobenzene amine, 2,3, the 4-trifluoromethyl aniline ,-5 amido benzotrifluoride, between toluylene diamine, 2-aminothiophenol, 2-amino-3-bromo-5-nitrobenzonitrile, diphenylamine, to amino-diphenyl-amine, the octyl group diphenylamine, 2-methyl-4-methoxyl group diphenylamine, N, N-phenylbenzene-P-pHENYLENE dI AMINE, dianisidine, 3,3 '-dichlorobenzidine, 4,4 '-diamino Stilbene-2,2 '-disulfonic acid, the benzyl ethylaniline, 1, the 8-naphthylene diamine, sodium naphthionate, 2-amino-1-naphthalene sulfonic aicd, H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, 1,4-diamino-2,3-dichloroanthraquinone etc.; With heterogeneous ring compound amine such as 3-amino-1,2,4-triazole, 2-aminopyridine, the 3-aminopyridine, 4-aminopyridine, alpha-amino group-ε-Ji Neixianan, acetylguanamine, 2,4-diamino-6-[2 '-methylimidazolyl-(1)] ethyl-S-triazine, 2,3 diamino pyridine, 2,5-diamino-pyridine, 2,3,5-triamino pyridine, 1-amino-4-methylpiperazine, 1-(2-amino-ethyl) piperazine, two (aminopropyl) piperazine, N-(3-aminopropyl) morpholine etc.In the middle of these, aromatic monoamine is preferred the use.
The alkylol cpd of mutual-through type (u) has no particular limits, as long as it is the polyol compound with two or more OH bases.Alkylol cpd comprises glycol such as ethylene glycol, glycol ether, triglycol, 1, ammediol, 1,2-propylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, hexylene glycol, 1,9-nonanediol, neopentyl glycol, methyl pentanediol etc.; Aliphatic polyol such as glycerine, Viscotrol C, TriMethylolPropane(TMP), trimethylolethane, hexanetriol, tetramethylolmethane, Alpha-Methyl glucosides, sorbyl alcohol, sucrose etc.; Polyvalent alcohol such as polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, adipic acid ester deutero-polyvalent alcohol, the epoxy group(ing) modified polyalcohol, polyester ether polylol, polycarbonate polyol, polycaprolactone glycol, the polyvalent alcohol of amine modification, the mixture (as glycerine and propylene glycol) that adds to a kind of polyhydroxy-alcohol or two or more polyhydroxy-alcohols by the mixture (for example oxyethane and propylene oxide) with a kind of oxyalkylene or two or more oxyalkylenes is gone up the polyether glycol that obtains, the acryl polyvalent alcohol, fluoridize polyvalent alcohol, polybutadiene polyol, poly-hydroxy polyvalent alcohol, Viscotrol C deutero-polyvalent alcohol, polymer polyatomic alcohol, halogen-containing polyvalent alcohol, phosphorated polyvalent alcohol etc.; With alkanolamine such as N-alkyl diethanolamine, N-alkyl diisopropanolamine (DIPA), trolamine, tri-isopropanolamine, N, N, N ', N '-four (2-hydroxyethyl) ethylene diamine, N, N, N ', N ' ,-four (2-hydroxypropyl) ethylene diamine etc.In the middle of these, glycol, aliphatic polyol, alkanolamine and the polyvalent alcohol with the molecular weight below 2,000 or 2,000 are preferred the uses.
The amine compound of general formula (XVII) for example comprise aromatic diamine as 4,4 '-diamino-3,3 '-the diethyl ditan, 4,4 '-diamino-benzanilide, 3, the 5-diaminochlorobenzene, diamino-diphenyl ether, 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane, 3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane, tolidine alkali, dianisidine, two [4-(m-aminophenyl oxygen base) phenyl] sulfone, two [4-(p-aminophenyl oxygen base) phenyl] sulfone, two [3-methyl-4-(p-aminophenyl oxygen base) phenyl] sulfone, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, o-tolidine sulfone, 2,4 '-benzidine, 2,2 '-benzidine, 4,4 '-benzidine, 2,2 '-two chloro-4,4 '-benzidine, 3,3 '-two chloro-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-thiobis aniline, 2,2 '-the dithio dianiline, 4,4 '-the dithio dianiline, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, two (3-amino-4-chloro-phenyl-) sulfone, two (3, the 4-diamino-phenyl) sulfone, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 3,4 '-diamino diphenyl sulfone, 3,3 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenylamine, 4,4 '-ethylenebis aniline, 4,4 '-diamino-2,2 '-the dimethyl dibenzyl, 3,3 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-phenoxy group) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 3-, 9, two (4-aminophenyl) fluorenes of 9-, 2, two (the 4-amino-benzene oxygen phenyl) propane of 2-, 4,4 '-two (4-amino-benzene oxygen) biphenyl, dianisidine, 3,3 '-dichlorobenzidine etc.Wherein γ 1 is that the amine compound of the general formula (XVII) of alkylsulfonyl or methylene radical is preferred.
In order to obtain each urea-urea hydride compounds of of the present invention first to the 4th aspect, isocyanic ester and corresponding reagent are mixed, in organic solvent or under the solvent-free situation, to react, after this, filter crystallization, desolvations etc. with the collection crystal, thereby obtain required compound.Reaction has the material of two or more groups in can excessive use molecule and another material with this radical reaction is carried out with the method that small portion adds to wherein.When this method of employing, might only make a reaction in two or more groups.In addition, preferred this system of thoroughly stirring is so that the material that adds fully disperses after interpolation immediately.More than be applicable to any of urea-urea hydride compounds of exemplifying here.The method of reaction is not limited to above method, can adopt any method, as long as can obtain as above identical result.As each reaction reagent, can use one or more compounds according to purpose.As solvent, can use any solvent, as long as it not with the functional group reactions of isocyanate group and reaction reagent.Solvent for example comprises aliphatic hydrocarbon, alicyclic hydro carbons, aromatic hydrocarbons, chlorination aliphatic hydrocarbon, chlorinating aromatic hydro carbons, alicyclic hydro carbons of chlorination and ketone.It is particularly preferred that dissolving isocyanic ester and reaction product have the methyl ethyl ketone, toluene of low solubility etc. therein.The reaction product that obtains by above reaction process is simplification compound always not, but can obtain the mixture of the different compound of substituting group position in some cases.
The specific examples of the urea-urea hydride compounds of of the present invention first to the 4th aspect is following compound ((S-1)-(S-70)).
Obtain that urea-urea alkane composition preferably includes 50wt% or more than the 50wt% according to each urea-urea alkane composition of the 5th to the 12 aspect of the present invention and the production method by the 13 to the 20 aspect of the present invention, more preferably 60wt% or more than the 60wt%, further preferred 70wt% or the above urea-urea hydride compounds of 70wt%, have in the molecule of described urea-urea hydride compounds at least one urea alkyl (NHCOO-) and at least one urea groups (NHCONH-), urea alkyl and urea groups add up to 2-10, and have 5,000 or 5,000 following molecular weight.
This urea-urea alkane composition can be used in combination with colourless or light dyestuff former, to obtain to be used for the color former of thermal recording medium or pressure sensitive recording material.This color former is very effective, and it has the excellent ability of adding lustre to and printed matter retention.
Urea-urea hydride compounds as the main component of urea-urea alkane composition has at least one urea groups and at least one urea alkyl in molecule.Urea groups and urea alkyl are preferably through at least one compound residue (hereinafter being referred to as this structure division urea-urea-alkyl structure part) adjacent one another are.Urea alkyl and urea groups total no more than 10 and be no less than 2, preferred no more than 10 and be no less than 3, more preferably no more than 10 and be no less than 4.
The urea alkyl in urea-urea hydride compounds molecule and the ratio of urea groups preferably 1: 3-3: 1, more preferably 1: 2-2: 1, most preferably 1: 1.The molecular weight of urea-urea hydride compounds is below 5,000 or 5,000, below preferred 2,000 or 2,000.
Urea-urea hydride compounds according to the content in each urea-urea alkane composition aspect the 5th to the 12 of the present invention is being 50wt% or more than the 50wt%.This urea-urea alkane composition can be produced by simple relatively production method.On the other hand, it can show excellent performance, because a high proportion of urea-urea hydride compounds can show excellent colour developing ability and retention, these are that color former is needed.In addition, as urea-urea hydride compounds, can use the mixture of simplification compound or two or more compounds (comprising isomer).
In addition, two or more mixtures that comprise the compound of isomer can be used as urea-urea hydride compounds, to improve colour developing ability, retention etc.
On the other hand, urea of the present invention-urea hydride compounds can suitably dilute with the material that can not weaken effect of the present invention.But this thinner for example comprises the material of hot melt, acid developer, and amine compound, isocyanate compound, carbamide compound, urea hydride compounds etc. are hereinafter with described.In the middle of these, carbamide compound and urea hydride compounds with the structure that is similar to urea-urea hydride compounds are preferred, because they can improve sensitivity.In addition, be preferred by the compound that the reaction of polyisocyanate compound and oxy-compound or aminocompound is obtained.This thinner preferably is contained in the gained dilution with the ratio based on the 0.0001-50wt% of urea-urea hydride compounds and thinner gross weight.The content of thinner is more preferably 40wt% or below the 40wt%, also more preferably 30wt% or below the 30wt%, so that show retention.The content of thinner is more preferably 0.01wt% or more than the 0.01wt%, also more preferably 1wt% or more than the 1wt%, to improve sensitivity.In some cases, this thinner of preparation in the building-up reactions of urea-urea hydride compounds.When adding thinner,, preferably in synthetic reaction process, add for improving sensitivity.For example, preferably comprise thinner and in molecular structure, have at least one urea groups and at least one urea alkyl (ading up to 2-10) and have 5,000 or 5, the urea of the urea of the molecular weight below 000-urea hydride compounds-urea alkane composition is characterized in that containing the thinner of 0.0001-50wt% ratio.Under the situation of the composition that the composition aspect the 8th to the 12 of the present invention and the production method by the 13 to the 20 aspect of the present invention are produced, also found identical effect.
Consider preferably have the colourless or light solid of fusing point according to each urea-urea alkane composition of the 5th to the 12 aspect of the present invention from the application thermal recording medium.Preferably 40 ℃-300 ℃ of the fusing points of composition are more preferably 60 ℃-260 ℃.
As any urea-urea alkane method for compositions of producing according to the 5th to the 12 aspect of the present invention, the preferred employing forms one or more urea alkyl from least one isocyanate group of polyisocyanate compound and the hydroxyl of oxy-compound, forms the method for one or more urea groups then from the amino of unreacted isocyanate group of the residue of identical polyisocyanate compound and aminocompound; Or form one or more urea groups from least one isocyanate group of polyisocyanate compound and the amino of aminocompound, form the method for one or more urea alkyl then from the hydroxyl of unreacted isocyanate group of the residue of identical polyisocyanate compound and oxy-compound.
When forming one or more urea alkyl from polyisocyanate compound and oxy-compound, can obtain urea-urea alkane composition effectively by the following method: use the polyisocyanate compound excessive with respect to hydroxyl, with amount and the oxy-compound bonding of polyisocyanate compound with the hydroxyl of 1 molecule/oxy-compound, so that the only isocyanic ester radical reaction of polyisocyanate compound and stay at least one unreacted isocyanate group, make the reaction of unreacted isocyanate group of residue and aminocompound then, to form one or more urea groups.In this case, preferably, polyisocyanate compound and oxy-compound form one or more urea alkyl by being reacted, make that the ratio of hydroxyl equivalent number of the mole number of polyisocyanate compound and oxy-compound is 100/1-1/2, the ratio of the isocyanate group equivalents of polyisocyanate compound and the hydroxyl equivalent number of oxy-compound is 1000/1-1/1.
When being added to oxy-compound in the polyisocyanate compound, oxy-compound preferably adds with aliquot, makes polyisocyanate compound always be present in the reaction system in the excessive mode of relative hydroxyl.When the ratio of the hydroxyl equivalent number of mole number that is reflected at polyisocyanate compound and oxy-compound near 1/1, when for example carrying out under the 5/1-1/2, this addition means is particularly preferred.
Similarly, when when polyisocyanate compound and aminocompound form one or more urea groups, urea-urea alkane composition can obtain effectively by the following method: use the polyisocyanate compound excessive with respect to amino, polyisocyanate compound is incorporated into aminocompound with the amount of the amino of 1 molecule/aminocompound, a so that isocyanic ester radical reaction of polyisocyanate compound and stay at least one unreacted isocyanate group, make the reaction of unreacted isocyanate group of residue and oxy-compound then, to form one or more urea alkyl.In this case, preferably, polyisocyanate compound and aminocompound form one or more urea groups by being reacted, make that the ratio of amino equivalent number of the mole number of polyisocyanate compound and aminocompound is 100/1-1/2, the ratio of the isocyanate group equivalents of polyisocyanate compound and the amino equivalent number of aminocompound is 1000/1-1/1.
When being added to aminocompound in the polyisocyanate compound, preferably add aminocompound with aliquot, make polyisocyanate compound amino relatively excessive being present in the reaction system always.When the ratio of the amino equivalent number of mole number that is reflected at polyisocyanate compound and aminocompound near 1/1, when for example carrying out under the 5/1-1/2, this addition means is particularly preferred.
In the method for producing according to any urea alkane-urea compositions aspect the 5th to the 12 of the present invention, the polyisocyanate compound that is used to form one or more urea alkyl preferably carries out under not having the situation of solvent with the reaction of oxy-compound or by not having the oxy-compound of solvent, the dilution of oxy-compound with solvent or the dispersion of oxy-compound in solvent continuously or by carrying out in the interpolation of part ground, the dilution that drips or be poured into the polyisocyanate compound with solvent or the dispersion of polyisocyanate compound in solvent.Similarly, the reaction that is used to form the polyisocyanate compound of one or more urea groups and aminocompound can be carried out under the situation of solvent not having, or by not carrying out having the aminocompound of solvent, the dilution of aminocompound with solvent or the dispersion of aminocompound in solvent to add, drip or be poured in the dilution of the polyisocyanate compound with solvent or the dispersion of polyisocyanate compound in solvent continuously or by part ground.
Comprise that be particularly preferred with the above production method that aliquot is added in the polyisocyanate compound with oxy-compound or aminocompound under the following situation: in the reaction method of producing urea-urea alkane composition, in the molecule of polyisocyanate compound, stay at least one isocyanate group, make the reaction of all the other isocyanate group and oxy-compound or aminocompound to form one or more urea alkyl or urea groups respectively.And, when the oxy-compound with two or more hydroxyls or aminocompound with two or more amino when having the polyisocyanate compound reaction of two or more isocyanate group, described production method is preferred.
When carrying out above reaction, preferred this system of thoroughly stirring, thus make the hydroxyl or the aminocompound that add, drip or pour in the polyisocyanates disperse immediately and fully.Preference is selected agitating vane or is set thoroughly stirring reaction system of baffle plate as by the stirring velocity in the conditioned reaction device.
The preferred reaction that forms the reaction of one or more urea alkyl separately and continuously and form one or more urea groups.When they carried out simultaneously, the urea in urea-urea alkane composition-urea hydride compounds content undesirably was lowered.The preferred reaction of carrying out these reactions that form the urea alkyl continuously and forming urea groups.In the method for the invention, because need not separate in process of production and purification step, can simplify production by carrying out two reactions steps continuously.
In production according to any urea-urea alkane composition aspect the 5th to the 12 of the present invention, when using the adducts of polyisocyanates and oxy-compound, this adducts is the isocyanic ester that has had one or more urea alkyl in the molecule, can obtain urea-urea alkane composition by this adducts and aminocompound are reacted.In this case, preferably, form one or more urea groups by reacting with amino equivalence ratio, and then remove unreacted aminocompound with 2/1 to 1/100 isocyanate group.
In production according to any urea-urea alkane composition aspect the 5th to the 12 of the present invention, when using the adducts of polyisocyanates and aminocompound, this adducts is the isocyanic ester that has had one or more urea groups in the molecule, can obtain urea-urea alkane composition by this adducts and oxy-compound are reacted.In this case, preferably, form one or more urea alkyl by reacting, and then remove unreacted oxy-compound with the equivalence ratio of 2/1 to 1/100 isocyanate group and hydroxyl.
When using solvent to react in according to the production of any urea-urea alkane composition aspect the 5th to the 12 of the present invention, solvent is not special restriction, if it not with reaction such as isocyanate group.Solvent for example comprises aliphatic hydrocarbon, alicyclic hydro carbons, aromatic hydrocarbons, chlorination aliphatic hydrocarbon, chlorinating aromatic hydro carbons, the alicyclic hydro carbons of chlorination, ketone and phosphoric acid ester.Dissolving isocyanic ester and reaction product have the acetone of low solubility therein, and methyl ethyl ketone, toluene etc. are particularly preferred.When needs have high solvency power to isocyanic ester, phosphoric acid ester, especially trimethyl phosphite 99 is preferred.
When using this solvent, the formation of one or more urea alkyl and the formation of one or more urea groups are preferably carried out in identical solvent, with reaction that is easy to re-use solvent and form urea groups continuously and the reaction that forms the urea alkyl.
Polyisocyanates and oxy-compound and/or aminocompound reaction are 0 ℃ to 300 ℃ with the temperature of reaction that forms one or more urea alkyl and/or one or more urea groups, preferred 5 ℃ to 200 ℃, and more preferably 10 ℃ to 150 ℃.According to selected polyisocyanate compound, oxy-compound and aminocompound come suitable conditioned reaction temperature.Can also be suitable for forming urea alkyl and urea groups under the differing temps of each self-forming.
In polyisocyanates and oxy-compound and/or aminocompound reaction, can use catalyzer, to form one or more urea alkyl and/or one or more urea groups.Catalyzer for example comprises tertiary amine compound such as triethylamine, 1, and 4-diazabicyclo (2,2,2) octane etc.; With organic acid tin salt such as dibutyl tin laurate etc.Usually catalyzer is 1-10 with respect to the concentration of isocyanate compound, 000ppm, preferred 10-2,000ppm.In the above catalyzer that exemplifies, tertiary amine compound is preferred.
Repeat production method step 2 of the present invention time or more than 2 times by the oxy-compound that uses the aminocompound for example have two or more amino and have two or more hydroxyls, can obtain to contain and in molecule, have a plurality of ureas-urea-urea alkane composition of the urea-urea hydride compounds of urea-alkyl structure part.Because in each step, can obtain sufficiently high reaction yield, so production method of the present invention can relatively easily be produced the urea-urea alkane composition with high performance nature.
The polyisocyanate compound of each use is not special restriction in the 5th to the 12 aspect of the present invention, as long as it has the two or more isocyanate group that are bonded in respectively on the carbon atom.Polyisocyanate compound for example comprises phenylene vulcabond, the metaphenylene vulcabond, adjacent phenylene vulcabond, 2,5-dimethoxy benzene-1,4-vulcabond, 2, the 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethanediisocyanate, the o-tolidine vulcabond, the diphenyl ether vulcabond, l,5 naphthylene diisocyanate, the dianisidine vulcabond, 9-ethyl carbazole-3,6-vulcabond, 3,3 '-dimethyl-4,4 '-diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, three (4-phenyl isocyanate) thiophosphatephosphorothioate, 4,4 ', 4 " three isocyanatos-2; 5-dimethoxytrityl amine, 4,4 '; 4 "-three isocyanatos-triphenylamine, between eylylene diisocyanate, lysinediisocyanate, dimer acid diisocyanate, isopropylidene is two-4-cyclohexyl-isocyanic ester, dicyclohexyl methane diisocyanate and methylcyclohexane diisocyanate.As polyisocyanate compound, can also use vulcabond dimer such as N, N '-(4,4 '-dimethyl-3,3 '-phenylbenzene two isocyanatos)-urea diketone (Desmodule TT, trade(brand)name), toluene diisocyanate dimer; With diisocyanate trimer as 4,4 ', 4 " trimethylammonium-3,3 ', 3 " three isocyanatos-2,4,6-triphenyl cyanurates.Can also use tolylene diisocyanate, the water adduction isocyanic ester of diphenylmethanediisocyanate etc., as 1, two (3-isocyanato-4-aminomethyl phenyl) ureas of 3-; The trimethylolpropane adduct of polyvalent alcohol adducts such as tolylene diisocyanate (Desmodule L and Coronate L, trade(brand)name); And amine adduct.Can also use the compound with two or more isocyanate group (content of these reference is quoted for reference here) of the row of the isocyanate compound described in the specification sheets of the specification sheets that belongs to JP-A-10-76757 and JP-A-10-95171 and isocyanic ester addition compound.The compound that more than exemplifies can separately or be used in combination.
In the above compound that exemplifies, the preferred embodiment of polyisocyanate compound is the aromatic polyisocyanate with the isocyanate group that is bonded in phenyl ring, as to phenylene vulcabond, the metaphenylene vulcabond, adjacent phenylene vulcabond, 2, the 4-tolylene diisocyanate, 2, the 6-tolylene diisocyanate, diphenylmethanediisocyanate, the o-tolidine vulcabond, diphenyl ether vulcabond, 1, the 5-naphthalene diisocyanate, triphenylmethane triisocyanate, N, N '-(4,4 '-dimethyl-3,3 '-phenylbenzene-two isocyanato) urea diketone (Desmodule TT, trade(brand)name), 4,4 ', 4 " trimethylammonium-3,3 ', 3 " three isocyanatos-2,4,6-triphenyl cyanurate, 1, two (3-isocyanato-4-aminomethyl phenyl) ureas of 3-, the trimethylolpropane adduct of tolylene diisocyanate (Desmodule L and Coronate L, trade(brand)name) etc.The particularly preferred example of polyisocyanate compound is a tolylene diisocyanate.In the middle of tolylene diisocyanate, 2,4 toluene diisocyanate is preferred.Except 2,4 toluene diisocyanate, 2,4 toluene diisocyanate and 2, the mixture of 6-tolylene diisocyanate are generally on sale on market, can low price obtain, and can be used as polyisocyanate compound.
As reacting to form the oxy-compound of one or more urea alkyl, can mention phenolic compound and alkylol cpd with polyisocyanates.
Phenolic compound for example comprises phenol; cresols; xylenol; p-ethyl phenol; o-isopropyl phenol; Resorcinol; p-tert-butylphenol; to tert-octyl phenol, 2-cyclohexylphenol, 2-chavicol; the 4-indanol; thymol, beta naphthal, p-NP; orthomonochlorphenol; para-chlorophenol, 2, two (4-the hydroxyphenyl)-propane of 2-; 2; two (hydroxyphenyl) butane of 2-, 2, two (hydroxyphenyl) pentanes of 2-; 2; two (hydroxyphenyl) heptane of 2-, catechol, 3-methyl catechol; 3-methoxyl group catechol; pyrogallol, quinhydrones, toluhydroquinone; the 4-phenylphenol; p, p '-bis-phenol, 4-cumyl phenol; two (4-hydroxyphenyl) butylacetate; two (4-hydroxyphenyl) jasmal, two (4-hydroxyphenyl) sulfone, two (3-methyl-4-hydroxyphenyl) sulfone; two (3; 5-dimethyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4 '-methyl phenyl sulfone, 3-chloro-4-hydroxyphenyl-4 '-methyl phenyl sulfone; 3; 4-dihydroxyphenyl-4 '-methyl phenyl sulfone, 4-sec.-propyl oxygen base phenyl-4 '-the hydroxyphenyl sulfone, two (2-allyl group-4-hydroxyphenyl) sulfone; 4-hydroxyphenyl-4 '-the benzyloxy phenylsulfone; 4-isopropyl phenyl-4 '-the hydroxyphenyl sulfone, 4-hydroxyl-4 '-sec.-propyl oxygen base sulfobenzide, two (the 2-methyl-3-tertiary butyl-4-hydroxyphenyl) sulphur; 4; 4 '-dihydroxydiphenyl ether, 4,4 '-the sulfo-diphenol; 4; 4 '-dihydroxy benaophenonel, 2, two (4-hydroxyphenyl) HFC-236fa of 2-; 4; 4 '-dihydroxyl-ditan, 3,3 '-the dihydroxyl diphenylamine; two (4-hydroxy-3-methyl phenyl) sulphur; two (4-(2-hydroxyl)-phenyl) sulfone, 2,4 dihydroxyl benzophenone; 2; 2 ', 4,4 '-tetrahydroxybenzophenone; salol; salicylamide, 4-methyl hydroxybenzoate, 4-hydroxy benzoic acid benzyl ester; the 4-hydroxy-benzoic acid (4 '-the benzyl chloride base) ester; 1,2-pair (4 '-hydroxy-benzoic acid) ethyl ester, 1; 5-pair (4 '-hydroxy-benzoic acid) pentyl ester; 1,6-pair (4 '-hydroxy-benzoic acid) own ester, 3-hydroxyl phthalic dimethyl ester; the gallic acid stearyl ester; Progallin LA, methyl gallate, 4-methoxyphenol; 4-(benzyloxy) phenol; the 4-hydroxy benzaldehyde, 4-n-octyloxy Whitfield's ointment, 4-n-butoxy Whitfield's ointment; 4-n-pentyloxy Whitfield's ointment; 3-dodecyl oxygen base Whitfield's ointment, the positive hot acyloxy Whitfield's ointment of 3-, 4-n-octyloxy carbonylamino Whitfield's ointment and the positive capryloyl oxygen of 4-base carbonylamino Whitfield's ointment.
In the above phenolic compound that exemplifies, phenol is preferred with the phenol derivatives of following formula (w) expression and the bisphenol cpd of being represented by following formula (XVI):
Wherein the hydrogen atom of phenyl ring can be replaced by alkyl, cycloalkyl, phenyl, amide group, alkoxyl group, nitro, itrile group, halogen atom, formyl radical, dialkyl amido, tosyl group, methylsulfonyl or OH base; With
Wherein the hydrogen atom of each phenyl ring can be substituted the base replacement; this substituting group is aromatic substance residue, aliphatic cpd residue or heterogeneous ring compound residue preferably; substituting group also can be hydroxyl, nitro, itrile group, formamyl, sulfamyl, carboxyl, nitroso-group, amino, oxygen amino, nitro amino, diazanyl, urea groups, isocyanate group, sulfydryl, sulfo group or halogen atom; each residue can have one or more substituting groups, and δ is selected from-SO
2-,-O-,-(S)
n-,-(CH
2)
n-,-CO-,-CONH-,-NH-,-CH (COOR
1)-,-C (CF
3)
2-and-CR
2R
3-in group or do not have R
1, R
2And R
3Be alkyl independently, n is 1 or 2.
The term " aliphatic series " that uses in the situation aspect the 5th to the 12 of the present invention comprises term " alicyclic ".
The term " aliphatic cpd residue " that uses in the situation aspect the 5th to the 12 of the present invention is meant the residue by the carbon atom keyed jointing of the part of the aliphatic hydrocrbon in the residue.Term used herein " aromatic substance residue " is meant the residue by the carbon atom keyed jointing of aromatic ring in the residue such as phenyl ring.Term used herein " heterocyclic compound compounds residue " is meant the residue by the formation heterocyclic carbon atom keyed jointing in the residue.
The substituent preferred embodiment of aliphatic cpd residue, heterogeneous ring compound residue or aromatic substance residue is alkyl, cycloalkyl, phenyl, amide group, alkoxyl group, nitro, itrile group, halogen atom, formyl radical, dialkyl amido, tosyl group and methyl sulphonyl.
As alkylol cpd, can mention the compound of at least one the OH base that has on the carbon atom that is bonded in aliphatic cpd.The example of alkylol cpd is at Solvent Handbook, Kodansha Scientific Co., Ltd., the 9th printing (1989), the alcohol of describing in 327-420 page or leaf and the 772-817 page or leaf.Alkylol cpd for example comprises fatty alcohol such as methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, cyclopentanol, tertiary amyl alcohol, 2-amylalcohol, primary isoamyl alcohol, hexanol, 3-hexanol, hexalin, hexahydrobenzyl alcohol, 4-methyl-2-amylalcohol, enanthol, iso-heptanol, octanol (octanol), 2-ethyl-1-hexanol, octanol (capryl alcohol), nonyl alcohol, isononyl alcohol, decyl alcohol, hendecanol, dodecanol, tridecyl alcohol, tetradecanol, cetyl alcohol, Stearyl alcohol, isooctadecanol etc.; Unsaturated aliphatic is pure as vinyl carbinol, methallyl alcohol, crotyl alcohol, propargyl alcohol etc.; Fatty alcohol with keyed jointing aromatic substance residue thereon, as benzylalcohol, styryl carbinol etc.; Fatty alcohol with keyed jointing heterogeneous ring compound residue thereon, as the 2-piconol, 3-piconol, 4-piconol, furfuryl alcohol etc.; Halogenation fatty alcohol such as ethylene chlorhydrin, 1-chloro-3-hydroxy propane etc.; Glycol ether is as glycol monomethyl methyl ether, ethylene glycol monomethyl ether, the glycol monomethyl propyl ether, glycol monomethyl isopropyl ether, ethylene glycol monobutyl ether, the glycol monomethyl isobutyl ether, ethylene glycol mono hexyl ether, glycol monomethyl phenyl ether, the diglycol monotertiary methyl ether, carbiphene, diglycol monotertiary propyl ether, the diglycol monotertiary isopropyl ether, diglycol monotertiary butyl ether, diglycol monotertiary isobutyl ether, the diglycol monotertiary hexyl ether, diglycol monotertiary phenyl ether, propylene glycol monomethyl ether, propylene glycol list ethyl ether, propylene glycol list propyl ether, propylene glycol monoisopropyl ether, the propylene glycol single-butyl ether, propylene glycol list isobutyl ether, propylene glycol list phenyl ether, DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol list propyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol single-butyl ether, dipropylene glycol list isobutyl ether, dipropylene glycol list phenyl ether etc.; Glycol such as ethylene glycol, glycol ether, triglycol, 1, ammediol, 1,2-propylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, hexylene glycol, 1,9-nonanediol, neopentyl glycol, methyl pentanediol etc.; Aliphatic polyol such as glycerine, Viscotrol C, TriMethylolPropane(TMP), trimethylolethane, hexanetriol, tetramethylolmethane, Alpha-Methyl glucosides, sorbyl alcohol, sucrose etc.; Polyvalent alcohol such as polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, adipic acid ester deutero-polyvalent alcohol, epoxy group(ing) modified polyalcohol, polyester ether polylol, polycarbonate polyol, polycaprolactone glycol, the amine modified polyalcohol, one or both or the multiple mixture (glycerine and propylene glycol) that join polyhydroxy-alcohol by the mixture (for example oxyethane and propylene oxide) with a kind of oxyalkylene or two or more oxyalkylenes are gone up the polyether glycol that obtains, the acryl polyvalent alcohol, fluoridize polyvalent alcohol, polybutadiene polyol, poly-hydroxy polyvalent alcohol, Viscotrol C deutero-polyvalent alcohol, polymer polyatomic alcohol, halogen-containing polyvalent alcohol, phosphorated polyvalent alcohol etc.; With alkanolamine such as N, N-dialkyl group-thanomin, N, N-dialkyl group Yi Bingchunan, N-alkyl diethanolamine, N-alkyl diisopropanolamine (DIPA), trolamine, tri-isopropanolamine, N, N, N ', N '-four (2-hydroxyethyl) quadrol, N, N, N ', N ' ,-four (2-hydroxypropyl) quadrol etc.
In the above-mentioned alkylol cpd that exemplifies, have the fatty alcohol of 10 or 10 following carbon atoms, glycol ether, glycol, aliphatic polyol, polyvalent alcohol and alkanolamine with the molecular weight below 2,000 or 2,000 are preferred.
The alkylol cpd that more than exemplifies can separately or be used in combination, and the above-mentioned phenolic compound that exemplifies also can separately or be used in combination.
As reacting to form the aminocompound of one or more urea groups, can use any compound, as long as it has the one or more amino that are bonded in respectively on the carbon atom with polyisocyanate compound.Aminocompound for example comprises aromatic amine such as aniline, Ortho Toluidine, meta-aminotoluene, para-totuidine, o-anisidine, P-anisidine, p-phenetidine, N, N-dimethyl-right-phenylenediamine, N, N-diethyl-P-pHENYLENE dI AMINE, 2, the 4-dimethoxyaniline, 2, the 5-dimethoxyaniline, 3, the 4-dimethoxyaniline is to amino-Acetanilide, para-amino benzoic acid, Ortho-Aminophenol, Metha Amino Phenon, p-aminophenol, 2, the 3-xylidene(s), toluene 24 diamine, 3, the 4-xylidene(s), 2, the 6-xylidene(s), the 4-aminobenzonitrile, anthranilic acid, p-cresol is fixed, 2,5-dichlorphenamide bulk powder, 2, the 6-dichlorphenamide bulk powder, 3, the 4-dichlorphenamide bulk powder, 3,5-dichlorphenamide bulk powder, 2,4,5-trichloroaniline, alpha-naphthylamine, amino anthracene, o ethyl aniline, Ortho-Chloro aniline, m-chloro aniline, p-Chlorobenzoic acid amide, methylphenylamine, N-ethylaniline, N propyl aniline, N-butylaniline, N, N-diglycidylaniline, N, N-diglycidyl-Ortho Toluidine, N, N-etheric acid aniline, bromination trimethylphenyl ammonium, 4,4 '-diamino-3,3 '-the diethyl ditan, 4,4 '-the diaminobenzene formylaniline, 3,5-diaminochlorobenzene, diamino-diphenyl ether, 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane, 3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane, tolidine alkali, adjacent phenylenediamine, m-phenylenediamine, P-pHENYLENE dI AMINE, 2-chloro-P-pHENYLENE dI AMINE, dianisidine, methyl p-aminobenzoate, parathesin, para-amino benzoic acid n-propyl, the para-amino benzoic acid isopropyl ester, planoform, para-amino benzoic acid dodecyl ester, para-amino benzoic acid benzyl ester, adjacent aminobenzophenone, m-aminophenyl ethyl ketone, para-aminoacetophenone, m-aminophenyl methane amide, anthranilamide, Para Amino Benzamide, right-amino-N-methyl-benzamide, 3-amino-4-methyl benzamide, 3-amino-4-methoxy benzamide, 3-amino-4-chlorobenzamide, right-(N-phenyl amino formyl radical) aniline, right-[N-(4-chloro-phenyl-) formamyl] aniline, right-[N-(4-aminophenyl)-formamyl] aniline, 2-methoxyl group-5-(N-phenyl amino formyl radical)-aniline, 2-methoxyl group-5-[N-(2 '-methyl-3 '-chloro-phenyl-) formamyl] aniline, 2-methoxyl group-5-[N-(2 '-chloro-phenyl-)-formamyl] aniline, 5-acetylamino-2-anisidine, the 4-acetylaminoaniline, 4-(N-methyl-N-kharophen) aniline, 2,5-diethoxy-4-(N-benzoyl-amido) aniline, 2,5-dimethoxy-4 '-(N-benzoyl-amido) aniline, 2-methoxyl group-4-(N-benzoyl-amino)-5-monomethylaniline, 4-sulfamyl aniline, 3-sulfamyl aniline, 2-(N-ethyl-N-phenyl amino alkylsulfonyl)-aniline, 4-dimethylamino alkylsulfonyl aniline, 4-diethylin alkylsulfonyl aniline, Sulphathiazole, 4-ADP base sulfone, 2-chloro-5-N-phenyl sulfamoyl base aniline, 2-methoxyl group-5-N, N-diethyl amino alkylsulfonyl aniline, 2,5-dimethoxy-4 '-N-phenyl sulfamoyl base aniline, 2-methoxyl group-5-benzyl alkylsulfonyl aniline, 2-phenoxy group alkylsulfonyl aniline, 2-(2 '-the chloro-phenoxy group) alkylsulfonyl aniline, 3-Phenylsulfamoyl base-4-monomethylaniline, two [4-(m-aminophenyl oxygen base) phenyl] sulfone, two [4-(p-aminophenyl oxygen base) phenyl] sulfone, two [3-methyl-4-(p-aminophenyl oxygen base) phenyl] sulfone, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, the o-tolidine sulfone, 2,4 '-benzidine, 2,2 '-benzidine, 4,4 '-benzidine, 2,2 '-two chloro-4,4 '-benzidine, 3,3 '-two chloro-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-thiobis aniline, 2,2 '-the dithio dianiline, 4,4 '-the dithio dianiline, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, two (3-amino-4-chloro-phenyl-) sulfone, two (3, the 4-diamino-phenyl) sulfone, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 3,4 '-diamino diphenyl sulfone, 3,3 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl amine, 4,4 '-ethylenebis aniline, 4,4 '-diamino-2,2 '-the dimethyl dibenzyl, 3,3 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-phenoxy group) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 3-, 9, two (4-aminophenyl) fluorenes of 9-, 2, two (the 4-amino-benzene oxygen phenyl) propane of 2-, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 3,3 ', 4,4 '-the tetramino diphenyl ether, 3,3 ', 4,4 '-the tetramino sulfobenzide, 3,3 ', 4,4 '-the tetramino benzophenone, the 3-aminobenzonitrile, the 4-phenoxybenzamine, 3-phenoxybenzamine, 4,4 '-methylene-bis-Ortho Toluidine, 4,4 '-(to the phenylene isopropylidene)-two-(2, the 6-xylidene(s)), adjacent chloro-p-Nitroaniline, adjacent nitro-p-Chlorobenzoic acid amide, 2,6-two chloro-4-N-methyl-p-nitroanilines, 5-chloro-2-N-methyl-p-nitroaniline, 2-amino-4-chlorophenol, o-Nitraniline, m-nitraniline, p-Nitroaniline, 2-methyl-4-N-methyl-p-nitroaniline, nitro-para-totuidine, 2-amino-5-nitrobenzonitrile, N-methyl p-aminophenol sulfate, 2, the 4-diaminophenol, N-(beta-hydroxyethyl)-Ortho-Aminophenol sulfuric ester, Sulphanilic Acid, m-sulfanilic acid, 4B acid, C acid, 2B acid, para-fluoroaniline, adjacent fluoroaniline, 3-chloro-4-fluoroaniline, 2,4 difluorobenzene amine, 2,3, the 4-trifluoromethyl aniline, between-5 amido benzotrifluoride, a toluylene diamine, 2-aminothiophenol, 2-amino-3-bromo-5-nitrobenzonitrile, diphenylamine is to amino-diphenyl-amine, the octyl group diphenylamine, 2-methyl-4-methoxyl group diphenylamine, N, N-phenylbenzene-P-pHENYLENE dI AMINE, dianisidine, 3,3 '-dichlorobenzidine, 4,4 '-diaminostilbene-2,2 '-disulfonic acid, the benzyl ethylaniline, 1, the 8-naphthylene diamine, sodium naphthionate, 2-amino-1-naphthalene sulfonic aicd, H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, 1,4-diamino-2,3-dichloroanthraquinone etc.; With heterogeneous ring compound amine such as 3-amino-1,2,4-triazole, 2-aminopyridine, the 3-aminopyridine, 4-aminopyridine, alpha-amino group-ε-Ji Neixianan, acetylguanamine, 2,4-diamino-6-[2 '-methylimidazolyl-(1)] ethyl-S-triazine, 2,3 diamino pyridine, 2,5-diamino-pyridine, 2,3,5-triamino pyridine, 1-amino-4-methylpiperazine, 1-(2-amino-ethyl) piperazine, two (aminopropyl) piperazine, N-(3-aminopropyl) morpholine etc.; With aliphatic amine such as methylamine, ethamine, dimethylamine, diethylamine, stearylamine, allyl amine, diallyl amine, isopropylamine, diisopropylamine, 2-DEHA, thanomin, 3-(2-ethyl hexyl oxy) propylamine, 3-ethoxycarbonyl propyl amine, diisobutyl amine, 3-(diethylin) propylamine, D2EHA di 2 ethylhexyl amine, 3-(dibutylamino) propylamine, tert-butylamine, propylamine, 3-(methylamino) propylamine, 3-(dimethylamino) propylamine, 3 methoxypropyl amine, methyl hydrazine, 1-methyl butyl amine, methane diamines, 1,4-diaminobutane, hexanaphthene methylamine, cyclo-hexylamine, 4-methylcyclohexyl amine, 2-bromotrifluoromethane amine, 2-methoxy ethyl amine, 2-ethoxyl methyl amine, 2-amino-1-propyl alcohol, the 2-amino butanol, 3-amino-1,2-propylene glycol, 1,3-diamino-2-hydroxy propane, 2-aminoothyl mercaptan, quadrol, diethylenetriamine, hexamethylene-diamine etc.
In addition, in the above aminocompound that exemplifies, aromatic amine is preferred, and has that at least one is amino and be particularly preferred with following formula (z) or the anils (VIII) represented:
R wherein
1And R
2Be hydrogen atom, halogen atom, alkyl, alkoxyl group or amino independently;
Or
R wherein
1, R
2, R
3And R
4Be hydrogen atom, halogen atom, alkyl, alkoxyl group or amino independently, X
1And X
3Be group amino or that represent with formula (b) independently:
Y
1Be-SO
2-,-O-,-(S)
n-,-(CH
2)
n-,-CO-,-CONH-,-NH-,-CH (COOR
1)-,-C (CF
3)
2-,-CR
2R
3-and with in the group of any one expression of formula (a) any one:
Or Y
1There is not R
1, R
2And R
3Each is alkyl naturally, and n is 1 or 2.
These amine compound can separately or be used in combination.
The of the present invention the 21 and the 22 aspect in each in be used as developer urea-urea hydride compounds be meant and in molecule, have at least one urea groups (NHCONH-) and at least one urea alkyl (compound NHCOO-).
Be known that the compound with one or more urea groups has color developing effect, but their use in practice, because the colour developing density that their produce is low and have an insufficient shelf stability.Yet, surprisingly, urea-urea the hydride compounds that has at least one urea groups and at least one urea alkyl in the molecule is colourless or the excellent developer of light dyestuff former, comprises the color composition of urea-urea hydride compounds and dyestuff former and has obtained high colorant density and had excellent shelf stability by the recording materials that use this color composition to obtain.
It is unclear that though this urea-urea hydride compounds has the mechanism of excellent color developing effect, this effect is owing to the interaction between intramolecularly urea groups and the urea alkyl by inference.
As the of the present invention the 21 and the 22 aspect each in be used as the urea-urea hydride compounds of developer, can use any compound, if it in molecule, have at least one urea groups (NHCONH-) and at least one urea alkyl (NHCOO-).Urea-urea hydride compounds is aromatic substance or heterogeneous ring compound preferably.In addition, preferably wherein aromatic substance residue or heterogeneous ring compound residue directly are bonded in the compound of each end of each urea groups and urea alkyl to urea-urea hydride compounds.More preferably, (NHCONH-) (NHCOO-), can there be one or more sulfonic group (SO in the molecule except urea groups with the urea alkyl
2-), amide group is (NHCO-) or isopropylidene (C (CH
3)
2-), and these groups directly are not incorporated into urea groups.
The molecular weight of urea-urea hydride compounds is preferably below 5,000 or 5,000, more preferably below 2,000 or 2,000.The urea groups in urea-urea hydride compounds and the sum of urea alkyl preferably below 20 or 20, are more preferably below 10 or 10.The urea groups in the molecular structure of urea-urea hydride compounds and the ratio of urea alkyl preferably 1: 3-3: 1, especially 1: 2-2: 1.
When being used for thermal recording medium, preferred urea-urea hydride compounds has fusing point.Fusing point is preferably at 40 ℃ to 500 ℃, especially in 60 ℃ to 300 ℃ the scope.
Synthesize the of the present invention the 21 and the 22 aspect each in be used as the urea-urea hydride compounds of developer method be not special restriction, as long as form at least one urea groups (NHCONH-) and at least one urea alkyl (NHCOO-).Produce the method for urea-urea hydride compounds because its simplicity but preferred by isocyanate compound and the reaction that contains the compound of OH base and amine compound.
In detail, in the present invention urea-urea hydride compounds is used as under the situation of developer, isocyanic ester with at least two isocyanate group is as starting raw material, and form one or more urea alkyl by making to react with the compound that contains the OH base except the isocyanate group at least one, after this, by being reacted, remaining isocyanate group and amine compound form one or more urea groups.Can also form one or more urea groups by making, form one or more urea alkyl by the residual isocyanate base is reacted with the compound that contains the OH base then except the isocyanate group at least one and amine compound at first react.
Initial isocyanic ester is not special restriction, as long as it has two or more isocyanate group.Initial isocyanic ester for example comprises phenylene vulcabond, 2, and 5-dimethoxy benzene-1, the 4-vulcabond, 2,4 toluene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethanediisocyanate, the o-tolidine vulcabond, diphenyl ether vulcabond, 1, the 5-naphthalene diisocyanate, dianisidine vulcabond, 9-ethyl carbazole-3, the 6-vulcabond, 3,3 '-dimethyl-4,4 '-diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, three (4-phenyl isocyanato) thiophosphatephosphorothioate, 4,4 ', 4 " three isocyanatos-2; 5-dimethoxytrityl amine, 4,4 '; 4 "-three isocyanatos-triphenylamine, between eylylene diisocyanate, lysinediisocyanate, dimer acids vulcabond, isopropylidene is two-4-cyclohexyl-isocyanic ester, dicyclohexyl methane diisocyanate and methylcyclohexane diisocyanate.As initial isocyanic ester, can also use vulcabond dimer such as N, N '-(4,4 '-dimethyl-3,3 '-phenylbenzene two isocyanatos)-urea diketone (Desmodule TT, trade(brand)name), toluene diisocyanate dimer; With diisocyanate trimer as 4,4 ', 4 " trimethylammonium-3,3 ', 3 " three isocyanatos-2,4,6-triphenyl cyanurates.Can also use tolylene diisocyanate, the water adduction isocyanic ester of diphenylmethanediisocyanate etc., as 1, two (3-isocyanato-4-aminomethyl phenyl) ureas of 3-; The trimethylolpropane adduct of polyvalent alcohol adducts such as tolylene diisocyanate (Desmodule L, trade(brand)name); And amine adduct.Can also use the compound with two or more isocyanate group of the row of the isocyanate compound described in the specification sheets of the specification sheets that belongs to JP-A-8-225445 and JP-A-8-250623 and isocyanic ester addition compound.
The particularly preferred example of initial isocyanic ester is a tolylene diisocyanate.In the middle of tolylene diisocyanate, 2,4 toluene diisocyanate is preferred.Except 2,4 toluene diisocyanate, 2,4 toluene diisocyanate and 2, the mixture of 6-tolylene diisocyanate are on sale on market usually, can obtain at a low price, also can be used as initial isocyanic ester.
As with the initial isocyanate reaction of developer urea-urea hydride compounds to form the amine compound of one or more urea groups, can use any compound, as long as it has one or more amino.Amine compound for example comprises aromatic amine such as aniline, Ortho Toluidine, meta-aminotoluene, para-totuidine, o-anisidine, P-anisidine, p-phenetidine, N, accelerine, N, N-Diethyl Aniline, N, N-dimethyl-right-phenylenediamine, N, N-diethyl-P-pHENYLENE dI AMINE, 2,4-dimethoxyaniline, 2, the 5-dimethoxyaniline, 3, the 4-dimethoxyaniline, to amino-Acetanilide, para-amino benzoic acid, Ortho-Aminophenol, Metha Amino Phenon, p-aminophenol, 2, the 3-xylidene(s), toluene 24 diamine, 3,4-xylidene(s), 2, the 6-xylidene(s), 4-aminobenzonitrile, anthranilic acid, p-cresol is fixed, and 2, the 5-dichlorphenamide bulk powder, 2,6-dichlorphenamide bulk powder, 3, the 4-dichlorphenamide bulk powder, 3, the 5-dichlorphenamide bulk powder, 245 trichloroaniline, alpha-naphthylamine, amino anthracene, o ethyl aniline, Ortho-Chloro aniline, m-chloro aniline, p-Chlorobenzoic acid amide, methylphenylamine, N-ethylaniline, N propyl aniline, the N-butylaniline, N, N-diglycidylaniline, N, N-diglycidyl-Ortho Toluidine, N, N-etheric acid aniline, bromination trimethylphenyl ammonium, 4,4 '-diamino-3,3 '-the diethyl ditan, 4,4 '-the diaminobenzene formylaniline, 3, the 5-diaminochlorobenzene, diamino-diphenyl ether, 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane, 3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane, tolidine alkali, adjacent phenylenediamine, m-phenylenediamine, P-pHENYLENE dI AMINE, 2-chloro-P-pHENYLENE dI AMINE, dianisidine, methyl p-aminobenzoate, parathesin, the para-amino benzoic acid n-propyl, para-amino benzoic acid isopropyl ester, planoform, the para-amino benzoic acid dodecyl ester, para-amino benzoic acid benzyl ester, adjacent aminobenzophenone, the m-aminophenyl ethyl ketone, para-aminoacetophenone, m-aminophenyl methane amide, anthranilamide, Para Amino Benzamide, right-amino-N-methyl-benzamide, 3-amino-4-methyl benzamide, 3-amino-4-methoxy benzamide, 3-amino-4-chlorobenzamide, right-(N-phenyl amino formyl radical) aniline, right-[N-(4-chloro-phenyl-) formamyl] aniline, right-[N-(4-aminophenyl)-formamyl] aniline, 2-methoxyl group-5-(N-phenyl amino formyl radical)-aniline, 2-methoxyl group-5-[N-(2 '-methyl-3 '-chloro-phenyl-) formamyl] aniline, 2-methoxyl group-5-[N-(2 '-chloro-phenyl-)-formamyl] aniline, 5-acetylamino-2-anisidine, 4-acetylaminoaniline, 4-(N-methyl-N-kharophen) aniline, 2,5-diethoxy-4-(N-benzoyl-amido) aniline, 2,5-dimethoxy-4 '-(N-benzoyl-amido) aniline, 2-methoxyl group-4-(N-benzoyl-amino)-5-monomethylaniline, 4-sulfamyl aniline, 3-sulfamyl aniline, 2-(N-ethyl-N-phenyl amino alkylsulfonyl)-aniline, 4-dimethylamino alkylsulfonyl aniline, 4-diethylin alkylsulfonyl aniline, Sulphathiazole, 4-ADP base sulfone, 2-chloro-5-N-phenyl sulfamoyl base aniline, 2-methoxyl group-5-N, N-diethyl amino alkylsulfonyl aniline, 2,5-dimethoxy-4 '-N-phenyl sulfamoyl base aniline, 2-methoxyl group-5-benzyl alkylsulfonyl aniline, 2-phenoxy group alkylsulfonyl aniline, 2-(2 '-the chloro-phenoxy group) alkylsulfonyl aniline, 3-phenylsulfamoyl-4-monomethylaniline, two [4-(m-aminophenyl oxygen base) phenyl] sulfone, two [4-(p-aminophenyl oxygen base) phenyl] sulfone, two [3-methyl-4-(p-aminophenyl oxygen base) phenyl] sulfone, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, the o-tolidine sulfone, 2,4 '-benzidine, 2,2 '-benzidine, 4,4 '-benzidine, 2,2 '-two chloro-4,4 '-benzidine, 3,3 '-two chloro-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-thiobis aniline, 2,2 '-the dithio dianiline, 4,4 '-the dithio dianiline, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, two (3-amino-4-chloro-phenyl-) sulfone, two (3, the 4-diamino-phenyl) sulfone, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 3,4 '-diamino diphenyl sulfone, 3,3 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl amine, 4,4 '-ethylenebis aniline, 4,4 '-diamino-2,2 '-the dimethyl dibenzyl, 3,3 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-phenoxy group) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 3-, 9, two (4-aminophenyl) fluorenes of 9-, 2, two (the 4-amino-benzene oxygen phenyl) propane of 2-, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 3,3 ', 4,4 '-the tetramino diphenyl ether, 3,3 ', 4,4 '-the tetramino sulfobenzide, 3,3 ', 4,4 '-the tetramino benzophenone, the 3-aminobenzonitrile, 4-phenoxybenzamine, 3-phenoxybenzamine, 4,4 '-methylene-bis-Ortho Toluidine, 4,4 '-(to the phenylene isopropylidene)-two-(2, the 6-xylidene(s)), adjacent chloro-p-Nitroaniline, adjacent nitro-p-Chlorobenzoic acid amide, 2,6-two chloro-4-N-methyl-p-nitroanilines, 5-chloro-2-N-methyl-p-nitroaniline, 2-amino-4-chlorophenol, o-Nitraniline, m-nitraniline, p-Nitroaniline, 2-methyl-4-N-methyl-p-nitroaniline, between nitro-para-totuidine, 2-amino-5-nitrobenzonitrile, N-methyl p-aminophenol sulfate, 2,4-diaminophenol, N-(beta-hydroxyethyl)-Ortho-Aminophenol sulfuric ester, Sulphanilic Acid, m-sulfanilic acid, 4B acid, C acid, 2B acid, para-fluoroaniline, adjacent fluoroaniline, 3-chloro-4-fluoroaniline, 2, the 4-difluoroaniline, 2,3, the 4-trifluoromethyl aniline ,-5 amido benzotrifluoride, a toluylene diamines, the 2-aminothiophenol, 2-amino-3-bromo-5-nitrobenzonitrile, diphenylamine, to amino-diphenyl-amine, octyl group diphenylamine, 2-methyl-4-methoxyl group diphenylamine, N, N-phenylbenzene-P-pHENYLENE dI AMINE, dianisidine, 3,3 '-dichlorobenzidine, 4,4 '-diaminostilbene-2,2 '-disulfonic acid, the benzyl ethylaniline, 1, the 8-naphthylene diamine, sodium naphthionate, 2-amino-1-naphthalene sulfonic aicd, H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, 1,4-diamino-2,3-dichloroanthraquinone etc.; With heterogeneous ring compound amine such as 3-amino-1,2,4-triazole, 2-aminopyridine, the 3-aminopyridine, 4-aminopyridine, alpha-amino group-ε-Ji Neixianan, acetylguanamine, 2,4-diamino-6-[2 '-methylimidazolyl-(1)] ethyl-S-triazine, 2,3 diamino pyridine, 2,5-diamino-pyridine, 2,3,5-triamino pyridine, 1-amino-4-methylpiperazine, 1-(2-amino-ethyl) piperazine, two (aminopropyl) piperazine, N-(3-aminopropyl) morpholine etc.; With aliphatic amine such as methylamine, ethamine, dimethylamine, diethylamine, stearylamine, allyl amine, diallyl amine, isopropylamine, diisopropylamine, 2-DEHA, thanomin, 3-(2-ethyl hexyl oxy) propylamine, 3-ethoxycarbonyl propyl amine, diisobutyl amine, 3-(diethylin) propylamine, D2EHA di 2 ethylhexyl amine, 3-(dibutylamino) propylamine, tert-butylamine, propylamine, 3-(methylamino) propylamine, 3-(dimethylamino) propylamine, 3 methoxypropyl amine, methyl hydrazine, 1-methyl butyl amine, methane diamines, 1,4-diaminobutane, hexanaphthene methylamine, cyclo-hexylamine, 4-methylcyclohexyl amine, 2-bromotrifluoromethane amine, 2-methoxy ethyl amine, 2-ethoxyl methyl amine, 2-amino-1-propyl alcohol, the 2-amino butanol, 3-amino-1,2-propylene glycol, 1,3-diamino-2-hydroxy propane, 2-ethylamine mercaptan, quadrol, diethylenetriamine, hexamethylene-diamine etc.
In the above amine compound that exemplifies, it is particularly preferred having at least one anils amino and that represent with following formula (VIII):
R wherein
1, R
2, R
3And R
4Be hydrogen atom, halogen atom, alkyl, alkoxyl group or amino independently, X
1And X
2Be group amino or that represent with formula (b) independently:
Y
1Be-SO
2-,-O-,-(S)
n-,-(CH
2)
n-,-CO-,-CONH-and with in the group of any one expression of formula (a) any one:
Or Y
1Do not exist, n is 1 or 2.
As with isocyanate reaction to form the compound that contains the OH base of one or more urea alkyl, can use any compound, as long as it contains one or more OH bases.The compound that contains the OH base for example comprises phenols such as phenol; cresols; xylenol; p-ethyl phenol; o-isopropyl phenol; Resorcinol; p-tert-butylphenol; to tert-octyl phenol, 2-cyclohexylphenol, 2-chavicol; the 4-indanol; thymol, beta naphthal, p-NP; ortho chloro phenol; para-chlorophenol, 2, two (4-the hydroxyphenyl)-propane of 2-; 2; two (hydroxyphenyl) butane of 2-, 2, two (hydroxyphenyl) pentanes of 2-; 2; two (hydroxyphenyl) heptane of 2-, catechol, 3-methyl catechol; 3-methoxyl group catechol; pyrogallol, quinhydrones, toluhydroquinone; the 4-phenylphenol; p, p '-bis-phenol, 4-cumyl phenol; two (4-hydroxyphenyl) butylacetate; two (4-hydroxyphenyl) jasmal, two (4-hydroxyphenyl) sulfone, two (3-methyl-4-hydroxyphenyl) sulfone; two (3; 5-dimethyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4 '-methyl phenyl sulfone, 3-chloro-4-hydroxyphenyl-4 '-methyl phenyl sulfone; 3; 4-dihydroxyphenyl-4 '-methyl phenyl sulfone, 4-sec.-propyl oxygen base phenyl-4 '-the hydroxyphenyl sulfone, two (2-allyl group-4-hydroxyphenyl) sulfone; 4-hydroxyphenyl-4 '-the benzyloxy phenylsulfone; 4-isopropyl phenyl-4 '-the hydroxyphenyl sulfone, 4-hydroxyl-4 '-the isopropoxy sulfobenzide, two (the 2-methyl-3-tertiary butyl-4-hydroxyphenyl) sulphur; 4; 4 '-dihydroxydiphenyl ether, 4,4 '-the sulfo-diphenol; 4; 4 '-dihydroxy benaophenonel, 2, two (4-hydroxyphenyl) HFC-236fa of 2-; 4; 4 '-dihydroxyl-ditan, 3,3 '-the dihydroxyl diphenylamine; two (4-hydroxy-3-methyl phenyl) sulphur; two (4-(2-hydroxyl)-phenyl) sulfone, 2,4 dihydroxyl benzophenone; 2; 2 ', 4,4 '-tetrahydroxybenzophenone; salol; salicylamide, 4-methyl hydroxybenzoate, 4-hydroxy benzoic acid benzyl ester; the 4-hydroxy-benzoic acid (4 '-the benzyl chloride base) ester; 1,2-pair (4 '-hydroxy-benzoic acid) ethyl ester, 1; 5-pair (4 '-hydroxy-benzoic acid) pentyl ester; 1,6-pair (4 '-hydroxy-benzoic acid) own ester, 3-hydroxyl phthalic dimethyl ester; the gallic acid stearyl ester; Progallin LA, methyl gallate, 4-methoxyphenol; 4-(benzyloxy) phenol; the 4-hydroxy benzaldehyde, 4-n-octyloxy Whitfield's ointment, 4-n-butoxy Whitfield's ointment; 4-n-pentyloxy Whitfield's ointment; 3-dodecyl oxygen base Whitfield's ointment, the positive hot acyloxy Whitfield's ointment of 3-, 4-n-octyloxy carbonylamino Whitfield's ointment and the positive capryloyl oxygen of 4-base carbonylamino Whitfield's ointment etc.Yet as these phenol, it is undesirable having amino those.Because amino have the higher reactivity to isocyanate group than OH base, amino before the OH base with isocyanate reaction, make to be difficult to obtain needed compound in some cases.
The compound that contains the OH base also can comprise alcohol as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, Virahol, isopropylcarbinol, primary isoamyl alcohol, 2-ethyl-1-hexanol, 1-decanol, 2-amylalcohol, 3-hexanol, the trimethyl carbinol, tertiary amyl alcohol, methyl cellosolve, ethylene glycol dibutyl ether, methyl carbitol, vinyl carbinol, methallyl alcohol, benzyl alcohol, 4-piconol, Rokafenol F 1, furfuryl alcohol, hexalin, hexahydrobenzyl alcohol, cyclopentanol, ethylene chlorhydrin, 1-chloro-3-hydroxy propane, glycerine etc.; Polyether polyol such as polypropylene glycol, polytetramethylene ether diol, hexanodioic acid deutero-polyvalent alcohol, epoxy group(ing) modified polyalcohol, polyester ether polylol, polycarbonate polyol, polycaprolactone glycol, phenols polyvalent alcohol, amine modified polyalcohol etc.; With polyvalent alcohol such as ethylene glycol, glycol ether, 1, ammediol; 1,2-propylene glycol, propylene glycol, dipropylene glycol; 1,4-butyleneglycol, 1,5-pentanediol; 1,6-hexylene glycol, 1,9-nonanediol; the acryl polyvalent alcohol, fluorohydrocarbon polyvalent alcohol, polybutadiene polyol, poly-hydroxy polyvalent alcohol; TriMethylolPropane(TMP), trimethylolethane, hexanetriol; phosphoric acid, neopentyl glycol, tetramethylolmethane; Viscotrol C deutero-polyvalent alcohol, polymer polyatomic alcohol, methyl pentanediol; halogen-containing polyvalent alcohol, phosphorated polyvalent alcohol, ethylene diamine; the Alpha-Methyl glucosides, sorbyl alcohol, sucrose etc.
The of the present invention the 21 and the 22 aspect each in be used as developer the urea-urea hydride compounds of urea-urea hydride compounds number of preferably having the number of urea groups (A) wherein and a urea alkyl (B) digital molecular structure below satisfying:
10≥(A+B)≥3
Each integer more than 1 or 1 naturally of A and B wherein.
Wherein the number of the number of urea groups (A) and urea alkyl (B) satisfy the urea-urea hydride compounds of digital 10 〉=(A+B) 〉=3 (wherein A and B each integer 1 or 1 or more) naturally be have wherein exist at least one urea groups (NHCONH-) and at least one urea alkyl (NHCOO-), and its sum no more than 10 and the compound that is no less than 3 molecular structure.
This compound was not reported, was novel fully.This novel cpd can be used for using the recording materials as record energy such as heat, pressure.
The method of urea-urea hydride compounds that the number of synthetic wherein urea groups (A) and the number of urea alkyl (B) satisfy is digital 10 〉=(A+B) 〉=3 (wherein A and B each integer 1 or 1 or more) naturally is not special restriction, if in total 3-10, exist at least a urea groups (NHCONH-) with at least one urea alkyl (NHCOO-).Produce the method for urea-urea hydride compounds because its simplification but preferred by isocyanate compound and the reaction that contains the compound of OH base and amine compound.
In detail, as the of the present invention the 21 and the 22 aspect each in be used as the urea-urea hydride compounds of developer, have at least one urea groups and at least one urea alkyl, and sum is at least urea-urea hydride compounds of 3 and for example can obtains by the following method: use to have the isocyanic ester of at least two isocyanate group as starting raw material, make except the isocyanate group at least one and the compound reaction that contains the OH base to form one or more urea alkyl, then by making water that the residual isocyanate base of two molecules of gained urea hydride compounds is reacted each other so that they are bonded to each other.
In addition, have at least one urea groups and at least one urea alkyl, and its sum is at least urea-urea hydride compounds of 3 and for example can obtains by the following method: use to have the isocyanic ester of at least two isocyanate group as starting raw material, make except the isocyanate group at least one and the compound reaction that contains the OH base to form one or more urea alkyl, make remaining isocyanate group and amine compound reaction with two or more amino, to form one or more urea groups, make the reaction of remaining amino and isocyanate compound again.
In addition, have at least one urea groups and at least one urea alkyl, and its sum is at least urea-urea hydride compounds of 3 and can also obtains by the following method: make except the isocyanate group at least one and amine compound and at first react to form one or more urea groups, make remaining isocyanate group and the compound reaction that contains two or more OH bases, to form one or more urea alkyl, make the reaction of gained compound and isocyanate compound then.In this case, have at least one urea groups and at least one urea alkyl, and the urea of its total 3-10-urea hydride compounds can have the isocyanic ester of the isocyanate compound of two or more isocyanate group as final reaction by use, and repeats to make residual isocyanate base and the operation that contains the compound of two or more OH groups or have an amine compound reaction of two or more amino to obtain.
Initial isocyanic ester is not special restriction, as long as it has two or more isocyanate group.Initial isocyanic ester for example comprises phenylene vulcabond, 2, and 5-dimethoxy benzene-1, the 4-vulcabond, 2,4 toluene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethanediisocyanate, the o-tolidine vulcabond, diphenyl ether vulcabond, 1, the 5-naphthalene diisocyanate, dianisidine vulcabond, 9-ethyl carbazole-3, the 6-vulcabond, 3,3 '-dimethyl-4,4 '-diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, three (4-phenyl isocyanate) thiophosphatephosphorothioate, 4,4 ', 4 " three isocyanatos-2; 5-dimethoxytrityl amine, 4,4 '; 4 "-three isocyanatos-triphenylamine, between eylylene diisocyanate, lysinediisocyanate, dimer acids vulcabond, isopropylidene is two-4-cyclohexyl-isocyanic ester, dicyclohexyl methane diisocyanate and methylcyclohexane diisocyanate.
As initial isocyanic ester, can also use vulcabond dimer such as N, N '-(4,4 '-dimethyl-3,3 '-phenylbenzene two isocyanatos)-urea diketone (Desmodule TT, trade(brand)name), toluene diisocyanate dimer; With diisocyanate trimer as 4,4 ', 4 " trimethylammonium-3,3 ', 3 " three isocyanatos-2,4,6-triphenyl cyanurates.Can also use the water adduction isocyanic ester of tolylene diisocyanate, diphenylmethanediisocyanate etc., as 1, two (3-isocyanato-4-aminomethyl phenyl) ureas of 3-; The trimethylolpropane adduct of polyvalent alcohol adducts such as tolylene diisocyanate (Desmodule L, trade(brand)name); And amine adduct.Can also use the compound with two or more isocyanate group (content of these reference is quoted for reference here) of the row of the isocyanate compound described in the specification sheets of the specification sheets that belongs to JP-A-10-76757 and JP-A-10-95171 and isocyanic ester addition compound.
The particularly preferred example of initial isocyanic ester is a tolylene diisocyanate.In the middle of tolylene diisocyanate, 2,4 toluene diisocyanate is preferred.Except 2,4 toluene diisocyanate, 2,4 toluene diisocyanate and 2, the mixture of 6-tolylene diisocyanate are generally on sale on market, can obtain at a low price, also can be used as initial isocyanic ester.These tolylene diisocyanate mixture of isomers are liquid at normal temperatures.
As with the initial isocyanate reaction of urea-urea hydride compounds to form the amine compound of one or more urea groups, can use any compound, as long as it has one or more amino.Amine compound for example comprises aromatic amine such as aniline, Ortho Toluidine, meta-aminotoluene, para-totuidine, o-anisidine, P-anisidine, p-phenetidine, N, accelerine, N, N-Diethyl Aniline, N, N-dimethyl-right-phenylenediamine, N, N-diethyl-P-pHENYLENE dI AMINE, 2,4-dimethoxyaniline, 2, the 5-dimethoxyaniline, 3, the 4-dimethoxyaniline, to amino-Acetanilide, para-amino benzoic acid, Ortho-Aminophenol, Metha Amino Phenon, p-aminophenol, 2, the 3-xylidene(s), toluene 24 diamine, 3,4-xylidene(s), 2, the 6-xylidene(s), 4-aminobenzonitrile, anthranilic acid, p-cresol is fixed, and 2, the 5-dichlorphenamide bulk powder, 2,6-dichlorphenamide bulk powder, 3, the 4-dichlorphenamide bulk powder, 3, the 5-dichlorphenamide bulk powder, 245 trichloroaniline, alpha-naphthylamine, amino anthracene, o ethyl aniline, Ortho-Chloro aniline, m-chloro aniline, p-Chlorobenzoic acid amide, methylphenylamine, N-ethylaniline, N propyl aniline, the N-butylaniline, N, N-diglycidylaniline, N, N-diglycidyl-Ortho Toluidine, N, N-etheric acid aniline, bromination trimethylphenyl ammonium, 4,4 '-diamino-3,3 '-the diethyl ditan, 4,4 '-the diaminobenzene formylaniline, 3, the 5-diaminochlorobenzene, diamino-diphenyl ether, 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane, 3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane, tolidine alkali, adjacent phenylenediamine, m-phenylenediamine, P-pHENYLENE dI AMINE, 2-chloro-P-pHENYLENE dI AMINE, dianisidine, methyl p-aminobenzoate, parathesin, the para-amino benzoic acid n-propyl, para-amino benzoic acid isopropyl ester, planoform, the para-amino benzoic acid dodecyl ester, para-amino benzoic acid benzyl ester, adjacent aminobenzophenone, the m-aminophenyl ethyl ketone, para-aminoacetophenone, m-aminophenyl methane amide, anthranilamide, Para Amino Benzamide, right-amino-N-methyl-benzamide, 3-amino-4-methyl benzamide, 3-amino-4-methoxy benzamide, 3-amino-4-chlorobenzamide, right-(N-phenyl amino formyl radical) aniline, right-[N-(4-chloro-phenyl-) formamyl] aniline, right-[N-(4-aminophenyl)-formamyl] aniline, 2-methoxyl group-5-(N-phenyl amino formyl radical)-aniline, 2-methoxyl group-5-[N-(2 '-methyl-3 '-chloro-phenyl-) formamyl] aniline, 2-methoxyl group-5-[N-(2 '-chloro-phenyl-)-formamyl] aniline, 5-acetylamino-2-anisidine, 4-acetylaminoaniline, 4-(N-methyl-N-kharophen) aniline, 2,5-diethoxy-4-(N-benzoyl-amido) aniline, 2,5-dimethoxy-4 '-(N-benzoyl-amido) aniline, 2-methoxyl group-4-(N-benzoyl-amino)-5-monomethylaniline, 4-sulfamyl aniline, 3-sulfamyl aniline, 2-(N-ethyl-N-phenyl amino alkylsulfonyl)-aniline, 4-dimethylamino alkylsulfonyl aniline, 4-diethylin alkylsulfonyl aniline, Sulphathiazole, 4-ADP base sulfone, 2-chloro-5-N-phenyl sulfamoyl base aniline, 2-methoxyl group-5-N, N-diethyl amino alkylsulfonyl aniline, 2,5-dimethoxy-4 '-N-phenyl sulfamoyl base aniline, 2-methoxyl group-5-benzyl alkylsulfonyl aniline, 2-phenoxy group alkylsulfonyl aniline, 2-(2 '-the chloro-phenoxy group) alkylsulfonyl aniline, 3-Phenylsulfamoyl base-4-monomethylaniline, two [4-(m-aminophenyl oxygen base) phenyl] sulfone, two [4-(p-aminophenyl oxygen base) phenyl] sulfone, two [3-methyl-4-(p-aminophenyl oxygen base) phenyl] sulfone, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, the o-tolidine sulfone, 2,4 '-benzidine, 2,2 '-benzidine, 4,4 '-benzidine, 2,2 '-two chloro-4,4 '-benzidine, 3,3 '-two chloro-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-thiobis aniline, 2,2 '-the dithio dianiline, 4,4 '-the dithio dianiline, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, two (3-amino-4-chloro-phenyl-) sulfone, two (3, the 4-diamino-phenyl) sulfone, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 3,4 '-diamino diphenyl sulfone, 3,3 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl amine, 4,4 '-ethylenebis aniline, 4,4 '-diamino-2,2 '-the dimethyl dibenzyl, 3,3 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-phenoxy group) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 3-, 9, two (4-aminophenyl) fluorenes of 9-, 2, two (the 4-amino-benzene oxygen phenyl) propane of 2-, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 3,3 ', 4,4 '-the tetramino diphenyl ether, 3,3 ', 4,4 '-the tetramino sulfobenzide, 3,3 ', 4,4 '-the tetramino benzophenone, the 3-aminobenzonitrile, 4-phenoxybenzamine, 3-phenoxybenzamine, 4,4 '-methylene-bis-Ortho Toluidine, 4,4 '-(to the phenylene isopropylidene)-two-(2, the 6-xylidene(s)), adjacent chloro-p-Nitroaniline, adjacent nitro-p-Chlorobenzoic acid amide, 2,6-two chloro-4-N-methyl-p-nitroanilines, 5-chloro-2-N-methyl-p-nitroaniline, 2-amino-4-chlorophenol, o-Nitraniline, m-nitraniline, p-Nitroaniline, 2-methyl-4-N-methyl-p-nitroaniline, between nitro-para-totuidine, 2-amino-5-nitrobenzonitrile, N-methyl p-aminophenol sulfate, 2,4-diaminophenol, N-(beta-hydroxyethyl)-Ortho-Aminophenol sulfuric ester, Sulphanilic Acid, m-sulfanilic acid, 4B acid, C acid, 2B acid, para-fluoroaniline, adjacent fluoroaniline, 3-chloro-4-fluoroaniline, 2, the 4-difluoroaniline, 2,3, the 4-trifluoromethyl aniline ,-5 amido benzotrifluoride, a toluylene diamines, the 2-aminothiophenol, 2-amino-3-bromo-5-nitrobenzonitrile, diphenylamine, to amino-diphenyl-amine, octyl group diphenylamine, 2-methyl-4-methoxyl group diphenylamine, N, N-phenylbenzene-P-pHENYLENE dI AMINE, dianisidine, 3,3 '-dichlorobenzidine, 4,4 '-diaminostilbene-2,2 '-disulfonic acid, the benzyl ethylaniline, 1, the 8-naphthylene diamine, sodium naphthionate, 2-amino-1-naphthalene sulfonic aicd, H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, 1,4-diamino-2,3-dichloroanthraquinone etc.; With heterogeneous ring compound amine such as 3-amino-1,2,4-triazole, 2-aminopyridine, the 3-aminopyridine, 4-aminopyridine, alpha-amino group-ε-Ji Neixianan, acetylguanamine, 2,4-diamino-6-[2 '-methylimidazolyl-(1)] ethyl-S-triazine, 2,3 diamino pyridine, 2,5-diamino-pyridine, 2,3,5-triamino pyridine, 1-amino-4-methylpiperazine, 1-(2-amino-ethyl) piperazine, two (aminopropyl) piperazine, N-(3-aminopropyl) morpholine etc.; With aliphatic amine such as methylamine, ethamine, dimethylamine, diethylamine, stearylamine, allyl amine, diallyl amine, isopropylamine, diisopropylamine, 2-DEHA, thanomin, 3-(2-ethyl hexyl oxy) propylamine, 3-ethoxycarbonyl propyl amine, diisobutyl amine, 3-(diethylin) propylamine, D2EHA di 2 ethylhexyl amine, 3-(dibutylamino) propylamine, tert-butylamine, propylamine, 3-(methylamino) propylamine, 3-(dimethylamino) propylamine, 3 methoxypropyl amine, methyl hydrazine, 1-methyl butyl amine, methane diamines, 1,4-diaminobutane, hexanaphthene methylamine, cyclo-hexylamine, 4-methylcyclohexyl amine, 2-bromotrifluoromethane amine, 2-methoxy ethyl amine, 2-ethoxyl methyl amine, 2-amino-1-propyl alcohol, the 2-amino butanol, 3-amino-1,2-propylene glycol, 1,3-diamino-2-hydroxy propane, 2-ethylamine mercaptan, quadrol, diethylenetriamine, hexamethylene-diamine etc.
In the above amine compound that exemplifies, it is particularly preferred having at least one anils amino and that represent with following formula (VIII):
R wherein
1, R
2, R
3And R
4Be hydrogen atom, halogen atom, alkyl, alkoxyl group or amino independently, X
1And X
2Be group amino or that represent with formula (b) independently:
Y
1Be-SO
2-,-O-,-(S)
n-,-(CH
2)
n-,-CO-,-CONH-and with in the group of any one expression of formula (a) any one:
Or Y
1Do not exist, n is 1 or 2.
As with isocyanate reaction to form the compound that contains the OH base of one or more urea alkyl, can use any compound, as long as it contains one or more OH bases.The compound that contains the OH base for example comprises phenols such as phenol, as with isocyanate reaction to form the compound that contains the OH base of one or more urea alkyl, can use any compound, as long as it contains one or more OH bases.The compound that contains the OH base for example comprises phenols such as phenol; cresols; xylenol; p-ethyl phenol; o-isopropyl phenol; Resorcinol; p-tert-butylphenol; to tert-octyl phenol, 2-cyclohexylphenol, 2-chavicol; the 4-indanol; thymol, beta naphthal, p-NP; ortho chloro phenol; para-chlorophenol, 2, two (4-the hydroxyphenyl)-propane of 2-; 2; two (hydroxyphenyl) butane of 2-, 2, two (hydroxyphenyl) pentanes of 2-; 2; two (hydroxyphenyl) heptane of 2-, catechol, 3-methyl catechol; 3-methoxyl group catechol; pyrogallol, quinhydrones, toluhydroquinone; the 4-phenylphenol; p, p '-bis-phenol, 4-cumyl phenol; two (4-hydroxyphenyl) butylacetate; two (4-hydroxyphenyl) jasmal, two (4-hydroxyphenyl) sulfone, two (3-methyl-4-hydroxyphenyl) sulfone; two (3; 5-dimethyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4 '-methyl phenyl sulfone, 3-chloro-4-hydroxyphenyl-4 '-methyl phenyl sulfone; 3; 4-dihydroxyphenyl-4 '-methyl phenyl sulfone, 4-sec.-propyl oxygen base phenyl-4 '-the hydroxyphenyl sulfone, two (2-allyl group-4-hydroxyphenyl) sulfone; 4-hydroxyphenyl-4 '-the benzyloxy phenylsulfone; 4-isopropyl phenyl-4 '-the hydroxyphenyl sulfone, 4-hydroxyl-4 '-the isopropoxy sulfobenzide, two (the 2-methyl-3-tertiary butyl-4-hydroxyphenyl) sulphur; 4; 4 '-dihydroxydiphenyl ether, 4,4 '-the sulfo-diphenol; 4; 4 '-dihydroxy benaophenonel, 2, two (4-hydroxyphenyl) HFC-236fa of 2-; 4; 4 '-dihydroxyl-ditan, 3,3 '-the dihydroxyl diphenylamine; two (4-hydroxy-3-methyl phenyl) sulphur; two (4-(2-hydroxyl)-phenyl) sulfone, 2,4 dihydroxyl benzophenone; 2; 2 ', 4,4 '-tetrahydroxybenzophenone; salol; salicylamide, 4-methyl hydroxybenzoate, 4-hydroxy benzoic acid benzyl ester; the 4-hydroxy-benzoic acid (4 '-the benzyl chloride base) ester; 1,2-pair (4 '-hydroxy-benzoic acid) ethyl ester, 1; 5-pair (4 '-hydroxy-benzoic acid) pentyl ester; 1,6-pair (4 '-hydroxy-benzoic acid) own ester, 3-hydroxyl phthalic dimethyl ester; the gallic acid stearyl ester; Progallin LA, methyl gallate, 4-methoxyphenol; 4-(benzyloxy) phenol; the 4-hydroxy benzaldehyde, 4-n-octyloxy Whitfield's ointment, 4-n-butoxy Whitfield's ointment; 4-n-pentyloxy Whitfield's ointment; 3-dodecyl oxygen base Whitfield's ointment, the positive hot acyloxy Whitfield's ointment of 3-, 4-n-octyloxy carbonylamino Whitfield's ointment and the positive capryloyl oxygen of 4-base carbonylamino Whitfield's ointment etc.Yet as these phenol, it is unfavorable having amino those.Because amino have the higher reactivity to isocyanate group than OH base, amino before the OH base with isocyanate reaction, make to be difficult to obtain required compound in some cases.The compound that contains the OH base also can comprise alcohol as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, Virahol, isopropylcarbinol, iso-heptanol, 2-ethyl-1-hexanol, 1-decanol, 2-amylalcohol, 3-hexanol, the trimethyl carbinol, tertiary amyl alcohol, methyl cellosolve, ethylene glycol dibutyl ether, methyl carbitol, vinyl carbinol, methallyl alcohol, benzyl alcohol, 4-piconol, Rokafenol F 1, furfuryl alcohol, hexalin, hexahydrobenzyl alcohol, cyclopentanol, ethylene chlorhydrin, 1-chloro-3-hydroxy propane, glycerine etc.; Polyether polyol such as polypropylene glycol, polytetramethylene ether diol, hexanodioic acid deutero-polyvalent alcohol, epoxy group(ing) modified polyalcohol, polyester ether polylol, polycarbonate polyol, polycaprolactone glycol, phenols polyvalent alcohol, amine modified polyalcohol etc.; With polyvalent alcohol such as ethylene glycol, glycol ether, 1, ammediol; 1,2-propylene glycol, propylene glycol, dipropylene glycol; 1,4-butyleneglycol, 1,5-pentanediol; 1,6-hexylene glycol, 1,9-nonanediol; the acryl polyvalent alcohol, fluorohydrocarbon polyvalent alcohol, polybutadiene polyol, poly-hydroxy polyvalent alcohol; TriMethylolPropane(TMP), trimethylolethane, hexanetriol; phosphoric acid, neopentyl glycol, tetramethylolmethane; Viscotrol C deutero-polyvalent alcohol, polymer polyatomic alcohol, methyl pentanediol; halogen-containing polyvalent alcohol, phosphorated polyvalent alcohol, ethylene diamine; the Alpha-Methyl glucosides, sorbyl alcohol, sucrose etc.
As the of the present invention the 21 and the 22 aspect each in be used as the urea-urea hydride compounds of developer, also be preferred with the urea-urea hydride compounds of any one expression in the following general formula (I)-(VII):
Wherein X and Z independently are aromatic substance residue, heterogeneous ring compound residue or aliphatic cpd residue, and each residue can have one or more substituting groups, Y
0Be to be selected from tolylene, xylylene, naphthylidene, hexa-methylene and-φ-CH
2Group in-φ-group, wherein-φ-be phenylene;
Wherein X and Y are aromatic substance residue, heterogeneous ring compound residue or aliphatic cpd residue independently, and each residue can have one or more substituting groups;
Wherein X and Y are aromatic substance residue, heterogeneous ring compound residue or aliphatic cpd residue independently, and α has divalent or the above residue of divalent, and n is the integer more than 2 or 2, and each residue can have one or more substituting groups;
Wherein Z and Y are aromatic substance residue, heterogeneous ring compound residue or aliphatic cpd residue independently, and β has divalent or the above residue of divalent, and n is the integer more than 2 or 2, and each residue can have one or more substituting groups;
Wherein the hydrogen atom of each phenyl ring can be substituted the base displacement; substituting group is aromatic substance residue, aliphatic cpd residue or heterogeneous ring compound residue preferably; substituting group also can be nitro, hydroxyl, carboxyl, nitroso-group, itrile group, formamyl, urea groups, isocyanate group, sulfydryl, sulfo group, sulfamyl or halogen atom; each substituting group can have one or more substituting groups, and γ is selected from-SO
2-,-O-,-(S)
n-,-(CH
2)
n-,-CO-,-CONH-and with the group in any group of formula (a) expression:
Perhaps γ does not exist, and n is 1 or 2;
Wherein the hydrogen atom of each phenyl ring can be substituted the base displacement; described substituting group is aromatic substance residue, aliphatic cpd residue or heterogeneous ring compound residue preferably; substituting group also can be hydroxyl, nitro, itrile group, formamyl, sulfamyl, carboxyl, nitroso-group, amino, oxygen amino, nitro amino, diazanyl, urea groups, isocyanate group, sulfydryl, sulfo group or halogen atom; each residue can have one or more substituting groups, and δ is selected from-SO
2-,-O-,-(S)
n-,-(CH
2)
n-,-CO-,-CONH-,-NH-,-CH (COOR
1)-,-C (CF
3)
2-and-CR
2R
3-in group or do not have R
1, R
2And R
3Each is alkyl naturally, and n is 1 or 2; With
Wherein X, Y and Z are aromatic substance residue, heterogeneous ring compound residue or aliphatic cpd residue independently, and each residue can have one or more substituting groups, and X, Y and Z be preferably aromatic substance residue or heterogeneous ring compound residue separately.
The urea of formula (I)-(VII)-urea hydride compounds also is novel fully.These compounds can be used for using the recording materials of record energy such as heat, pressure.
To produce the of the present invention the 21 and the 22 aspect in the formula (I) used in each urea-urea hydride compounds method without limits.This compound for example can be by making following general formula (IX) the compound that contains the OH base and the isocyanate compound of following general formula (X) and the amine compound of following general formula (XI) for example obtain according to reaction formula shown below (A) reaction:
X-OH (IX)
OCN-Y
0-NCO (X)
Z-NH
2 (XI)
Wherein X and Z are aromatic substance residue, heterogeneous ring compound residue or aliphatic cpd residue independently, and each residue can have one or more substituting groups, Y
0Be be selected from tolylene, xylylene, naphthylidene, hexa-methylene and-φ-CH
2Group in-φ-group, wherein-φ-be phenylene.
Term used herein " aliphatic series " comprises term " alicyclic ".
The of the present invention the 21 and the 22 aspect each in the production method of urea-urea hydride compounds of the formula (II) used do not limit.This compound for example can be by making general formula (IX) the compound that contains the OH base and the isocyanate compound and the water of following general formula (XII) for example obtain according to reaction formula shown below (B) reaction:
OCN-Y-NCO (XII)
Wherein Y is aromatic substance residue, heterogeneous ring compound residue or aliphatic cpd residue, and each residue can have one or more substituting groups.
The of the present invention the 21 and the 22 aspect each in the production method of urea-urea hydride compounds of the formula (III) used do not limit.The amine compound of the compound that contains OH that this compound for example can be by making general formula (IX) and the isocyanate compound of general formula (XII) and following general formula (XIII) for example according to following reaction formula (C) or (D) reaction obtain:
α
NH
2)
n (XIII)
Wherein α has divalent or the above residue of divalent, and n is the integer more than 2 or 2.
The of the present invention the 21 and the 22 aspect each in the production method of urea-urea hydride compounds of the formula (IV) used do not limit.The compound that contains OH of the amine compound that this compound for example can be by making general formula (XI) and the isocyanate compound of general formula (XII) and following general formula (XIV) for example according to reaction formula shown below (E) or (F) reaction obtain:
β
1 
OH)n (XIV)
Wherein β has divalent or the above residue of divalent, and n is the integer more than 2 or 2.
Below explain in detail the compound of general formula (IX)-(XIV), they can be used in the urea-urea hydride compounds of synthetic following formula (I)-(IV).
The compound that contains the OH base of general formula (IX) is not special restriction, as long as it has one or more OH bases.This compound for example comprises monohydric phenol; as phenol; cresols, xylenol, p-ethyl phenol; o-isopropyl phenol; Resorcinol, p-tert-butylphenol is to tert-octyl phenol; the 2-cyclohexylphenol; the 2-chavicol, 4-indanol, thymol; beta naphthal; p-NP, ortho chloro phenol, para-chlorophenol; the 4-phenylphenol; 4-hydroxyphenyl-4 '-methyl phenyl sulfone, 3-chloro-4-hydroxyphenyl-4 '-methyl phenyl sulfone, 4-isopropyl phenyl-4 '-the hydroxyphenyl sulfone; 4-sec.-propyl oxygen base phenyl-4 '-the hydroxyphenyl sulfone; 4-hydroxyphenyl-4 '-the benzyloxy phenylsulfone, 4-isopropyl phenyl-4 '-the hydroxyphenyl sulfone, 4-hydroxyl-4 '-sec.-propyl oxygen base sulfobenzide; salol; salicylamide, 4-methyl hydroxybenzoate, 4-hydroxy benzoic acid benzyl ester; the 4-hydroxy-benzoic acid (4 '-the benzyl chloride base) ester; 1,2-pair (4 '-hydroxy-benzoic acid) ethyl ester, 1; 5-pair (4 '-hydroxy-benzoic acid) pentyl ester; 1,6-pair (4 '-hydroxy-benzoic acid) own ester, 3-hydroxyl phthalic dimethyl ester; the 4-methoxyphenol; 4-(benzyloxy) phenol, 4-hydroxy benzaldehyde, 4-n-octyloxy Whitfield's ointment; 4-n-butoxy Whitfield's ointment; 4-n-pentyloxy Whitfield's ointment, 3-dodecyl oxygen base Whitfield's ointment, the positive hot acyloxy Whitfield's ointment of 3-; 4-n-octyloxy carbonylamino Whitfield's ointment, the positive capryloyl oxygen of 4-base carbonylamino Whitfield's ointment etc.The compound of general formula (IX) also comprises dihydric phenol as 2, two (4-hydroxyphenyl) propane of 2-, 2, two (hydroxyphenyl) butane of 2-, 2, two (hydroxyphenyl) pentanes of 2-, 2, two (the hydroxyphenyl)-heptane of 2-, catechol, the 3-methyl catechol, 3-methoxyl group catechol, pyrogallol, quinhydrones, toluhydroquinone, 4-phenylphenol, 4,4 '-bis-phenol, the 4-cumyl phenol, two (4-hydroxyphenyl) butylacetate, two (4-hydroxyphenyl) jasmal, two (4-hydroxyphenyl) sulfone, two (3-methyl-4-hydroxyphenyl) sulfone, two (3,5-dimethyl-4-hydroxyphenyl) sulfone, 3,4-dihydroxyphenyl-4 '-methyl phenyl sulfone, two (2-allyl group-4-hydroxyphenyl) sulfone, two (the 2-methyl-3-tertiary butyl-4-hydroxyphenyl) sulphur, 4,4 '-dihydroxydiphenyl ether, 4,4 '-thiobisphenol, 4,4 '-dihydroxy benaophenonel, 2, two (4-hydroxyphenyl) HFC-236fa of 2-, 4,4 '-the dihydroxyl ditan, 3,3 '-the dihydroxyl diphenylamine, two (4-hydroxy-3-methyl phenyl) sulphur etc.Yet as this compound that contains the OH base, it is unfavorable having amino those.When amino existed with the OH base, amino had the higher reactivity to isocyanate group than OH base, therefore before the OH base with the isocyanic ester radical reaction, make to be difficult to obtain required compound in some cases.The compound of general formula (IX) further comprises monohydroxy-alcohol such as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, Virahol, isopropylcarbinol, primary isoamyl alcohol, 2-ethyl-1-hexanol, 1-decanol, 2-amylalcohol, the 3-hexanol, the trimethyl carbinol, tertiary amyl alcohol, methyl cellosolve, ethylene glycol dibutyl ether, methyl carbitol, vinyl carbinol, methallyl alcohol, benzyl alcohol, the 4-piconol, Rokafenol F 1, furfuryl alcohol, hexalin, hexahydrobenzyl alcohol, cyclopentanol, ethylene chlorhydrin, 1-chloro-3-hydroxy propane, glycerine etc.As the compound of general formula (IX), can also use polyether polyol such as polypropylene glycol, polytetramethylene ether diol, hexanodioic acid deutero-polyvalent alcohol, the polyvalent alcohol of epoxy group(ing) modification, polyester ether polylol, polycarbonate polyol, polycaprolactone glycol, phenols polyvalent alcohol, amine modified polyalcohol etc.; With polyvalent alcohol such as ethylene glycol, glycol ether, 1, ammediol; 1,2-propylene glycol, propylene glycol, dipropylene glycol; 1,4-butyleneglycol, 1,5-pentanediol; 1,6-hexylene glycol, 1,9-nonanediol; the acryl polyvalent alcohol, fluorohydrocarbon polyvalent alcohol, polybutadiene polyol, poly-hydroxy polyvalent alcohol; TriMethylolPropane(TMP), trimethylolethane, hexanetriol; phosphoric acid, neopentyl glycol, tetramethylolmethane; Viscotrol C deutero-polyvalent alcohol, polymer polyatomic alcohol, methyl pentanediol; halogen-containing polyvalent alcohol, phosphorated polyvalent alcohol, ethylene diamine; the Alpha-Methyl glucosides, sorbyl alcohol, sucrose etc.In the middle of these, preferably use monohydric phenol.
The isocyanate compound of general formula (X) comprises 2,4 toluene diisocyanate, 2, and 6-tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, l,5 naphthylene diisocyanate, an eylylene diisocyanate etc.In the middle of these, tolylene diisocyanate is preferred.
The isocyanate compound of general formula (XII) is not special restriction, as long as it has two or more isocyanate group.This compound for example comprises phenylene vulcabond, 2, and 5-dimethoxy benzene-1, the 4-vulcabond, 2,4 toluene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethanediisocyanate, the o-tolidine vulcabond, l,5 naphthylene diisocyanate, the dianisidine vulcabond, 9-ethyl-carbazole-3,6-vulcabond, 3,3 '-dimethyl-4,4 '-diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, three (4-phenyl isocyanato) thiophosphatephosphorothioate, 4,4 ', 4 " three isocyanatos-2,5-dimethoxytrityl amine; 4; 4 ', 4 " three isocyanatos-triphenylamine, an eylylene diisocyanate, lysinediisocyanate, dimer acid diisocyanate, isopropylidene is two-4-cyclohexyl isocyanate, dicyclohexyl methane diisocyanate and methylcyclohexane diisocyanate.As the isocyanate compound of general formula (XII), can also use vulcabond dimer such as N, N '-(4,4 '-dimethyl-3,3 '-phenylbenzene two isocyanatos)-urea diketone (Desmodule TT, trade(brand)name), toluene diisocyanate dimer; With diisocyanate trimer as 4,4 ', 4 " trimethylammonium-3,3 ', 3 " three isocyanatos-2,4,6-triphenyl cyanurates.Can also use the water adduction isocyanic ester of tolylene diisocyanate, diphenylmethanediisocyanate etc., as 1, two (3-isocyanato-4-aminomethyl phenyl) ureas of 3-; The trimethylolpropane adduct of polyvalent alcohol adducts such as tolylene diisocyanate (Desmodule L, trade(brand)name); And amine adduct.
Can also use the compound with two or more isocyanate group of the row of the isocyanate compound described in the specification sheets that belongs to JP-A-10-76757 and JP-A-10-95171 and isocyanic ester addition compound.The particularly preferred example of the isocyanate compound of general formula (XII) is a tolylene diisocyanate.
The amine compound of general formula (XI) is not special restriction, as long as it has one or more amino.This compound for example comprises aromatic monoamine such as aniline, Ortho Toluidine, meta-aminotoluene, para-totuidine, o-anisidine, P-anisidine, p-phenetidine, 2, the 4-dimethoxyaniline, 2,5-dimethoxyaniline, 3, the 4-dimethoxyaniline, to amino-Acetanilide, para-amino benzoic acid, Ortho-Aminophenol, Metha Amino Phenon, p-aminophenol, 2,3-xylidene(s), 2, the 4-xylidene(s), 3, the 4-xylidene(s), 2,6-xylidene(s), 4-aminobenzonitrile, anthranilic acid, p-cresol is fixed, and 2, the 5-dichlorphenamide bulk powder, 2, the 6-dichlorphenamide bulk powder, 3,4-dichlorphenamide bulk powder, 3, the 5-dichlorphenamide bulk powder, 2,4, the 5-trichloroaniline, alpha-naphthylamine, amino anthracene, o ethyl aniline, Ortho-Chloro aniline, m-chloro aniline, p-Chlorobenzoic acid amide, methyl p-aminobenzoate, parathesin, para-amino benzoic acid n-propyl, the para-amino benzoic acid isopropyl ester, planoform, para-amino benzoic acid dodecyl ester, para-amino benzoic acid benzyl ester, adjacent aminobenzophenone, the m-aminophenyl ethyl ketone, para-aminoacetophenone, m-aminophenyl methane amide, anthranilamide, Para Amino Benzamide, right-amino-N-methyl-benzamide, 3-amino-4-methyl benzamide, 3-amino-4-methoxy benzamide, 3-amino-4-chlorobenzamide, right-(N-phenyl amino formyl radical) aniline, right-[N-(4-chloro-phenyl-) formamyl] aniline, right-[N-(4-aminophenyl)-formamyl] aniline, 2-methoxyl group-5-(N-phenyl amino formyl radical)-aniline, 2-methoxyl group-5-[N-(2 '-methyl-3 '-chloro-phenyl-) formamyl] aniline, 2-methoxyl group-5-[N-(2 '-chloro-phenyl-)-formamyl] aniline, 5-acetylaminohydroxyphenylarsonic acid 2-anisidine, the 4-acetylaminoaniline, 2-methoxyl group-4-(N-benzoyl-amino)-5-monomethylaniline, 4-sulfamyl aniline, 3-sulfamyl aniline, 2-(N-ethyl-N-phenyl amino alkylsulfonyl)-aniline, 4-dimethylamino alkylsulfonyl aniline, 4-diethylin alkylsulfonyl aniline, Sulphathiazole, 4-ADP base sulfone, 2-chloro-5-N-phenyl sulfamoyl base aniline, 2-methoxyl group-5-N, N-diethyl amino alkylsulfonyl aniline, 2,5-dimethoxy-4 '-N-phenyl sulfamoyl base aniline, 2-methoxyl group-5-benzyl alkylsulfonyl aniline, 2-phenoxy group alkylsulfonyl aniline, 2-(2 '-the chloro-phenoxy group) alkylsulfonyl aniline, 3-Phenylsulfamoyl base-4-monomethylaniline, adjacent chloro-p-Nitroaniline, adjacent nitro-p-Chlorobenzoic acid amide, 2,6-two chloro-4-N-methyl-p-nitroanilines, 5-chloro-2-N-methyl-p-nitroaniline, 2-amino-4-chlorophenol, o-Nitraniline, m-nitraniline, p-Nitroaniline, 2-methyl-4-N-methyl-p-nitroaniline, between nitro-para-totuidine, 2-amino-5-nitrobenzonitrile, Sulphanilic Acid, m-sulfanilic acid, 4B acid, C acid, 2B acid, para-fluoroaniline, adjacent fluoroaniline, 3-chloro-4-fluoroaniline, 2, the 4-difluoroaniline, 2,3, the 4-trifluoromethyl aniline, between-5 amido benzotrifluoride, 2-amino-3-bromo-5-nitrobenzonitrile etc.; With aromatic diamine as 4,4 '-diamino-3,3 '-the diethyl ditan, 4,4 '-the diaminobenzene formylaniline, 3, the 5-diaminochlorobenzene, diamino-diphenyl ether, 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane, 3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane, tolidine alkali, dianisidine, two [4-(m-aminophenyl oxygen base) phenyl] sulfone, two [4-(p-aminophenyl oxygen base) phenyl] sulfone, two [3-methyl-4-(p-aminophenyl oxygen base) phenyl] sulfone, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, o-tolidine sulfone, 2,4 '-benzidine, 2,2 '-benzidine, 4,4 '-benzidine, 2,2 '-two chloro-4,4 '-benzidine, 3,3 '-two chloro-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-thiobis aniline, 2,2 '-the dithio dianiline, 4,4 '-the dithio dianiline, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, two (3-amino-4-chloro-phenyl-) sulfone, two (3, the 4-diamino-phenyl) sulfone, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 3,4 '-diamino diphenyl sulfone, 3,3 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl amine, 4,4 '-ethylenebis aniline, 4,4 '-diamino-2,2 '-the dimethyl dibenzyl, 3,3 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-phenoxy group) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 3-, 9, two (4-aminophenyl) fluorenes of 9-, 2, two (the 4-amino-benzene oxygen phenyl) propane of 2-, 4,4 '-two (4-amino-benzene oxygen) biphenyl, dianisidine, 3,3 '-dichlorobenzidine.The amine compound of general formula (XI) also for example comprises heterogeneous ring compound amine such as 3-amino-1,2,4-triazole, 2-aminopyridine, the 3-aminopyridine, 4-aminopyridine, alpha-amino group-ε-Ji Neixianan, acetylguanamine, 2,4-diamino-6-[2 '-methylimidazolyl-(1)] ethyl-S-triazine, 2,3 diamino pyridine, 2,5-diamino-pyridine, 2,3,5-triamino pyridine, 1-amino-4-methylpiperazine, 1-(2-amino-ethyl) piperazine, two (aminopropyl) piperazine, N-(3-aminopropyl) morpholine etc.; With aliphatic amine such as methylamine, ethamine, stearylamine, allyl amine, isopropylamine, 2-DEHA, thanomin, 3-(2-ethyl hexyl oxy) propylamine, 3-ethoxycarbonyl propyl amine, 3-(diethylin) propylamine, 3-(dibutylamino) propylamine, tert-butylamine, propylamine, 3-(methylamino) propylamine, 3-(dimethylamino) propylamine, 3 methoxypropyl amine, methyl hydrazine, 1-methyl butyl amine, methane diamines, 1,4-diaminobutane, hexanaphthene methylamine, cyclo-hexylamine, 4-methylcyclohexyl amine, 2-bromine ethamine, the 2-methoxyethyl amine, 2-oxyethyl group methylamine, 2-amino-1-propyl alcohol, the 2-amino butanol, 3-amino-1,2-propylene glycol, 1,3-diamino-2-hydroxy propane, 2-ethylamine mercaptan, quadrol, diethylenetriamine, hexamethylene-diamine etc.In the middle of these, aromatic monoamine is preferred the use.
The amine compound of general formula (XIII) is not special restriction, as long as it has two or more amino.This compound for example comprise aromatic amine as 4,4 '-diamino-3,3 '-the diethyl ditan, 4,4 '-the diaminobenzene formylaniline, 3, the 5-diaminochlorobenzene, diamino-diphenyl ether, 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane, 3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane, tolidine alkali, dianisidine, two [4-(m-aminophenyl oxygen base) phenyl] sulfone, two [4-(p-aminophenyl oxygen base) phenyl] sulfone, two [3-methyl-4-(p-aminophenyl oxygen base) phenyl] sulfone, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, o-tolidine sulfone, 2,4 '-benzidine, 2,2 '-benzidine, 4,4 '-benzidine, 2,2 '-two chloro-4,4 '-benzidine, 3,3 '-two chloro-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-thiobis aniline, 2,2 '-the dithio dianiline, 4,4 '-the dithio dianiline, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, two (3-amino-4-chloro-phenyl-) sulfone, two (3, the 4-diamino-phenyl) sulfone, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 3,4 '-diamino diphenyl sulfone, 3,3 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl amine, 4,4 '-ethylenebis aniline, 4,4 '-diamino-2,2 '-the dimethyl dibenzyl, 3,3 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-phenoxy group) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 3-, 9, two (4-aminophenyl) fluorenes of 9-, 2, two (the 4-amino-benzene oxygen phenyl) propane of 2-, 4,4 '-two (4-amino-benzene oxygen) biphenyl, dianisidine, 3,3 '-dichlorobenzidine, tolidine alkali, adjacent phenylenediamine, m-phenylenediamine, P-pHENYLENE dI AMINE etc.In the above amine compound that exemplifies, have at least two amino and be particularly preferred with the anils of following formula (VIII) expression:
R wherein
1, R
2, R
3And R
4Be hydrogen atom, halogen atom, alkyl, alkoxyl group or amino independently, X
1And X
2Be group amino or that represent with following formula (b) independently:
Y
1Be-SO
2-,-O-,-(S)
n-,-(CH
2)
n-,-CO-,-CONH-and with in the group of any one expression of formula (a) any one:
Or Y
1Do not exist, n is 1 or 2.
The compound that contains the OH base of general formula (XIV) is not special restriction, as long as it has two or more OH bases.This compound for example comprises dihydric phenol as 2, two (4-hydroxyphenyl) propane of 2-, 2, two (hydroxyphenyl) butane of 2-, 2, two (hydroxyphenyl) pentanes of 2-, 2, two (hydroxyphenyl) heptane of 2-, catechol, the 3-methyl catechol, 3-methoxyl group catechol, pyrogallol, quinhydrones, toluhydroquinone, p, p '-bis-phenol, two (4-hydroxyphenyl) butylacetate, two (4-hydroxyphenyl) jasmal, two (4-hydroxyphenyl) sulfone, two (3-methyl-4-hydroxyphenyl) sulfone, two (3,5-dimethyl-4-hydroxyphenyl) sulfone, 3,4-dihydroxy phenyl-4 '-methyl phenyl sulfone, two (2-allyl group-4-hydroxyphenyl) sulfone, two (the 2-methyl-3-tertiary butyl-4-hydroxyphenyl) sulphur, 4,4 '-dihydroxydiphenyl ether, 4,4 '-thiobisphenol, 4,4 '-dihydroxy benaophenonel, 2, two (4-hydroxyphenyl) HFC-236fa of 2-, 4,4 '-the dihydroxyl ditan, 3,3 '-the dihydroxyl diphenylamine, two (4-hydroxy-3-methyl phenyl) sulphur etc.Yet as this dihydric phenol, it is unfavorable having amino those.Because amino have the higher reactivity to isocyanate group than OH base, amino before the OH base with the isocyanic ester radical reaction, make to be difficult to obtain required compound in some cases.The compound that contains the OH base of general formula (XIV) also comprises polyether polyol such as polypropylene glycol, polytetramethylene ether diol, hexanodioic acid deutero-polyvalent alcohol, the polyvalent alcohol of epoxy group(ing) modification, polyester ether polylol, polycarbonate polyol, polycaprolactone glycol, phenols polyvalent alcohol, amine modified polyalcohol etc.; With polyvalent alcohol such as ethylene glycol, glycol ether, 1, ammediol; 1,2-propylene glycol, propylene glycol, dipropylene glycol; 1,4-butyleneglycol, 1,5-pentanediol; 1,6-hexylene glycol, 1,9-nonanediol; the acryl polyvalent alcohol, fluorohydrocarbon polyvalent alcohol, polybutadiene polyol, poly-hydroxy polyvalent alcohol; TriMethylolPropane(TMP), trimethylolethane, hexanetriol; phosphoric acid, neopentyl glycol, tetramethylolmethane; castor oil modified polyvalent alcohol, polymer polyatomic alcohol, methyl pentanediol; halogen-containing polyvalent alcohol, phosphorus-containing polyol, quadrol; the Alpha-Methyl glucosides, sorbyl alcohol, sucrose etc.
The of the present invention the 21 and the 22 aspect each in the production method of urea-urea hydride compounds of the formula V that uses do not limit.This compound for example can be by making monohydric phenol compound and aromatic diisocyanate compound and following general formula (XV) diamine compound for example according to reaction formula shown below (G) or (H) reaction obtain:
Wherein the hydrogen atom of each phenyl ring can be substituted the base displacement; substituting group is the aromatic substance residue preferably; aliphatic cpd residue or heterogeneous ring compound residue; substituting group also can be that nitro, hydroxyl, carboxyl, nitroso-group, itrile group, formamyl, urea groups, isocyanate group, sulfydryl, sulfo group, sulfamyl or halogen atom, each residue can have one or more substituting groups, and γ is-SO
2-,-O-,-(S)
n-,-(CH
2)
n-,-CO-,-CONH-and with in the group of any one expression of formula (a) any one:
Perhaps γ does not exist, and n is 1 or 2.
The of the present invention the 21 and the 22 aspect each in the production method of urea-urea hydride compounds of the formula (VI) used do not limit.This compound for example can be by making anils and aromatic diisocyanate compound and following general formula (XVI) oxy-compound for example according to reaction formula shown below (J) or (K) reaction obtain:
Wherein the hydrogen atom of each phenyl ring can be substituted the base displacement; substituting group is aromatic substance residue, aliphatic cpd residue or heterogeneous ring compound residue preferably; substituting group also can be hydroxyl, nitro, itrile group, formamyl, sulfamyl, carboxyl, nitroso-group, amino, oxygen amino, nitro amino, diazanyl, urea groups, isocyanate group, sulfydryl, sulfo group or halogen atom; each residue can have one or more substituting groups, and δ is-SO
2-,-O-,-(S)
n-,-(CH
2)
n-,-CO-,-CONH-,-NH-,-CH (COOR
1)-,-C (CF
3)
2-and-CR
2R
3-in any one or do not have R
1, R
2And R
3Be alkyl independently, n is 1 or 2.
Below will explain in detail can be used for synthesizing the of the present invention the 21 and the 22 aspect each in the formula V that uses or the compound of urea (VI)-urea hydride compounds.
The phenolic compound that can be used for the urea-urea hydride compounds of synthetic formula V is not special restriction, as long as it has one or more OH on phenyl ring.In addition; the hydrogen atom of phenyl ring can be by the substituting group of non-OH base, and promptly aromatic substance residue, aliphatic cpd residue, heterogeneous ring compound residue, nitro, carboxyl, nitroso-group, itrile group, formamyl, urea groups, isocyanate group, sulfydryl, sulfo group, sulfamyl or halogen atom replace.
The preferred embodiment of phenolic compound is phenol such as phenol; cresols; xylenol; p-ethyl phenol; o-isopropyl phenol; Resorcinol; p-tert-butylphenol; to tert-octyl phenol; the 2-cyclohexylphenol; the 2-chavicol; the 4-indanol, thymol, beta naphthal; the phenol (as p-NP) that nitro replaces; the phenol (as ortho chloro phenol and para-chlorophenol) that halogen replaces, the 4-phenylphenol, 4-hydroxyphenyl-4 '-methyl phenyl sulfone; 3-chloro-4-hydroxyphenyl-4 '-methyl phenyl sulfone; 4-isopropyl phenyl-4 '-the hydroxy phenyl sulfone, 4-isopropyl phenyl-4 '-the hydroxyphenyl sulfone, 4-hydroxyphenyl-4 '-the benzyloxy phenylsulfone; 4-isopropyl phenyl-4 '-the hydroxyphenyl sulfone; 4-hydroxyl-4 '-sec.-propyl oxygen base sulfobenzide, salol, salicylamide; the 4-methyl hydroxybenzoate; the 4-hydroxy benzoic acid benzyl ester, the 4-hydroxy-benzoic acid (4 '-the benzyl chloride base) ester, 3-hydroxyl phthalic dimethyl ester; the 4-methoxyphenol; 4-(benzyloxy) phenol, 4-hydroxy benzaldehyde, 4-n-octyloxy Whitfield's ointment; 4-n-butoxy Whitfield's ointment; 4-n-pentyloxy Whitfield's ointment, 3-dodecyl oxygen base Whitfield's ointment, the positive hot acyloxy Whitfield's ointment of 3-; 4-n-octyloxy carbonylamino Whitfield's ointment, the positive capryloyl oxygen of 4-base carbonylamino Whitfield's ointment etc.As phenolic compound, can also use to have one or more substituent phenolic compounds, comprise carboxyl, nitroso-group, itrile group, formamyl, urea groups, isocyanate group, sulfydryl, sulfo group, sulfamyl etc.Yet as this phenol, it is undesirable having amino those.Because amino have the reactivity higher to isocyanate group than OH base, amino before the OH base with the isocyanic ester radical reaction, make to be difficult to obtain required compound in some cases.
The aromatic diisocyanate compound that can be used for synthetic formula V or urea (VI)-urea hydride compounds is not special restriction, as long as it has two isocyanate group that are bonded in its phenyl ring.The aromatic diisocyanate compound for example comprises phenylene vulcabond, 2, and 5-dimethoxy benzene-1,4-vulcabond, 2,4 toluene diisocyanate and 2,6-tolylene diisocyanate.The especially preferred example of aromatic diisocyanate compound is a tolylene diisocyanate.In the middle of tolylene diisocyanate, 2,4 toluene diisocyanate is preferred.Except 2,4 toluene diisocyanate, 2,4 toluene diisocyanate and 2, the mixture of 6-tolylene diisocyanate are on sale on market usually, can obtain at a low price, and also can be used as aromatic diisocyanate.These tolylene diisocyanate mixture of isomers are liquid at normal temperatures.
The diamine compound of general formula (XV) that can be used for the urea-urea hydride compounds of synthetic formula V for example comprise aromatic diamine as 4,4 '-diamino-3,3 '-the diethyl ditan, 4,4 '-the diaminobenzene formylaniline, 3, the 5-diaminochlorobenzene, diamino-diphenyl ether, 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane, 3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane, tolidine alkali, dianisidine, two [4-(m-aminophenyl oxygen base) phenyl] sulfone, two [4-(p-aminophenyl oxygen base) phenyl] sulfone, two [3-methyl-4-(p-aminophenyl oxygen base) phenyl] sulfone, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, Ortho Toluidine sulfone, 2,4 '-benzidine, 2,2 '-benzidine, 4,4 '-benzidine, 2,2 '-two chloro-4,4 '-benzidine, 3,3 '-two chloro-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-thiobis aniline, 2,2 '-the dithio dianiline, 4,4 '-the dithio dianiline, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, two (3-amino-4-chloro-phenyl-) sulfone, two (3, the 4-diamino-phenyl) sulfone, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 3,4 '-diamino diphenyl sulfone, 3,3 '-diamino-ditan, 4,4 '-diamino-diphenyl amine, 4,4 '-ethylenebis aniline, 4,4 '-diamino-2,2 '-the dimethyl dibenzyl, 3,3 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-phenoxy group) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 3-, 9, two (4-aminophenyl) fluorenes of 9-, 2, two (the 4-amino-benzene oxygen phenyl) propane of 2-, 4,4 '-two (4-amino-benzene oxygen) biphenyl, dianisidine, 3,3 '-dichlorobenzidine etc.
The anils that can be used for the urea-urea hydride compounds of synthesis type (VI) is not special restriction, as long as it is the aniline compound that has one or more amino on phenyl ring.In addition, the hydrogen atom of phenyl ring can be replaced by aromatic substance residue, aliphatic cpd residue, heterogeneous ring compound residue, hydroxyl, nitro, itrile group, formamyl, sulfamyl, carboxyl, nitroso-group, amino, oxygen amino, nitro amino, diazanyl, urea groups, isocyanate group, sulfydryl, sulfo group or halogen atom.
The preferred embodiment of this aniline compound is an aniline, Ortho Toluidine, meta-aminotoluene; para-totuidine, o-anisidine, P-anisidine; p-phenetidine, N, N-dimethyl-right-phenylenediamine; N, N-diethyl-P-pHENYLENE dI AMINE, 2; the 4-dimethoxyaniline, 2, the 5-dimethoxyaniline; 3, the 4-dimethoxyaniline is to amino-Acetanilide; the aniline that the aniline of carboxyl substituted (for example para-amino benzoic acid), hydroxyl replace (Ortho-Aminophenol for example, Metha Amino Phenon; 2-amino-4-chlorophenol and p-aminophenol), 2, the 3-xylidene(s); toluene 24 diamine, 3; the 4-xylidene(s), 2, the 6-xylidene(s); the aniline (for example 4-aminobenzonitrile) that nitrile replaces, anthranilic acid, p-cresol is fixed; the aniline that halogen replaces (for example 2,5-dichlorphenamide bulk powder, 2; the 6-dichlorphenamide bulk powder, 3, the 4-dichlorphenamide bulk powder; 3,5-dichlorphenamide bulk powder, 2; 4; the 5-trichloroaniline, Ortho-Chloro aniline, m-chloro aniline and p-Chlorobenzoic acid amide); alpha-naphthylamine; amino anthracene, o ethyl aniline, methyl p-aminobenzoate; parathesin; the para-amino benzoic acid n-propyl, para-amino benzoic acid isopropyl ester, planoform; the para-amino benzoic acid dodecyl ester; para-amino benzoic acid benzyl ester, adjacent aminobenzophenone, m-aminophenyl ethyl ketone; para-aminoacetophenone; the m-aminophenyl methane amide, anthranilamide, Para Amino Benzamide; right-amino-N-methyl-benzamide; 3-amino-4-methyl benzamide, 3-amino-4-methoxy benzamide, 3-amino-4-chlorobenzamide; formamyl aniline is (for example right-(N-phenyl amino formyl radical) aniline; right-[N-(4-chloro-phenyl-) formamyl] aniline, right-[N-(4-aminophenyl)-formamyl] aniline, 2-methoxyl group-5-(N-phenyl amino formyl radical)-aniline; 2-methoxyl group-5-[N-(2 '-methyl-3 '-chloro-phenyl-) formamyl] aniline and 2-methoxyl group-5-[N-(2 '-chloro-phenyl-)-formamyl] aniline); 5-acetylamino-2-anisidine, 4-acetylaminoaniline, 4-(N-methyl-N-kharophen) aniline; 2; 5-diethoxy-4-(N-benzoyl-amido) aniline, 2,5-dimethoxy-4 '-(N-benzoyl-amido) aniline; 2-methoxyl group-4-(N-benzoyl-amino)-5-monomethylaniline; sulfamyl aniline (4-sulfamyl aniline for example, 3-sulfamyl aniline, 2-chloro-5-N-phenyl sulfamoyl base aniline; 2-methoxyl group-5-N; N-diethyl amino alkylsulfonyl aniline and 2,5-dimethoxy-4 '-N-phenyl sulfamoyl base aniline), 2-(N-ethyl-N-phenyl amino alkylsulfonyl)-aniline; 4-dimethylamino alkylsulfonyl aniline; 4-diethylin alkylsulfonyl aniline, Sulphathiazole, 4-ADP base sulfone; 2-methoxyl group-5-benzyl alkylsulfonyl aniline; 2-phenoxy group alkylsulfonyl aniline, 2-(2 '-the chloro-phenoxy group) alkylsulfonyl aniline, 3-Phenylsulfamoyl base-4-monomethylaniline; aniline (for example adjacent chloro-p-Nitroaniline that nitro replaces; adjacent nitro-p-Chlorobenzoic acid amide, 2,6-two chloro-4-N-methyl-p-nitroanilines; 5-chloro-2-N-methyl-p-nitroaniline; o-Nitraniline, m-nitraniline, p-Nitroaniline; 2-methyl-4-N-methyl-p-nitroaniline; between nitro-para-totuidine and 2-amino-5-nitrobenzonitrile), para-fluoroaniline, adjacent fluoroaniline; 3-chloro-4-fluoroaniline; 2,4 difluorobenzene amine, 2; 3; the 4-trifluoromethyl aniline ,-5 amido benzotrifluoride, 2-amino-3-bromo-5-nitrobenzonitrile etc.
As anils, can also use to have one or more substituent anilss, substituting group comprises carboxyl, nitroso-group, oxygen amino, nitro amino, diazanyl, urea groups, isocyanate group, sulfydryl, sulfo group etc.
The dihydroxy compound of general formula (XVI) that can be used for the urea-urea hydride compounds of synthesis type (VI) comprises dihydric phenol as 2, two (4-hydroxyphenyl) propane of 2-, 2, two (hydroxyphenyl) butane of 2-, 2, two (hydroxyphenyl) pentanes of 2-, 2, two (hydroxyphenyl) heptane of 2-, 4,4 '-bis-phenol, two (4-hydroxyphenyl) butylacetate, two (4-hydroxyphenyl) jasmal, two (4-hydroxyphenyl) sulfone, two (3-methyl-4-hydroxyphenyl) sulfone, two (3,5-dimethyl-4-hydroxyphenyl) sulfone, two (2-allyl group-4-hydroxyphenyl) sulfone, two (the 2-methyl-3-tertiary butyl-4-hydroxyphenyl) sulphur, 4,4 '-dihydroxydiphenyl ether, 4,4 '-thiobisphenol, 4,4 '-dihydroxy benaophenonel, 2, two (4-hydroxyphenyl) HFC-236fa of 2-, 4,4 '-the dihydroxyl ditan, 3,3 '-the dihydroxyl diphenylamine, two (4-hydroxy-3-methyl phenyl) sulphur etc.Yet as this dihydric phenol, it is undesirable having amino those.Because amino have the higher reactivity to isocyanate group than OH base, amino before the OH base with the isocyanic ester radical reaction, make to be difficult to obtain required compound in some cases.
The of the present invention the 21 and the 22 aspect each in the synthetic method of urea-urea hydride compounds of the formula (VII) used be not special restriction.This compound for example can be by making general formula (IX) the compound of hydroxyl and the isocyanate compound of general formula (XII) and the amine compound of general formula (XI) for example obtain according to following reaction formula (L) reaction:
As the substituting group of the X of the urea groups of the urea that is bonded in general formula (VII)-urea hydride compounds, alkyl, thiazolinyl, phenyl, cycloalkyl, amide group, alkoxyl group, nitro, nitroso-group, itrile group, tosyl group, methylsulfonyl, ethanoyl, halogen atom, formyl radical, dialkyl amido and isocyanate group are preferred.
In these ureas-urea hydride compounds as the general formula (I)-(VII) of developer, the compound of general formula (II)-(VI) is preferred, and logical formula V and compound (VI) are particularly preferred.
In addition, following structural formula (XX) or compound (XXI) are particularly preferred.
Be used as in aspect the of the present invention the 21 and the 22 each under the urea-urea hydride compounds and situation of developer as the formula (I)-(IV) of developer and compound (VII), if being bonded in the residue of its urea groups or urea alkyl is the aliphatic cpd residues, colorant density and print retention in some cases can variation.Therefore, preferably aromatic substance residue or heterogeneous ring compound residue of the residue that is bonded in urea groups or urea alkyl.Yet, may can lower by the sum that increases urea groups and urea alkyl by introducing the colorant density that the aliphatic cpd residue causes and the decline of print retention.Under the situation of the compound of formula (III) and formula (IV),, can cause the problem of relevant performance aspect hardly even the aliphatic cpd residue belongs to the residue that is bonded in urea groups or urea alkyl.
The of the present invention the 21 and each of the 22 aspect in urea-urea hydride compounds of using can be by in organic solvent or do not have to mix isocyanic ester and corresponding reagent under the situation of solvent, make their reactions, obtain by filtering collection gained crystal then.As each reagent, can use one or more compounds according to purpose.As solvent, can use any solvent, as long as the functional group of it and isocyanate group and reagent does not react.Solvent for example comprises aliphatic hydrocarbon, alicyclic hydro carbons, aromatic hydrocarbons, chlorination aliphatic hydrocarbon, chlorinating aromatic hydro carbons, alicyclic hydro carbons of chlorination and ketone.It is particularly preferred dissolving methyl ethyl ketone that isocyanic ester and reaction product have low solubility therein, toluene etc.The reaction product that obtains by above reaction process is simplification compound always not, in some cases, but obtains as the mixture of the different compound of substituting group position.
The of the present invention the 21 and the 22 aspect each in the specific examples of urea-urea hydride compounds of using be following compound ((E-1)-(E-43)).
Urea-urea hydride compounds as developer normally is the colourless or light compound of solid at normal temperatures in the present invention.
In the present invention as the molecular weight of the urea-urea hydride compounds of developer preferably below 5,000 or 5,000, more preferably below 2,000 or 2,000.
, be more preferably below 10 or 10 preferably below 20 or 20 as the sum of urea groups in the urea-urea hydride compounds of developer and urea alkyl in the present invention.Urea groups and the urea alkyl ratio in the molecular structure of urea-urea hydride compounds preferably 1: 3-3: 1, particularly 1: 2-2: 1.
For by using urea-urea hydride compounds to produce recording materials as developer, can use a kind of urea-urea hydride compounds, or if necessary, the binding substances of two or more ureas-urea hydride compounds.
When being used for thermal recording medium, preferred urea-urea hydride compounds has fusing point.The fusing point that is used as the urea-urea hydride compounds of developer in the present invention is preferably 40 ℃ to 500 ℃, especially 60 ℃ to 300 ℃.
Colourless or the light dyestuff former that uses in aspect the 22 of the present invention is the compound that is commonly referred to as coupler that uses in pressure sensitive recording material and thermal recording medium, and is not special the restriction.As dyestuff former, leuco dye is particularly preferred, and triarylmethane type leuco dye, fluorane type leuco dye, fluorenes type leuco dye, ditan type leuco dye etc. are preferred.Below provided the representative instance of leuco dye.
(1) triarylmethane type compound
3, two (right-the dimethylamino phenyl)-6-dimethylamino benzo [c] furanones (crystal violet lactone) of 3-, 3, two (right-the dimethylamino phenyl) benzo [c] furanones of 3-, 3-(right-the dimethylamino phenyl)-3-(1,2-dimethyl indole-3-yl) benzo [c] furanone, 3-(right-the dimethylamino phenyl)-3-(2 methyl indole-3-yl) benzo [c] furanone, 3-(to the dimethylamino phenyl)-3-(2-phenylindone-3-yl) benzo [c] furanone, 3,3-two (1,2-dimethyl indole-3-yl)-and 5-dimethylamino benzo [c] furanone, 3,3-two (1,2-dimethyl indole-3-yl)-6-dimethylamino benzo [c] furanone, 3, two (9-ethyl carbazole-3-yl)-5-dimethylamino benzo [c] furanones of 3-, 3, two (2-phenylindone-3-yl)-5-dimethylamino benzo [c] furanones of 3-, 3-is right-dimethylamino phenyl-3-(1-methylpyrrole-2-yl)-6-dimethylamino benzo [c] furanone etc.
(2) ditan type compound
4,4 '-Bis-dimethylamino phenyl diphenyl-methyl benzyl oxide, N-halogenophenyl-colourless auramine, N-2,4, the colourless auramine of 5-trichlorophenyl etc.
(3) xanthene type compound
Rhodamine B anilino lactan, rhodamine B-right-chloroanilino lactan, 3-dimethylamino-6-methyl-7-(m-trifluoromethyl anilino) fluorane, 3-diethylin-6-methyl fluoran, 3-diethylin-7-methyl fluoran, 3-diethylin-7-chlorine fluorane, 3-diethylin-7-dibenzyl amino fluorane, 3-diethylin-6-methyl-7-chlorine fluorane, the amino fluorane of 3-diethylin-7-octyl group, 3-diethylin-7-phenyl fluorane, 3-diethylin-6-methyl-7-anilino fluorane, 3-diethylin-6-methyl-7-is to the toluidine fluorane, 3-diethylin-6-chloro-7-methyl fluoran, 3-diethylin-7-(3,4-dichlorobenzene amido)-fluorane, 3-diethylin-7-(2-chloroanilino) fluorane, 3-diethylin-6-methyl-7-(neighbour, right-the dimethyl benzene amido) fluorane, 3-(N-ethyl-N-tolyl) amino-6-methyl-7-styroyl fluorane, 3-diethylin-7-(4-oil of mirbane amido) fluorane, 3-diethylin-6-methyl-7-(m-trifluoromethyl anilino) fluorane, 3-diethylin-6-methyl-7-(Ortho-Chloro aniline base) fluorane, 3-diethylin-6-methyl-7-(p-Chlorobenzoic acid amide base) fluorane, 3-diethylin-6-methyl-7-(adjacent fluoroanilino) fluorane, 3-diethylin-6-methyl-7-(right-the n-butylbenzene amido) fluorane, the amino fluorane of 3-diethylin-6-methyl-7-n-octyl, 3-diethylin-6-chloro-7-anilino fluorane, 3-diethylin-6-ethoxyethyl group-7-anilino fluorane, 3-diethylin-benzo [a] fluorane, 3-diethylin-benzo [c] fluorane, 3-diethylin-6-methyl-7-benzylamino fluorane, 3-diethylin-6-methyl-7-dibenzyl amino fluorane, the amino fluorane of 3-diethylin-7-two (right-methyl-benzyl), the amino fluorane of 3-diethylin-6-methyl-7-diphenyl methyl, 3-diethylin-7-dinaphthyl methylamino fluorane, 10-diethylin-4-dimethylamino benzo [a] fluorane, 3-diethylin-7,8-benzo fluorane, 3-diethylin-6-methyl-7-(-the trichlorobenzene amido) fluorane, 3-diethylin-7-(Ortho-Chloro aniline base) fluorane, 3-dibutylamino-7-(Ortho-Chloro aniline base) fluorane, 3-diethylin-6-methyl-7-(2 ', 4 '-the dimethyl benzene amido) fluorane, 3-(N, the N-diethylin)-5-methyl-7-(N, N-dibenzyl amino) fluorane, morpholinyl-7-(N-propyl group trifluoromethylbenzene amido) fluorane, 3-pyrrolidyl-7-trifluoromethylbenzene amido fluorane, 3-diethylin-5-chloro-7-(N-benzyl-trifluoromethylbenzene amido) fluorane, 3-pyrrolidyl-7-(two-right-chloro-phenyl-) methylamino fluorane, 3-diethylin-5-chloro-7-(α-styroyl amino) fluorane, 3-(N-ethyl-N-right-toluino)-7-(α-styroyl amino) fluorane, 3-diethylin-7-(neighbour-methoxycarbonyl styroyl) fluorane, 3-diethylin-5-methyl-7-(α-styroyl amino) fluorane, the amino fluorane of 3-diethylin-7-piperidino-(1-position only), 3-chloro-3-(N-methyl toluino)-7-(right-N-butylbenzene amido) fluorane, 3-(N-ethyl-N-cyclohexyl amino)-5,6-benzo-7-α-naphthylamino-4 '-the bromine fluorane, 3-diethylin-6-methyl-7-mesidino (mesitidino)-4 ', 5 '-the benzo fluorane, 3-dibutylamino-6-methyl fluoran, 3-dibutylamino-6-methyl-7-chlorine fluorane, 3-dibutylamino-6-methyl-7-anilino fluorane, 3-dibutylamino-6-methyl-7-is to the toluidine fluorane, 3-dibutylamino-6-methyl-7-(neighbour, right-the dimethyl benzene amido) fluorane, 3-dibutylamino-6-methyl-7-(m-trifluoromethyl anilino) fluorane, 3-dibutylamino-6-methyl-7-(Ortho-Chloro aniline base) fluorane, 3-dibutylamino-6-methyl-7-(p-Chlorobenzoic acid amide base) fluorane, 3-dibutylamino-6-methyl-7-(adjacent fluoroanilino) fluorane, 3-dibutylamino-6-methyl-7-(right-the n-butylbenzene amido) fluorane, the amino fluorane of 3-dibutylamino-6-methyl-7-n-octyl, 3-dibutylamino-6-chloro-7-anilino fluorane, 3-dibutylamino-6-ethoxyethyl group-7-anilino fluorane, 3-two n-pentyls amino-6-methyl-7-anilino fluorane, 3-two n-pentyls amino-6-methyl-7-(neighbour, right-dimethyl-anilino) fluorane, 3-two n-pentyls amino-6-methyl-7-(m-trifluoromethyl anilino) fluorane, 3-two n-pentyls amino-6-methyl-7-(Ortho-Chloro aniline base) fluorane, 3-two n-pentyls amino-6-methyl-7-(p-Chlorobenzoic acid amide base) fluorane, 3-two n-pentyls amino-6-methyl-7-(adjacent fluoroanilino) fluorane, 3-pyrrolidyl-6-methyl-7-anilino fluorane, 3-piperidino-(1-position only)-6-methyl-7-anilino fluorane, 3-cyclohexyl amino-6-chloro-fluorane, 3-dimethylamino-5,7-dimethyl fluorane, 3-(N-methyl-N-isopropyl amyl group amino)-6-methyl-7-anilino fluorane, 3-(N-methyl-N-n-propyl amino)-6-methyl-7-anilino fluorane, 3-(N-methyl-N-amyl group amino)-6-methyl-7-anilino fluorane, 3-(N, N-two n-pentyl amino)-6-methyl-7-anilino fluorane, 3-(N-methyl-N-isopropyl propyl group amino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-n-propyl amino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-sec.-propyl amino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-n-butyl amine base)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-isobutylamino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-n-hexyl amino)-6-methyl-7-is to the toluidine fluorane, 3-(N-ethyl-N-n-hexyl amino)-6-methyl-7-(neighbour, right-the dimethyl benzene amido) fluorane, 3-(N-ethyl-N-n-hexyl amino)-6-methyl-7-(m-trifluoromethyl anilino) fluorane, 3-(N-ethyl-N-n-hexyl amino)-6-methyl-7-(Ortho-Chloro aniline base) fluorane, 3-(N-ethyl-N-isopentyl amino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-isopentyl amino)-6-chloro-7-anilino fluorane, 3-(N-ethyl-N-3-methyl butyl amino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-is to toluino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-right-toluino)-6-methyl-7-(to toluidine) fluorane, 3-(N-ethyl-N-right-toluino)-6-methyl-7-(neighbour, right-the dimethyl benzene amido) fluorane, 3-(N-ethyl-N-tetrahydrofurfuryl amino)-6-methyl-7-anilino fluorane, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilino fluorane, 3-(N-cyclohexyl-N-methylamino)-7-anilino fluorane, 3-(N-ethyl-N-3-methoxy-propyl amino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-3-ethoxycarbonyl propyl amino)-6-methyl-7-anilino fluorane, 2-(4-oxa-hexyl)-3-dimethylamino-6-methyl-7-anilino fluorane, 2-(4-oxa-hexyl)-3-diethylamino-6-methyl-7-anilino fluorane, 2-(4-oxa-hexyl)-3-dipropyl-amino-6-methyl-7-anilino fluorane, 3, two (diethylamino)-fluorane-γ of 6--(2 '-nitro) the anilino lactan, 3, two (diethylamino) fluorane-γ of 6--(3 '-nitro) the anilino lactan, 3, two (diethylin) fluorane-γ of 6--(4 '-nitro) the anilino lactan, 3, two (diethylin) fluorane-γ of 6--anilino lactan etc.
(4) thiazine type compound
The benzoyl leucomethylene blue, p-nitrophenyl formyl radical leucomethylene blue etc.
(5) spiro-compounds
3-methylspiro dinaphthopyran, 3-ethyl spiral shell dinaphthopyran, 3,3-dichloro spiral shell dinaphthopyran, 3-benzyl spiral shell dinaphthopyran, 3-methyl naphtho--(3-methoxyl group-benzo) spiro-pyrans, 3-propyl group spirobenzopyran etc.
Leuco dye for example also comprise can absorption near infrared ray following compound: 3, two (dimethylamino) fluorenes of 6--9-spiral shell-3 '-(6 '-dimethylamino benzo [c] furanone), 3-diethylin-6-dimethylamino fluorenes-9-spiral shell-3 '-(6 '-dimethylamino benzo [c] furanone), 3, two (diethylin) fluorenes of 6--9-spiral shell-3 '-(6 '-dimethylamino benzo [c] furanone), 3-dibutylamino-6-dimethylamino fluorenes-9-spiral shell-3 '-(6 '-dimethylamino benzo [c] furanone), 3-dibutylamino-6-(diethylin fluorenes-9-spiral shell-3 '-(6 '-dimethylamino benzo [c] furanone), 3, two (the dimethylamino)-fluorenes of 6--9-spiral shell-3 '-(6 '-diethylin benzo [c] furanone), 3-diethylin-6-dimethylamino fluorenes-9-spiral shell-3 '-(6 '-diethylin benzo [c] furanone), 3-dibutylamino-6-dimethylamino fluorenes-9-spiral shell-3 '-(6 '-diethylin benzo [c] furanone), 3, two (diethylin) fluorenes of 6--9-spiral shell-3 '-(6 '-diethylin benzo [c] furanone), 3, two (dimethylamino) fluorenes of 6--9-spiral shell-3 '-(6 '-dibutylamino benzo [c] furanone), 3-dibutylamino-6-diethylin fluorenes-9-spiral shell-3 '-(6 '-diethylin benzo [c] furanone), 3-diethylin-6-dimethylamino fluorenes-9-spiral shell-3 '-(6 '-dibutylamino benzo [c] furanone), 3, two [2-(4-dimethylamino phenyl)-2-(4-p-methoxy-phenyl) vinyl]-4 of 3-, 5,6,7-tetrachloro benzo [c] furanone etc.
In the above leuco dye that exemplifies, triarylmethane type leuco dye, fluorane type leuco dye, fluorenes type leuco dye and ditan type leuco dye see it is preferred from the angle of sensitivity and plasticizer resistance properties, and the compound that has with following chemical formula (i) or the structure (j) represented is preferred:
Y wherein
2And Y
3The two is alkyl or alkoxyalkyl, Y
4Be hydrogen atom, alkyl or alkoxyl group, Y
5And Y
6Each is hydrogen atom, halogen atom, alkyl or alkoxyl group naturally; Or
R wherein
5And R
6Each uses the group of formula (k) or formula (1) expression naturally:
(R wherein
11-R
15Each is hydrogen atom, halogen atom, C naturally
1-C
8Alkyl, C
1-C
8Alkoxyl group or-NR
16R
17, R wherein
16And R
17Each is C naturally
1-C
8Alkyl); Or
(R wherein
18And R
19Each is hydrogen atom, C naturally
1-C
8Alkyl or phenyl) R
7-R
10Each is hydrogen atom, halogen atom, C naturally
1-C
8Alkyl, C
1-C
8Alkoxyl group or-NR
20R
21, R wherein
20And R
21Each is C naturally
1-C
8Alkyl.
If necessary, these colourless or light dyestuff formers can use with their two or more binding substances.
As the urea-urea hydride compounds of developer with preferred 5-1,000 weight part, more preferably 20-500 weight part/100 weight parts ratio colourless or light dyestuff former is used.About the ratio of developer urea-urea hydride compounds, 5 weight parts or be enough to make dyestuff former colour developing more than 5 weight parts.Under this ratio, colorant density is high.When the ratio as the urea-urea hydride compounds of developer is 1,000 weight part or 1,000 weight part when following, urea-urea hydride compounds developer remains hardly, and this is favourable economically and is preferred therefore.
Urea-urea hydride compounds or urea-urea alkane composition as being used as developer in aspect nineteen of the present invention can use any urea-urea hydride compounds of of the present invention first to the 4th aspect or any urea-urea alkane composition in the 5th to the 12 aspect of the present invention.The synthetic method of these compounds and composition is described in detail in the explanation aspect the first to the 12 of the present invention.
Isocyanate compound is incorporated into the shelf stability of having improved composition in the color former of the present invention.Be incorporated into isocyanate compound in the color former of the present invention and be meant colourless or light for solid at normal temperatures, aromatics or heterocycle isocyanate compound.For example, one or more of the following isocyanate compound of use.
The isocyanate compound of being introduced comprises 2,6-dichlorophenyl isocyanate, rubigan isocyanic ester, 1,3-phenylene vulcabond, 1, the 4-phenylene vulcabond, 1,3-dimethyl benzene-4, the 6-vulcabond, 1,4-dimethyl benzene-2, the 5-vulcabond, 1-anisole-2,4-vulcabond, 1-anisole-2,5-vulcabond, 1-phenetole-2, the 4-vulcabond, 2,5-dimethoxy benzene-1, the 4-vulcabond, 2,5-diethoxybenzene-1, the 4-vulcabond, 2,5-dibutoxy benzene-1, the 4-vulcabond, nitrogen benzide-4,4 '-vulcabond, diphenyl ether-4,4 '-vulcabond, naphthalene-1, the 4-vulcabond, naphthalene-1,5-vulcabond, naphthalene-2,6-vulcabond, naphthalene-2, the 7-vulcabond, 3,3 '-dimethyl-xenyl-4,4 '-vulcabond, 3,3 '-dimethoxy-xenyl-4,4 '-vulcabond, ditan-4,4 '-vulcabond, phenylbenzene dimethylmethane-4,4 '-vulcabond, phenylbenzene dimethylmethane-4,4 '-vulcabond, benzophenone-3,3 '-vulcabond, fluorenes-2, the 7-vulcabond, anthraquinone-2,6-vulcabond, 9-ethyl carbazole-3, the 6-vulcabond, pyrene-3,8-vulcabond, naphthalene-1,3, the 7-triisocyanate, xenyl-2,4,4 '-triisocyanate, 4,4 ', 4 " three isocyanatos-2; 5-dimethoxytrityl amine; 4,4 ', 4 " three isocyanatos-triphenylamine, right-the Dimethylaminobenzene based isocyanate, three (4-phenyl isocyanato) thiophosphatephosphorothioate etc.If necessary, these isocyanic ester can be with so-called blocked isocyanate, promptly use with the form of the addition compound of phenol, lactan, oxime etc., they can be with vulcabond dimer such as 1-methylbenzene-2,4-vulcabond dimer, or use as the form of two isocyanurate trimer of isocyanuric acid ester, and the form of any polyisocyanates that obtains as adducts that they can be by using various polyvalent alcohols uses, and other or the like.Can also use 2,4 toluene diisocyanate, the water adduction isocyanic ester of diphenylmethanediisocyanate etc., as 1, two (3-isocyanato-4-aminomethyl phenyl) ureas of 3-; The trimethylolpropane adduct of polyvalent alcohol adducts such as tolylene diisocyanate (DesmoduleL, trade(brand)name); Phenol adduction isocyanic ester; Amine adduction isocyanic ester; With at isocyanate compound and the isocyanic ester addition compound described in the specification sheets of the specification sheets of JP-A-10-76757 and JP-A-10-95171.
Isocyanate compound is preferably with the 5-500 weight part, and more preferably the ratio of the colourless or light dyestuff former of 20-200 weight part/100 weight parts is used.When the ratio of isocyanate compound is 5 weight parts or 5 weight parts when above, the effect and the colorant density that can obtain fully to improve shelf stability are high.When the ratio of isocyanate compound is 500 weight parts or 500 weight parts when following, isocyanate compound remains hardly, and this is favourable economically, is preferred therefore.
Imino-compound is incorporated into further improved shelf stability in the color former of the present invention.
The imino-compound that can be incorporated in the color former of the present invention is to have at least one imino-and be the colourless or light compound of solid at normal temperatures.According to purpose, can be in conjunction with introducing two or more imino-compounds.As imino-compound, can mention that the content of this reference is quoted for reference here at described in the JP-A-9-142032 those.In the imino-compound described in this reference, imino--isoindoline derivative is preferred, 1,3-diimino-4,5,6,7-tetrachloro isoindoline, 3-imino--4,5,6,7-tetrachloro 1-isoindolinone and 1,3-diimino-4,5,6,7-tetrabromo isoindoline is preferred.
Preferred imino-compound is with the 5-500 weight part, and more preferably the ratio of the colourless or light dyestuff former of 20-200 weight part/100 weight parts is used.When the ratio of imino-compound is 5 weight parts or 5 weight parts when above, obtained to improve the effect of shelf stability.When the ratio of imino-compound is 500 weight parts or 500 weight parts when following, imino-compound remains hardly, and this is favourable economically, is preferred therefore.
In addition, aminocompound is incorporated into the retention that has improved source recording material surface and print in the color former of the present invention.The aminocompound that can introduce be have at least one primary, the colourless or light material of the second month in a season and uncle's amino.As this aminocompound, can mention those that in JP-A-9-142032, describe.In the middle of the aminocompound described in this reference, it is particularly preferred having at least one anils amino and that represent with following formula (VIII):
R wherein
1, R
2, R
3And R
4Be hydrogen atom, halogen atom, alkyl, alkoxyl group or amino independently, X
1And X
2Be group amino or that represent with following formula (b) independently:
Y
1Be-SO
2-,-O-,-(S)
n-,-(CH
2)
n-,-CO-,-CONH-and with in the group of any one expression of formula (a) any one:
Or Y
1Do not exist, n is 1 or 2.
These aminocompounds can be separately or are used as their mixture.In order to improve the print retention in the plasticizer resistance properties, the ratio of aminocompound is the colourless or light dyestuff former of 1-500 weight part/100 weight parts preferably.When the content of aminocompound is the urea-urea hydride compounds of 1 weight part or more than 1 weight part/weight part, can improve the print retention.When this content is 500 weight parts or 500 weight parts when following, can fully improve the performance of resulting composition, and this content is favourable from the angle of cost.
Acid developer is incorporated into also improved sensitivity in the color former of the present invention and can make color former produce bright color.
As the acid developer when color former of the present invention uses, use common be subjected to electronics material, especially amphyl in thermal recording medium; Aromatic carboxylic acid's derivative or their metallic compound; Salicyclic acid derivatives or their metal-salt; N, N-diaryl thiourea derivative; Sulfonyl urea derivates etc. are preferred.Amphyl is particularly preferred.Amphyl specific examples be 2, two (4-hydroxyphenyl) propane of 2-, 2, two (hydroxyphenyl) butane of 2-, 2, two (the hydroxyphenyl)-pentanes of 2-, 2, two (hydroxyphenyl) heptane of 2-, 1, two (4-hydroxyphenyl) hexanaphthenes of 1-, two (4-hydroxyphenyl)-butylacetates, two (4-hydroxyphenyl) jasmal, two (4-hydroxyphenyl) sulfone, two (3-methyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4 '-methyl phenyl sulfone, 3-chloro-4-hydroxyphenyl-4 '-methyl phenyl sulfone, 3,4-dihydroxyphenyl-4 '-methyl phenyl sulfone, 4-isopropyl phenyl-4 '-the hydroxyphenyl sulfone, 4-isopropyl phenyl-4 '-the hydroxyphenyl sulfone, two (2-allyl group-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4 '-the benzyloxy phenylsulfone, 4-isopropyl phenyl-4 '-the hydroxyphenyl sulfone, two (the 2-methyl-3-tertiary butyl-4-hydroxyphenyl) sulphur, the 4-methyl hydroxybenzoate, the 4-hydroxy benzoic acid benzyl ester, the 4-hydroxy-benzoic acid (4 '-the benzyl chloride base) ester, 1,2-pair (4 '-hydroxy-benzoic acid) ethyl ester, 1,5-pair (4 '-hydroxy-benzoic acid) pentyl ester, 1,6-pair (4 '-hydroxy-benzoic acid) own ester, 3-hydroxyl-dimethyl phthalate, gallic acid stearyl ester, Progallin LA etc.Salicyclic acid derivatives comprises 4-n-octyloxy Whitfield's ointment, 4-n-butoxy Whitfield's ointment, 4-n-pentyloxy Whitfield's ointment; 3-n-dodecane oxygen base Whitfield's ointment; the positive capryloyl oxygen of 3-base Whitfield's ointment, 4-n-octyloxy carbonylamino Whitfield's ointment, the positive capryloyl oxygen of 4-base carbonylamino Whitfield's ointment etc.Sulfonyl urea derivates for example comprises the compound that contains one or more arlysulfonylamino urea groups; as 4; two (ptoluene-sulfonyl amino carbonyl amino) ditans of 4-; 4, two (neighbour-tosyl group amino carbonyl amino) ditans of 4-, 4; two (ptoluene-sulfonyl the amino carbonyl amino)-phenylbenzene sulphur of 4-; 4, two (ptoluene-sulfonyl amino carbonyl amino) diphenyl ethers of 4-, N-(p-toluenesulfonyl)-N '-phenylurea etc.In addition, for example can also use 4,4 '-mixture (for example D-90 (trade(brand)name, by Nippon Soda Co., Ltd. produces)) that [oxygen two (ethyleneoxy group-to phenylene-alkylsulfonyl)] diphenol and main compounds are thus formed.
In the above acid developer that exemplifies; 2; two (4-hydroxyphenyl) propane of 2-; 4-isopropyl phenyl-4 '-the hydroxyphenyl sulfone; two (3-allyl group-4-hydroxyphenyl) sulfone, 2,4 '-dihydroxy-diphenyl sulfone and 4; 4 '-[oxygen two (ethyleneoxy group-right-phenylene alkylsulfonyl)] diphenol is particularly preferred, because they have improved sensitivity and might obtain to produce the thermal recording medium of light tone.
Fuzzy in order to improve (fog); thermal responses etc. can also be added phenolic compound such as N-stearyl-N '-(2-hydroxyphenyl) urea, N-stearyl-N '-(3-hydroxyphenyl) urea; N-stearyl-N '-(4-hydroxyphenyl) urea, right-the stearyl-amino phenol, neighbour-stearyl--amino phenol; right-the lauroyl amino phenol; right-the butyryl radicals amino phenol ,-acetylamino phenol, o-acetyl-base amino phenol; right-acetylamino phenol; neighbour-butyl aminocarboxyl phenol, neighbour-stearyl aminocarboxyl phenol is right-stearyl aminocarboxyl phenol; 1; 1,3-three (3-tertiary butyl-4-hydroxy-6-aminomethyl phenyl) butane, 1; 1; 3-three (3-tertiary butyl-4-hydroxy-6-ethylphenyl) butane, 1,1; 3-three (3; 5-di-t-butyl-4-hydroxyphenyl) butane, 1,1; 3-three (3-tertiary butyl-4-hydroxy-6-aminomethyl phenyl) propane; 1,2,3-three (3-tertiary butyl-4-hydroxy-6-aminomethyl phenyl) butane; 1; 1,3-three (3-phenyl-4-hydroxyphenyl) butane, 1; 1; 3-three (3-cyclohexyl-4-hydroxy-5-methyl base phenyl) butane, 1,1; 3-three (3-cyclohexyl-4-hydroxyl-6-aminomethyl phenyl) butane; 1,1,3-four (3-phenyl-4-hydroxy phenyl) propane; 1; 1,3,3-four (3-cyclohexyl-4-hydroxyl-6-aminomethyl phenyl) propane; 1; two (3-tertiary butyl-4-hydroxy-6-aminomethyl phenyl) butane of 1-, 1, two (3-cyclohexyl-4-hydroxyl-6-aminomethyl phenyl) butane of 1-or the like.
Preferred above-mentioned acid developer is with the 5-500 weight part, and more preferably the ratio of the colourless or light dyestuff former of 20-200 weight part/100 weight parts is used.When the ratio of acid developer is 5 weight parts or 5 weight parts when above, the colour developing of dyestuff former is gratifying and colorant density is high.
When the ratio of acid developer is 500 weight parts or 500 weight parts when following, acid developer remains hardly, and this is favourable economically, is preferred therefore.
When color former of the present invention uses in the pressure sensitive recording material, acid developer is incorporated into also improved colorant density and can make pressure sensitive recording material production bright color in the color former.
As this acid developer, also use and be subjected to electronic material.Acid developer for example comprises mineral compound such as acid clay, activated clay, attapulgite, wilkinite, zeolite, colloidal silica, Magnesium Silicate q-agent, talcum, pure aluminium silicate etc.; Phenol, cresols, butylphenol, octyl phenol, phenyl phenol, chlorophenol, Whitfield's ointment etc., or the metal-salt of deutero-aldol condensation novolac resin and they thus; With salicyclic acid derivatives such as 3-sec.-propyl Whitfield's ointment, 3-phenylsalicylic acid, 3-cyclohexyl Whitfield's ointment, 3,5-di-tert-butyl salicylic acid, 3,5-two (α-Jia Jibianji)-Whitfield's ointment, 3,5-two uncle's octyl group Whitfield's ointments, 3-methyl-5-benzyl Whitfield's ointment, 3,5-two (α, α-Er Jiajibianji)-Whitfield's ointment, 3-phenyl-5-(α, α-Er Jiajibianji)-Whitfield's ointment etc., and their metal-salt.
Fluorescence dye is incorporated into also improved whiteness in the color former of the present invention.As the fluorescence dye that is incorporated in the color former of the present invention, can use various known fluorescence dyes, can mention stilbene derivative, coumarin derivatives, pyrazoline derivative, bis-styrylbiphenyl derivative, Naphthalamide derivatives, two benzoxazolyl group derivatives etc.Diamino Stilbene disulfonic acid derivatives is particularly preferred, but fluorescence dye is not limited to them.
As for the consumption of fluorescence dye, preferred fluorescence dye is in the 0.01-3wt% based on the gross weight (by solid) of color former, and more preferably the amount of 0.1-2wt% exists.When the consumption of fluorescence dye was higher than 3wt%, color former was colored in some cases.When this amount was less than 0.01wt%, fluorescence dye was weakened the effect of whiteness.
Secondly, color former of the present invention can contain the shelf stability imparting agent.Can be used for shelf stability imparting agent of the present invention and be additive such as image stability agent, photostabilizer, antioxidant etc.
By being used in combination these shelf stability imparting agents and urea-urea hydride compounds developer (developer that promptly comprises urea-urea hydride compounds) and colourless and light dyestuff former, can improve the photostabilization and the recording materials that can obtain the photostabilization excellence of color former.
For example comprise 1 as the image stability agent of the preferred embodiment of the shelf stability imparting agent of use in the present invention, 1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,1,3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl)-butane, sterically hindered phenolic compound [for example 4,4 '-butylidene two (the 2-tertiary butyl-5-sylvan), 4,4 '-thiobis (the 2-tertiary butyl-5-sylvan), 2,2 '-thiobis (the 6-tertiary butyl-4-sylvan) and 2,2 '-methylene-bis (the 6-tertiary butyl-4-methylphenol)], 4-benzyloxy-4 '-(2-methyl glycidyl oxygen base) sulfobenzide, 4,4 '-diglycidyl oxygen base sulfobenzide, 1,4-diglycidyl oxygen base benzene, 2,2 '-methylene-bis (4,6-di-t-butyl oxygen base benzene) sodium phosphate, 2-propanol derivative and salicyclic acid derivatives.Usually, these image stability agent are preferably with 5-1,000 weight part, and more preferably 10-500 weight part/100 weight parts ratio colourless or light dyestuff former is used.When the ratio of image stability agent is 5 weight parts or 5 weight parts when above, the good and colorant density of photostabilization is high.When the ratio of image stability agent was higher than 1,000 weight part, they did not increase sunproof effect, and this ratio is disadvantageous economically.
As the photostabilizer of the preferred embodiment of the shelf stability imparting agent that uses in the present invention for example comprise 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(3 ', 5 '-di-t-butyl-2 '-hydroxyphenyl) benzotriazole, 2-(5 '-tertiary butyl-2 '-hydroxyphenyl) benzotriazole, 2-[2 '-hydroxyl-5 '-(1,1,3, the 3-tetramethyl butyl) phenyl] benzotriazole, 2-(3 ', 5 '-di-t-butyl-2 '-hydroxyphenyl)-the 5-chlorobenzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-aminomethyl phenyl)-the 5-chlorobenzotriazole, 2-(2 '-hydroxyl-4 '-octyloxyphenyl) benzotriazole, 2-(3 ', 5 '-two tert-pentyls-2 '-hydroxyphenyl) benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-the carbonyl octyloxy ethylphenyl)-the 5-chlorobenzotriazole etc.; The 4-hydroxyl, the 4-methoxyl group-, the 4-octyloxy-, 4-oxygen in last of the ten Heavenly stems base-, the 4-dodecyloxy-, the 4-benzyloxy-, 4,2 ', 4 '-trihydroxy--, 2 '-hydroxyl-4,4 '-dimethoxy-or 4-(2-ethyl hexyl oxy)-2-hydroxyl benzophenone derivant etc.; Whitfield's ointment 4-tert-butyl-phenyl ester, salol, Whitfield's ointment octyl phenyl ester, dibenzoyl resorcinols, two (4-tert.-butylbenzene formyl radical) Resorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butyl-phenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid cetyl ester etc.; Alpha-cyano-β, β-diphenyl-ethyl acrylate, alpha-cyano-β, β-diphenylacrylate isooctyl acrylate, α-methoxycarbonyl-methyl cinnamate, alpha-cyano-Beta-methyl-right-p-Methoxymethylcinnamate etc.; Two (2,2,6,6-tetramethyl--4-piperidyl) sebate, two (2,2,6,6-tetramethyl--4-piperidyl) succinate, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate, two (1-octyloxy-2,2,6,6-tetramethyl--4-piperidyl) sebate, two (1,2,2,6,6-pentamethyl--4-piperidyl) adipic acid ester etc.; 4,4 '-two octyloxies-oxanilide, 2,2 '-diethoxy oxygen base-oxanilide, 2,2 '-two octyloxies-5,5 '-di-t-butyl-oxanilide, 2,2 '-two-dodecyloxy-5,5 '-di-t-butyl-oxanilide, 2-oxyethyl group-2 '-ethyl-N, oxanilide N, N, N '-two (3-dimethylamino-propyl)-N, oxanilide N, the 2-oxyethyl group-5-tertiary butyl-2 '-oxyethyl group-oxanilide etc.; With 2,4,6-three (2-hydroxyl-4-octyloxyphenyl)-1,3,5-triazines, 2-(2-hydroxyl-4-octyloxyphenyl)-4, two (2, the 4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-, 2-(2, the 4-dihydroxyphenyl)-4, two (2, the 4-3,5-dimethylphenyl)-1 of 6-, 3,5-triazine, 2, two (the 2-hydroxyls-4-propoxy-phenyl-6-(2 of 4-, the 4-3,5-dimethylphenyl)-and 1,3,5-triazines, 2-(2-hydroxyl-4-dodecyloxy phenyl)-4, two (2, the 4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-etc.Usually, these photostabilizers are preferably with 5-1,000 weight part, and more preferably 10-500 weight part/100 weight parts ratio colourless or light dyestuff former is used.When the ratio of photostabilizer is 5 weight parts or 5 weight parts when above, photostabilization good and and colorant density be high.When the ratio of photostabilizer was higher than 1,000 weight part, they did not increase sunproof effect, and this ratio is disadvantageous economically.
For example comprise 2 as the antioxidant of the preferred embodiment of the storage stability imparting agent that uses in the present invention, 6-di-t-butyl-4-sylvan, the 2-tertiary butyl-4, the 6-dimethyl phenol, 2,6-di-t-butyl-4-ethyl phenol, 2,6-di-t-butyl-4-normal-butyl phenol, 2,6-di-t-butyl-4-isobutyl-phenol, 2,6-two cyclopentyl-4-sylvan, 2-(Alpha-Methyl cyclohexyl)-4,6-dimethyl phenol, 2, the two octadecyls of 6--4-sylvan, 2,4,6-thricyclohexyl phenol, 2,6-dinonyl-4-sylvan, 2,6-di-t-butyl-4-methoxymethyl phenol, 2,4-dimethyl-6-(1 '-methyl-undecane-1 '-yl)-and phenol, 2,4-dimethyl-6-(1 '-methyl-heptadecane-1 '-yl)-phenol, 2,4-dimethyl-6-(1 '-methyl-tridecane-1 '-yl)-phenol and their mixture; 2,4-dioctyl sulphomethyl-6-tert-butyl phenol, 2,4-dioctyl sulphomethyl-6-sylvan, 2,4-dioctyl sulphomethyl-6-ethyl phenol, 2,6-pair-dodecyl-sulphomethyl-4-nonyl phenol and their mixture; 2,6-two-tertiary butyl-4-methoxyl group phenol, 2, the 5-di-tert-butyl hydroquinone, 2,5 di tert amlyl hydroquinone, 2,6-phenylbenzene-4-octadecane oxygen base phenol, 2, the 6-di-tert-butyl hydroquinone, 2,5-di-t-butyl-4-hydroxyanisol, 3,5-di-t-butyl-4-hydroxyanisol, stearic acid 3,5-di-t-butyl-4-hydroxyphenyl ester, two (3,5-di-t-butyl-4-hydroxyphenyl) adipic acid ester and their mixture; 2,4-pair-octyl group sulfydryl-6-(3,5-di-t-butyl-4-hydroxybenzene amido)-1,3, the 5-triazine, 2-octyl group sulfydryl-4, two (3,5-di-t-butyl-4-hydroxybenzene amido)-1 of 6-, 3, the 5-triazine, 2-octyl group sulfydryl-4,6-two (3,5-di-t-butyl-4-hydroxyphenoxy)-1,2, the 3-triazine, 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-and isocyanuric acid ester, 1,3,5-three (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) isocyanuric acid ester, 2,4,6-three (3,5-di-t-butyl-4-hydroxyphenyl ethyl)-1,3,5-triazine, 1,3,5-three (3,5-di-t-butyl-4-hydroxyphenyl propionyl)-six hydrogen-1,3,5-triazine, 1,3,5-three (3,5-dicyclohexyl-4-acrinyl)-isocyanuric acid ester etc.; 2,2 '-methylene-bis (the 6-tertiary butyl-4-sylvan), 2,2 '-methylene radical-two (the 6-tertiary butyls-4-ethyl phenol), 2,2 '-ethylenebis (4,2,2 the 6-di-tert-butylphenol), '-ethylenebis (the 6-tertiary butyl-4-isobutyl-phenol), 4,4 '-methylene-bis (2, the 6-di-tert-butylphenol), 4,4 '-methylene-bis (the 6-tertiary butyl-2-sylvan), 1, two (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane of 1-, ethylene glycol bis [3,3 '-two (3 '-tertiary butyl-4 '-hydroxyphenyl) butyric ester] etc.; 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-2,4,6-Three methyl Benzene, 1, two (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-2,3,5 of 4-, 6-tetramethyl-benzene, 2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-phenol etc.Usually, preferably these antioxidants are with 5-1,000 weight part, and more preferably 10-500 weight part/100 weight parts ratio colourless or light dyestuff former is used.When the ratio of antioxidant is 5 weight parts or 5 weight parts when above, photostabilization is good and colorant density is high.When the ratio of antioxidant was higher than 1,000 weight part, they did not increase sunproof effect, and this ratio is disadvantageous economically.
Color former of the present invention can be made recording materials by using such as method layer that adds lustre to of formation composition on certain base material of coating.The structure of recording materials changes according to the type of recording materials.
Color former of the present invention can be used in various recording materials such as thermal recording medium, pressure sensitive recording material etc. any, and be particularly suitable for thermal recording medium.
When color former is used for thermal recording medium, can colorific heat sensitive recording layer when on base material, being formed on heating.Specifically, should be with above-mentioned urea-urea hydride compounds, above-mentioned colourless or light dyestuff former such as leuco dye, but the material of hot melt hereinafter described etc. be applied on the base material with other necessary component with the form of separately dispersion, form heat sensitive recording layer.By preparing dispersion as one or more compounds of above-mentioned each component with fine grinding in the aqueous solution that contains compound with dispersive ability such as water-soluble polymers, tensio-active agent etc. such as sand mill.Preferably the granularity of each dispersion that will obtain like this is adjusted to .0.1-10 μ m, especially about 1 μ m.The specific examples of the compound with dispersive ability that can use in the present invention is that water-soluble polymers is as poly-(vinyl alcohol), carboxyl acid modified poly-(vinyl alcohol), poly-(vinyl alcohol) of sulfonic acid modified, methylcellulose gum, Vltra tears, hydroxypropylcellulose etc.; Anion surfactant such as condensation naphthalenesulfonate, Voranol EP 2001 sodium sulfovinate (polyoxyethylene lauryl ether sodium sulfate for example, Voranol EP 2001 sodium sulfate and polyoxyethylene alkyl phenyl ether sodium sulfate), dialkyl sulphosuccinate sodium, alkylphosphonic (for example alkylphosphonic acid carboxylic acid diethanolamine and alkylphosphonic acid carboxylic acid potassium), special carboxylic acid group polymer etc.; Nonionogenic tenside such as Voranol EP 2001, polyoxyethylene alkyl phenyl ether, Vykamol Sorbitol 8B, fatty mono glyceride, cithrol etc.; With cats product such as dicyanamide Quito amine, tertiary ammonium salt, quaternary ammonium salt etc.In the middle of these, polyvinyl alcohol, carboxyl acid modified polyvinyl alcohol, the polyvinyl alcohol of sulfonic acid modified and methylcellulose gum are particularly preferred.The compound that more than exemplifies can be separately or is used as their mixture.
When urea according to the present invention-when urea hydride compounds developer is used for thermal recording medium, the mean particle size of urea-urea hydride compounds developer is adjusted to be not more than 5 μ m and to be not less than 0.05 μ m makes the thermal recording medium that might obtain to have abundant developing sensitivity, obtain highly stable printing colour developing image, and had good plasticizer resistance properties.Mean particle size is more preferably no more than 3 μ m and be not less than 0.1 μ m.When mean particle size during less than 0.05 μ m, the retention of the anti-softening agent of source recording material surface reduces.On the other hand, when mean particle size during greater than 5 μ m, the sensitivity of thermal recording medium reduces.
Especially when urea-urea hydride compounds carried out wet grinding in aqueous medium, the temperature of aqueous medium was preferably below 60 ℃ or 60 ℃.When grinding, urea-urea hydride compounds developer contacts with water, makes its hydrolysis of urea alkyl carry out according to condition.Therefore, the sensitivity by use urea-thermal recording medium that urea hydride compounds developer obtains often reduces.When especially the medium temperature when grinding was higher than 60 ℃, sensitivity significantly reduced.Medium temperature during grinding is more preferably below 40 ℃ or 40 ℃.
In addition, when grinding urea-urea hydride compounds developer, preferably grind in the neutral pH scope of 5-10.When the pH when grinding was lower than 5, mineral dye etc. decomposed in the production of temperature-sensitive coating fluid, make sensitivity often reduce.On the other hand, when pH was higher than 10, urea-urea hydride compounds developer was hydrolyzed, and makes sensitivity reduce in some cases.The specific examples that can be used for the dispersion agent of the dispersion by grinding preparation urea-urea hydride compounds developer in the present invention is that water-soluble polymers is as poly-(vinyl alcohol), carboxyl acid modified poly-(vinyl alcohol), poly-(vinyl alcohol) of sulfonic acid modified, methylcellulose gum, Vltra tears, hydroxypropylcellulose etc.; The naphthalenesulfonate of anion surfactant such as condensation, Voranol EP 2001 sulfuric acid (polyoxyethylene lauryl ether sodium sulfate for example, Voranol EP 2001 sodium sulfate and polyoxyethylene alkyl phenyl ether sodium sulfate), dialkyl sulphosuccinate sodium, alkylphosphonic (for example alkylphosphonic acid carboxylic acid diethanolamine and alkylphosphonic acid carboxylic acid potassium), special carboxylic acid type polymkeric substance etc.; Nonionogenic tenside such as polyoxyethylene alkyl phenyl ether, Vykamol Sorbitol 8B, fatty mono glyceride, cithrol etc.; With cats product such as dicyanamide Quito amine, tertiary ammonium salt, quaternary ammonium salt etc.In the middle of these, water-soluble polymers and anion surfactant are particularly preferred, because they make may obtain no matter the condition of dispersed urea-urea hydride compounds developer how, all has highly sensitive thermal recording medium, and no matter the mean particle size of urea-urea hydride compounds developer how, all has the retention of improved source recording material surface antagonism softening agent.Poly-(vinyl alcohol), poly-(vinyl alcohol) of modification, methylcellulose gum, Vltra tears, the sodium naphthalene sulfonate of condensation, the poly carboxylic acid ammonium salt, water-soluble low molecular weight multipolymer and sulfo-succinic acid 2-ethylhexyl sodium are preferred.In the middle of these, methylcellulose gum, Vltra tears, the sodium naphthalene sulfonate of condensation and water-soluble low molecular weight multipolymer are preferred, Vltra tears is most preferred.The dispersion agent that more than exemplifies can be separately or is used with their mixture.
Can use and the identical compound of dispersion agent that is used for dispersed urea-urea hydride compounds developer by grinding the dispersion agent of the dispersion for preparing colourless or light dyestuff former as being used in the present invention.In the middle of these compounds, water-soluble polymers, the mixed dispersant of anion surfactant and this compound of two types is particularly preferred for the retention of sensitivity that improves thermal recording medium and source recording material surface antagonism softening agent.By being preferred as the methylcellulose gum of water-soluble polymers or Vltra tears and the mixed dispersant formed as the polyoxyethylene alkyl ether sulfate salt or the sulfo-succinic acid 2-ethylhexyl sodium of anion surfactant.The mixed dispersant of Vltra tears and sulfo-succinic acid 2-ethylhexyl sodium is most preferred.
The pH 5-12 preferably that contains the coating fluid of urea-urea hydride compounds and colourless or light dyestuff former.
Except said components, heat sensitive recording layer can contain pigment such as diatomite, talcum, kaolin, calcined kaolin, lime carbonate, magnesiumcarbonate, titanium dioxide, zinc oxide, silicon-dioxide, aluminium hydroxide, urea-formaldehyde resins etc.In addition, if necessary, thermal recording medium can contain the metal-salt of higher fatty acid, as Zinic stearas, and calcium stearate etc.; With wax such as paraffin, oxidized petroleum wax, polyethylene, oxidic polyethylene, stearylamide, castor wax etc. for example are used to prevent the abrasion and the adhesion of record-header.If necessary, thermal recording medium can also contain dispersion agent such as sodium dioctyl sulfosuccinate etc.; UV light absorber such as benzophenone, benzotriazole category; Tensio-active agent; Fluorescence dye; Or the like.
As the binding agent that is used to form heat sensitive recording layer, for example can mention water-soluble binder such as starch, Natvosol, methylcellulose gum, carboxymethyl cellulose, gelatin, casein, poly-(vinyl alcohol), poly-(vinyl alcohol) of modification, poly-(vinylformic acid) sodium, the acrylamide-acrylicacid ester copolymer, acrylamide-acrylicacid ester-methacrylic acid ter-polymer, an alkali metal salt of styrene-maleic anhydride copolymer, an alkali metal salt of ethene-copolymer-maleic anhydride etc.; Latex type water-insoluble binding agent with styrene-butadiene copolymer, acrylonitrile butadiene copolymer, methyl acrylate butadiene copolymer etc.
As the base material that is used for heat sensitive recording layer, though can use various Woven fabrics except paper according to purpose, supatex fabric, synthetic resin film, laminated paper, synthetic paper, tinsel, and any by in the composite sheet of two or more acquisitions of combination in them, but mainly use paper.The quantitatively 40g/m preferably of base material
2-200g/m
2Base material is preferably excellent on surface smoothness and planeness, has high as far as possible planeness because wish by the thermal recording medium that uses base material to obtain.Therefore, preferably by applying heat with any in roller calender, soft roller calender, the supercalender etc. and pressure carries out surface treatment to base material.
The surface p H of base material is 3-9 preferably, more preferably 5-9, most preferably 6-8.When the surface p H of base material is lower than 3, often take place fuzzy.When the surface p H of base material was higher than 12, urea-urea hydride compounds developer was decomposed, and makes colorant density reduce in some cases.
Heat sensitive recording layer can be made up of individual layer or two or multilayer.Heat sensitive recording layer can for example have by the component of will respectively adding lustre to and is incorporated into the multilayered structure that forms in one deck.Can on heat sensitive recording layer, form the protective layer of forming by individual layer or bilayer or multilayer, between base material and heat sensitive recording layer, can also form by individual layer or middle layer two-layer or that multilayer is formed.Heat sensitive recording layer can mix with binding agent by the aqueous dispersion of preparations such as fine grinding is respectively added lustre to component or any other component, and the gained mixture is applied on the base material, and drying composite obtains again.The glue spread of this coating fluid preferably when coating fluid be 1-15g/m during for drying regime
2
When color former of the present invention is used for thermal recording medium, but the material of hot melt can be incorporated in the color former, so that improve sensitivity.But the material of hot melt preferably has the material of 60-180 ℃ fusing point, especially has the material of 80-140 ℃ fusing point.But the material of hot melt for example comprises right-benzyloxy peruscabin, stearylamide or its emulsification product, palmitic amide; N-methylol-stearylamide, betanaphthyl benzylic ether, N-stearyl urea; N, N '-distearyl urea, β-naphthoate; 1-hydroxyl-2-naphthoate, 2-Naphthol (right-methyl-benzyl) ether, 1; the 4-dimethoxy-naphthalene; 1-methoxyl group-4-benzyloxy-naphthalene, N-stearyl-urea, right-Benzyldiphenyl; 1; 2-two (-methylphenoxy) ethane, 1-phenoxy group-2-(4-chloro-phenoxy group) ethane, 1; 4-butyleneglycol phenyl ether; dimethyl terephthalate (DMT), meta-terphenyl, dibenzyl oxalate and (right-the benzyl chloride base) barkite.
In addition, 4,4 '-dimethoxy-benzophenone, 4,4 '-dichloro benzophenone, 4,4 '-difluoro benzophenone, sulfobenzide, 4,4 '-dichloro diphenylsulfone, 4,4 '-difluorodiphenyl base sulfone, 4,4 '-dichloro phenylbenzene two sulphur, diphenylamine, 2-methyl-4-methoxyl group diphenylamine, N, N '-phenylbenzene-right-phenylenediamine, 1-(N-phenyl amino) naphthalene, benzil, 1, but the material of conduct hot melts such as 3-diphenylpropane-1 is preferred, because they are very effective to improving sensitivity.
But as the material of hot melt, can also use the 4-hydroxy benzoic acid benzyl ester, 4-(benzyloxy) phenol; 2,4 dihydroxyl benzophenone, 2; 2 ', 4,4 '-tetrahydroxybenzophenone; 4,4 '-dihydroxy benaophenonel, 2; two (4-hydroxyphenyl) propane of 2-, 4,4 '-dihydroxy-diphenyl sulfone; two (3-methyl-4-hydroxyphenyl) sulfone, two (3,5-dimethyl-4-hydroxyphenyl) sulfone; 3,4-dihydroxyphenyl-4 '-methyl phenyl sulfone, two (the 2-methyl-3-tertiary butyl-4-hydroxyphenyl) sulphur; 4,4 '-dihydroxydiphenyl ether, 4; 4 '-the sulfo-diphenol, 4,4 '-the dihydroxyl ditan; 3,3 '-the dihydroxyl diphenylamine, two (4-hydroxy-3-methyl phenyl) sulphur; 4-hydroxyl-4 '-the isopropoxy sulfobenzide, 4,4 '-the thiobis benzenethiol; Salicylanlide, 4,4 '-diamino-3; 3 '-the diethyl ditan, 4,4 '-the diaminobenzene formylaniline; 3; 3 '-two chloro-4,4 '-diaminodiphenyl-methane, 3; 3 '-dimethyl-4; 4 '-diaminodiphenyl-methane, 4,4 '-thiobis aniline; 2; 2 '-the dithio dianiline, 4,4 '-the dithio dianiline; 4; 4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether; 3; 4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl-methane; 3; 4 '-diaminodiphenyl-methane, two (3-amino-4-chloro-phenyl-) sulfone, two (3; the 4-diamino-phenyl) sulfone; 4,4 '-diamino diphenyl sulfone, 3; 3 '-diamino diphenyl sulfone; 3,4 '-diamino diphenyl sulfone, 3; 3 '-diaminodiphenyl-methane; 4,4 '-diamino-diphenyl amine, 3; 3 '-diaminobenzophenone; 4,4 '-diaminobenzophenone, the adjacent chloro aminobenzen of N-acetoacetyl; N; the N-acetoacetyl aniline, N-acetoacetyl Ortho Toluidine, N-acetoacetyl para-totuidine; the acetoacetyl o-anisidine, acetoacetyl m-xylene base amine and right-ethanoyl Tolylamine etc.
In the middle of these, sulfobenzide, oxalic acid two-right-methyl-benzyl ester, benzil, the betanaphthyl benzylic ether, right-benzyl-biphenyl, 1,2-two (-methylphenoxy) ethane, 1,2-hexichol oxygen ylmethyl benzene, meta-terphenyl and stearylamide are preferred the uses.
In addition, but belong to the above hot melt that exemplifies material row following structural formula (XVIII) but the application of material in thermal recording medium of hot melt for the sensitivity that increases recording materials and improve the anti-softening agent of printing and the thermotolerance of source recording material surface is significantly effectively.With following structural formula (XIX) but the material of hot melt of expression is particularly preferred.
Wherein Y is-SO
2-,-(S)
n-,-O-,-CO-,-CH
2-,-CH (C
6H
5)-,-C (CH
3)
2-,-COCO-,-CO
3-,-COCH
2CO-,-COOCH
2-,-CONH-,-OCH
2-and-among the NH-any one; n is 1 or 2, and the hydrogen atom of each phenyl ring can be replaced by halogen atom, hydroxyl, nitro, nitroso-group, itrile group, isocyanate group, isothiocyanate group, sulfydryl, sulfamyl, sulfuryl, amino, aromatic substance residue, aliphatic cpd residue or heterogeneous ring compound residue.
Wherein the hydrogen atom of each phenyl ring can be replaced by halogen atom, hydroxyl, nitro, nitroso-group, itrile group, isocyanate group, isothiocyanate group, sulfydryl, sulfamyl, sulfuryl, amino, aromatic substance residue, aliphatic cpd residue or heterogeneous ring compound residue.
But the material of the hot melt that more than exemplifies can be separately or is used with their mixture.In order to obtain sufficient thermal response, but the material of preferred hot melt with the 10-300 weight part, more preferably 20-250 weight part/100 weight parts ratio colourless or light dyestuff former is used.
But, can use and be used as the identical compound of dispersion agent of dispersed urea-urea hydride compounds developer as the dispersion agent that is used in the present invention by the dispersion of grinding the material for preparing hot melt.In the middle of these compounds, water-soluble polymers and anion surfactant are particularly preferred for the retention of the source recording material surface antagonism softening agent that improves thermal recording medium.Poly-(vinyl alcohol), poly-(vinyl alcohol) of modification, methylcellulose gum, the hydroxyphenyl methylcellulose gum, the sodium naphthalene sulfonate of condensation, the poly carboxylic acid ammonium salt, water-soluble low molecular weight multipolymer and sulfo-succinic acid 2-ethylhexyl sodium are preferred.In the middle of these, modification gathers (vinyl alcohol), methylcellulose gum, and Vltra tears, condensation sodium naphthalene sulfonate, poly carboxylic acid ammonium salt are also preferred, Vltra tears is most preferred.The dispersion agent that more than exemplifies can use separately or as mixture.
When grinding urea-urea hydride compounds developer, with each compound of fine grinding and subsequently the compound of mixed grinding compare, together fine grinding (grind altogether) but the material of developer and above-mentioned hot melt has further improved the anti-softening agent of sensitivity and thermal recording medium.The reason that obtains these effects imperfectly understands.
In addition, the moistureproofness of the non-printing (original surface) of thermal recording medium can be selected from the dispersion agent of at least a urea-urea hydride compounds developer in methylcellulose gum, Vltra tears, condensation sodium naphthalene sulfonate and the water-soluble low molecular weight multipolymer by use, and be selected from modification poly-(vinyl alcohol), methylcellulose gum, Vltra tears, but the dispersion agent of the material of at least a hot melt in condensation sodium naphthalene sulfonate and the poly carboxylic acid ammonium salt improves.
Color former of the present invention can be used in various thermal recording mediums, and is particularly suitable for the heat-sensitive magnetic recording material, the label of thermal photography, polychrome thermal recording medium and the thermal recording medium that is used for laser labelling.
When color former of the present invention was used for the heat-sensitive magnetic recording material, recording materials were preferably following form: form on a face of base material and contain the heat sensitive recording layer of urea-urea hydride compounds developer and form magnetic recording layer on another side.
By with ferromagnetic powder such as barium ferrite, strontium ferrites, Co-γ-Fe
2O
2, γ-Fe
2O
2Or analogue is dispersed in that prepared coating is coated on the base material in aqueous binders such as the water miscible liquid resin, and drying coated then material forms the magnetic recording layer of heat-sensitive magnetic recording material.In this case, various additives such as static inhibitor (for example carbon graphite), lubricant (for example wax) is used for the tinting pigment that tone is regulated, and the toughner of filming [for example poly-(oxyethane)] etc. can add according to purpose separately.
Heat-sensitive magnetic recording material of the present invention is suitable as the heat-sensitive magnetic recording material as railway tickets, ticket, prepaid card etc.
When color former of the present invention was used for the label of thermal photography, preferred tag was following form: form the heat sensitive recording layer that contains urea-urea hydride compounds developer on a face of base material, form binder layer again on another side.
The binder layer of this thermal recording medium mainly is made up of pressure sensitive adhesive.Pressure sensitive adhesive for example comprises synthetic rubber class Emulsion Adhesive, ACRYLIC EMULSION type tackiness agent, natural rubber kind solvent type tackiness agent, vinylformic acid Solvent Adhesive and silica-based Solvent Adhesive.In the middle of these, ACRYLIC EMULSION type tackiness agent is particularly preferred.
If necessary, when the label of producing in the method according to this invention that is used for thermal photography forms reverse side layer (back coating) between binder layer and base material, might get rid of bending at the label that is used for thermal photography, prevent that static charge from occurring and the adjusting frictional coefficient.As the component of the coating fluid of reverse side layer, the coating process of coating fluid etc. can use and component identical in the formation of heat sensitive recording layer, method etc.The dry-coated amount of coating fluid is 0.2-10.0g/m preferably
2
The coating order of production that is used for the label of thermal photography is not special restriction.For example, can use any one in the following order: the one side at base material forms heat sensitive recording layer, forms back coating then on another side, after this, forms binder layer on back coating; Perhaps on face of base material, form back coating, on another side, form heat sensitive recording layer then, after this on back coating, form binder layer.
As for the method that on back coating, forms binder layer, can directly be applied over the liquid that is used to form binder layer on the back coating, dry again, maybe will be by on interleaving paper, applying the liquid that is used to form binder layer in advance, the back coating face of the thermal recording medium of the material applying formation thereon binder layer that subsequent drying obtains.
In addition, thermal response can be improved by individual layer or middle layer two-layer or that multilayer is formed by forming between heat sensitive recording layer and base material.The middle layer is mainly by organic or inorganic pigment, and hollow particle and aqueous binders such as water-soluble polymers or latex are formed.As organic or inorganic pigment and aqueous binders, can use and identical organic or inorganic pigment and the aqueous binders that in heat sensitive recording layer, use.The method that is used to form the middle layer is not special restriction.As this method, can adopt the method identical with the method that forms heat sensitive recording layer.The dry-coated amount that forms the middle layer is preferably 2.0-15.0g/m
2
When color former of the present invention is used for the polychrome thermal recording medium, these recording materials are preferably following form: form two-layer at least heat sensitive recording layer on a face of base material, and the one deck at least in the described heat sensitive recording layer contains urea-urea hydride compounds developer.
As base materials employed, can use following base material: by under heating, mediating polyolefin resin and white inorganic pigment, extrude the kneading product through mould, on long axis direction, stretch and extrude product, lamination is made by polyolefin resin and white inorganic pigment on each face of drawn material one or two-layer film, cross directional stretch gained assembly makes its synthetic paper translucent or opaque production again; By under heating, mediating thermoplastic resin such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer resin, poly-(vinylchlorid), polystyrene polyester etc. a kind of or two or more mixture are extruded the kneading product through mould, then the film that obtains of the product of biaxial stretch-formed kneading; By the mixture of white mineral dye and any more than the resin that exemplifies, the opaque film of biaxial stretch-formed acquisition subsequently; With the base material of producing from paper pulp fiber, as no wood pulp paper, intermediate paper, machine-glazed paper, recycled writing paper, enamelled paper etc.The base material of being made by paper pulp fiber preferably covers with heat-sensitive layer after being pre-formed the layer that is used to be coated with, so that improve the homogeneity of image.
The temperature-sensitive according to the present invention layer that adds lustre to comprises as the tackiness agent of its main component and can material be in contact with one another cause the color former of color reaction because of heating.The specific examples of color former is colourless or light dyestuff former and the time can makes the composition of the above-mentioned urea-urea alkane developer of described dyestuff former colour developing in heating, and diazonium compound and can by with the binding substances of the coupler of diazonium compound reaction solution.If necessary, can be with linking agent, but the material of pigment and hot melt is incorporated in the color former.Usually, from the viewpoint of developing sensitivity and colorant density, the add lustre to glue spread 3-15g/m preferably of layer of temperature-sensitive
2
As the dyestuff that can develop the color, use the colourless or light dyestuff former described, when under heating during with urea-urea hydride compounds developer reaction, it can develop the color.
On the other hand, comprise as the diazonium compound of its main component and can by with the heat sensitive recording layer of the coupler of described diazonium compound reaction solution in, these compounds are decomposable diazonium compounds of known light and can be by forming the coupler of pigment with described diazonium compound reaction.If necessary, can add alkaline matter etc., so that quicken the reaction of diazonium compound and coupler.Coupler and alkaline matter be preferably respectively with 10-1,000 weight part and 10-2, and the ratio of 000 weight part/100 weight part diazonium compounds is used with the form of mixture.
Term used herein " the decomposable diazonium compound of light " be meant can when heating by forming the diazonium-type photoactive substance of pigment with the quality component reaction, as diazonium salt, diazosulfonic acid salt compound, diazoamino compound, quinone di-azido compound or analogue.Diazonium salt is meant the compound of representing with following general formula:
Ar-N
2 +·X
-
Wherein Ar is the aromatics part, N
2 +Be diazo, X
-It is counterion.Depend on the substituent position and the kind of Ar part, these compounds have different maximum absorption wavelengths.
The specific examples of the diazonium compound that uses among the present invention is a 4-dimethylamino phenyl diazonium salt; 4-diethylin phenyl diazonium salt; 4-dipropyl amino-benzene diazonium salt; 4-methyl-benzyl amino-benzene diazonium salt; 4-dibenzyl amino phenyl diazonium salt; 4-ethyl-hydroxyethyl amino-benzene diazonium salt; 4-diethylin-2-anisole diazonium salt; 4-dimethyl-3-methylbenzene diazonium salt; 4-benzoyl-amido-2; 5-diethoxy phenyl diazonium salt; 4-morpholinyl phenyl diazonium salt, 4-morpholinyl-2,5-diethoxy phenyl diazonium salt; 4-morpholinyl-2; 5-dibutoxy phenyl diazonium salt, 4-anilino phenyl diazonium salt, 4-toluyl sulfydryl-2; 5-diethoxy phenyl diazonium salt; 4-(N, N-dioctyl formamyl) phenyl diazonium salt, 2-octadecane oxygen base phenyl diazonium salt; 4-(uncle's 4-Octylphenoxy) phenyl diazonium salt; 4-(2,4-two tert-pentyl phenoxy groups) phenyl diazonium salt, 2-(uncle's 4-Octylphenoxy) phenyl diazonium salt; 5-chloro-2-(uncle's 4-Octylphenoxy) phenyl diazonium salt; 2,5-pair-octadecane oxygen base phenyl diazonium salt, 2; 4-pair-octadecane oxygen base phenyl diazonium salt, 4-(N-octyl group lauroyl amino) phenyl diazonium salt etc.The specific examples of the balance anion of employed diazonium salt is Cl1/2Z among the present invention
nCl
2 -, BF
4 -, PF
6 -, B (ph)
4 -, C
nF
2n+1COO
-(n is 3-9), C
mF
2m+1SO
3 -(m is 2-8), (C
kF
2k+1SO
2)
2CH
-(k is 1-18) etc.
The diazosulfonic acid salt compound that uses among the present invention is the compound of representing with following general formula:
Ar-N
2-SO
3Na
Wherein Ar is the aromatics part.The specific examples of the diazosulfonic acid salt compound that uses among the present invention is to have one or more substituent benzene diazosulfonic acid sodium, and substituting group comprises the 2-methoxyl group, the 2-phenoxy group, 2-methoxyl group-4-phenoxy group, 2, the 4-dimethoxy, 2-methyl-4-methoxyl group, 2, the 4-dimethyl, 2,4, the 6-trimethylammonium, 2,4, the 6-trimethoxy, 2,4-dimethoxy-5-chlorine, 2-methoxyl group-5-nitro, 2-methoxyl group-5-kharophen, 2-methoxyl group-5-N, N-diethyl sulfonamido, 2-methoxyl group-5-N-phenyl amino formyl radical, 3-methyl, 4-methyl, the 4-methoxyl group, 4-oxyethyl group, 4-phenyl, the 4-phenoxy group, 4-kharophen etc.; Have one or more substituent benzene diazosulfonic acid sodium, substituting group comprises 4-(N-ethyl-N-benzylamino), 4-(N; the N-dimethylamino), 4-(N, N-diethylin); 4-(N, N-diethylin)-3-chlorine, 4-(N-ethylamino)-3-methyl; 4-(N, N-diethylin)-2-methyl, 4-(N-ethyl-N-beta-hydroxy ethylamino); 4-pyrrolidyl-3-chlorine, 4-pyrrolidyl-3,5-dichloro; the 4-morpholinyl; 4-morpholinyl-3-chlorine, 4-morpholinyl-2-methoxyl group, 4-morpholinyl-2; the 5-diethoxy; 4-morpholinyl-2, the 5-dibutoxy, 4-(4 '-the tolyl sulfydryl)-2; the 5-dibutoxy; 4-(4 '-the tolyl sulfydryl)-2, the 5-diethoxy, 4-(4 '-anisoyl amino)-2; the 5-dibutoxy, 4-diphenylamino etc.When using any of these diazosulfonic acid salt compound, preferably before printing, activate the diazosulfonic acid salt compound by rayed.
Being used for diazoamino compound of the present invention is by coupling diazonium groups and Dyhard RU 100, sarkosine, N-methyltaurine, N-ethyl anthranilic acid-5-sulfonic acid, monoethanolamine, diethanolamine, the compound that guanidine or analogue obtain.
Employed quinone two nitrine are inner salt type diazonium salts from structure among the present invention, for example are o-quinone two nitrine or adjacent naphtho-quinone two nitrine.Quinone two nitrine comprise 1,2-quinone two nitrine-4-sulfonic acid, 1,2-naphtho-quinone two nitrine-5-sulfonic acid, 1, salt, ester and the amide compound of 2-naphtho-quinone two nitrine-4-sulfonic acid etc.The specific examples of quinone two nitrine that use among the present invention is 1,2-quinone two nitrine-4-sodium sulfonate, 1,2-naphtho-quinone two nitrine-5-sodium sulfonate, 1,2-naphtho-quinone two nitrine-4-sodium sulfonate, 1,2-naphtho-quinone two nitrine-5-sulfonic acid is right-the cumyl phenylester, and 1,2-naphtho-quinone two nitrine-4-sulfonic acid is right-the cumyl phenylester, 1,2-naphtho-quinone two nitrine-5-methylmesylate, 1,2-naphtho-quinone two nitrine-5-sulfonic acid ethyl ester, 1,2-naphtho-quinone two nitrine-5-sulfonic acid dimethylformamide, 1, the ester of 2-naphtho-quinone two nitrine-5-sulfonic acid and novolac resin etc.In addition, the decomposable diazonium compound of these light can separately or be used in combination.
The coupler that uses among the present invention is to react to form the sort of of pigment with diazonium compound.For example, the typical coupler that can form yellow ultramarine is to have by the compound of its adjacent carbonyl activatory methylene radical and can use general formula R COCH
2CO-R ' represents that wherein R is alkyl or allyl group, and R ' is an aromatic amine.Magenta colour coupler for example is 1) the cyano group acetyl derivative of ring compound, or 2) on heterocycle, have active methylene group or any other a heterogeneous ring compound of coupling part.Magenta colour coupler for example comprises pyrazolinone compounds and indazolone compound.Cyan coupler for example comprises phenol and naphthols.
The specific examples of the coupler that uses among the present invention is 4-(p-toluenesulfonyl amino)-ω-benzoyl Acetanilide, α-benzoyl-neighbour-methoxyacetanilide, 2-cyano group ethanoyl-cumarone; 1-(2,4, the 6-trichlorophenyl)-3-is right-nitro amino-2-pyrazolin-5-one; Resorcinol; Phloroglucinol, 2, the 3-dihydroxy naphthlene; 2; 6-two bromo-1,5-dihydroxy naphthlene, N-(o-acetyl-amino-benzene ethyl)-1-hydroxyl-2-naphthoamide etc.In addition, these couplers can separately or be used in combination.
For the dye-forming reaction that makes diazonium compound and coupler carries out under alkaline atmosphere more reposefully, preferably alkaline matter is incorporated into temperature-sensitive and adds lustre in the layer.As alkaline matter, use slightly water-soluble or water-insoluble alkaline matter or when heating, can produce the material of alkali.Alkaline matter for example comprises nitrogenous compound such as inorganic and organic ammonium salt, organic amine, acid amides, urea and thiocarbamide and their derivative, thiazole, pyrroles, pyrimidine, piperazine, guanidine, imidazoles, tetrahydroglyoxaline, triazole, morpholine, piperidines, amidine, carbonamidine, pyridine etc.
The specific examples of these compounds is a thricyclohexyl amine, tribenzyl amine, octadecyl benzyl amine, stearic amine; allyl urea, thiocarbamide, methylthiourea, thiosinamine; ethylene thiourea, 2-benzyl-imidazoles, 4-phenylimidazole, 2-phenyl-4-methyl-imidazoles; 2-undecyl imidazole quinoline, 2,4,5-three furyls-2-tetrahydroglyoxaline; 1,2-phenylbenzene-4,4-dimethyl-2-tetrahydroglyoxaline, 2-phenyl-2-tetrahydroglyoxaline; 1,2,3-triphenyl guanidine, 1; 2-dicyclohexyl guanidine, 1,2; 3-thricyclohexyl guanidine, trichoroacetic acid(TCA) guanidine, N; N '-dibenzyl piperazine, 4,4 '-dithiomorpholine; the trichoroacetic acid(TCA) morpholine, 2-aminobenzothiazole, 2-benzoyl diazanyl benzothiazole etc.These alkaline matters can separately or be used in combination.
In the present invention, stability in storage can be by with acidulous material such as citric acid, and tartrate, oxalic acid, boric acid, phosphoric acid, tetra-sodium or analogue are added to temperature-sensitive that the composition by diazonium compound and coupler forms and add lustre to and improve in the layer.
Much less, the component of using among the present invention of adding lustre to can be to use by each component being dispersed in the solid dispersion state that obtains in the water-soluble polymers aqueous solution, and coating subsequently and dry is as in the common method that adopts in the thermal recording medium.As at JP-A-59-190886, JP-A-60-49991, such described in the JP-A-61-169281 etc., can also be by being encapsulated as toner to form microcapsule and to avoid coupler and developer to contact at normal temperatures by the isolation effect that utilizes microcapsule wall and improve original stability.Microcapsule are characterised in that they can make coupler and developer only just contact with each other in the heat-processed under certain temperature or higher temperature.Temperature when coupler begins to contact with developer can by suitable selection be used for capsule wall material, be used for capsular core material, additive waits and controls.
As the material that is used for microcapsule wall among the present invention, can mention the common material that is used for microcapsule wall, as urethane, polyureas, polyester, polycarbonate, urea-formaldehyde resins, melamine resin, polystyrene, vinylbenzene-alkylmethacrylate polymer, gelatin, poly-(vinyl pyrrolidone), poly-(vinyl alcohol) etc.These polymkeric substance can separately or be used in combination.
In the present invention, as the tackiness agent that in temperature-sensitive is added lustre to layer, contains, can use the dispersible resin of water soluble resin or water.Yet when these resins any mixed with the dispersion of above-mentioned dyestuff that develops the color and developer respectively, the gained mixture should be not painted, assembles and do not have a high viscosity.In addition, be tough and tensile and not have desensitization effect as filming of heat sensitive recording layer formation.Temperature-sensitive is added lustre to binder content in the layer preferably based on the add lustre to 8-20% of amount (by solid) of layer of temperature-sensitive, and it is disadvantageous being less than 8% content, because the intensity of filming is low.Be higher than 20% content and involve the problem that sensitivity reduces.For improve temperature-sensitive add lustre to the layer water tolerance, can use the linking agent that is used for cured resin.
In polychrome thermal recording medium of the present invention, between heat sensitive recording layer, form the middle layer and can effectively improve the heat distribution.The middle layer comprise as its main ingredient with the identical resin of the dispersible resin of water-soluble or water that in heat sensitive recording layer, is used as tackiness agent, and may further include pigment, linking agent etc.The glue spread in middle layer is 1.0-5.0g/m preferably
2When glue spread is less than 1.0g/m
2The time, can not obtain abundant preventive effect to the diffusion between recording layer, cause the quality of image to reduce.When glue spread is higher than 5.0g/m
2The time, sensitivity is lowered unfriendly.
Particularly preferred form as polychrome thermal recording medium of the present invention, can mention the polychrome thermal recording medium, wherein having different colour temps respectively is laminated on the one side of base material with the two heat sensitive recording layers that develop the color with different tones respectively, and in these recording layers, last heat sensitive recording layer contains the reagent that is used as developer and tonal rendering agent simultaneously, or reversible developer, and heat sensitive recording layer contains urea-urea hydride compounds developer down.
In the middle of these, reagent as developer and tonal rendering agent is amphoteric substance simultaneously in last heat sensitive recording layer, it has the acidic-group with coloring function and the basic group with colour killing function, performance coloring function and show the colour killing function when at high temperature heating when it heats at low temperatures.The representative instance of acidic-group is phenolic hydroxyl or carboxyl.The representative instance of basic group is amino.Though amphoteric substance can have the basic group as functional group, preferably it has the basic group as the part of salt compound, as in the title complex of phenol carboxylic acid cpd and amine compound.As follows as the specific examples of this reagent of developer and tonal rendering agent simultaneously.Constitute the phenol carboxylic acid cpd that is used as the reagent of developer and tonal rendering agent simultaneously and comprise 2 hydroxybenzoic acid, 3-hydroxy-benzoic acid, 4-hydroxy-benzoic acid, 3, the 4-resorcylic acid, 3, the 5-resorcylic acid, 2,3-resorcylic acid, 2, the 4-resorcylic acid, 2, the 5-resorcylic acid, 2,6-resorcylic acid, gallic acid, two (4-hydroxy phenyl) acetate, 3, two (4-hydroxyphenyl) propionic acid of 3-etc.
The amine compound that forms salt or complex salts with the phenol carboxylic acid cpd comprises octyl amine, nonyl amine, decyl amine, lauryl amine, tetradecylamine, heptadecyl amine, stearic amine, docosyl amine, 2-METHOXY PROPYL AMINE, hexamethylene-diamine etc.
Reversible developer for example is phenolic compound or phosphinic acid compounds, and this compounds has the aliphatic hydrocarbyl of 8 or 8 above carbon atoms.The specific examples of this reversible developer is the following compound of mentioning.Reversible developer is not limited to following these that mention, can use any reversible developer, as long as it heats time performance coloring function at low temperatures and shows the colour killing function when at high temperature heating.
Reversible developer comprises 4-(octadecane sulfenyl) phenol, 4-(docosane sulfenyl) phenol, 4-(octadecane oxygen base) phenol, 4-(docosane oxygen base) phenol, N-octadecyl-4-hydroxybenzamide, 4 '-hydroxyl docosane aniline, N-(4-hydroxyphenyl)-N '-Octadecane base urea, docosyl phosphonic acids etc.When the polychrome thermal recording medium of the application of the invention writes down with thermal printer etc., only cause with the printing of low-temperature heat and to develop the color in the cryogenic displaying color layer, the printing colour killing and only causing that causes low temperature to add lustre in the layer with the printing of heat develops the color in high temperature adds lustre to layer.
The application of urea-urea hydride compounds makes might obtain the sufficient laser labelling goods of colorant density, and described goods can provide and promptly use fat to contact with oil, chemical, finger mark etc., the highly stable printing colour developing image that image also decolours hardly or fades.Therefore, from the prolonged preservation angle of record thing, this application is particularly advantageous.
The heat sensitive recording layer of laser labelling goods of the present invention preferably contains the recording sensitivity improving agent.
As recording sensitivity improving agent used herein, use can absorb the compound of the laser beam that is used to shine.Their specific examples is various mineral compound such as aluminium hydroxide, wollastonite, wilkinite, mica (for example white mica and phlogopite), Calucium Silicate powder, talcum, kaolin, clay, and silicate minerals (for example foyaite, hornblende and albite).Aluminium hydroxide, white mica, wollastonite and kaolin are particularly preferred.These mineral compound can use separately or as mixture.
In the present invention, the colourless or light dyestuff former that uses in the heat sensitive recording layer and the ratio of recording sensitivity improving agent are not special the restrictions, can suitably select according to the kind and the employed recording sensitivity improving agent of dyestuff former.Usually, the coupler of per 100 weight parts, the usage quantity of recording sensitivity improving agent is 10-5,000 weight part, preferred 100-2,000 weight part.
Dyestuff former, urea-urea hydride compounds developer and the content of recording sensitivity improving agent in heat sensitive recording layer can be regulated as follows: according to the gross weight (by solid) of described layer, the content of dyestuff former is 5-30wt%, preferred 10-25wt%, the content of urea-urea hydride compounds developer is 10-60wt%, preferred 20-50wt%, the content of recording sensitivity improving agent is 5-40wt%, preferred 10-30wt%.
Acid developer is incorporated into has improved sensitivity in the heat sensitive recording layer of laser labelling goods of the present invention and can make the goods of laser labelling produce bright color.As acid developer, the common electronics material that is subjected to that exemplifies more than the use.
For the further sensitivity of the goods of improvement laser labelling of the present invention, but the material of hot melt can be incorporated in the heat sensitive recording layer.But the material of hot melt preferably has 60 ℃ to 180 ℃, especially the material of 80 ℃ to 140 ℃ fusing point.
The marking composition that adds lustre to of the present invention can be by using above-mentioned colourless or light dyestuff former, urea-urea hydride compounds developer, recording sensitivity improving agent and aqueous binders and water as neccessary composition, and if necessary, mix obtaining again with various auxiliary agents.
The glassware for drinking water that uses in the marking composition that adds lustre to has 5-12, the pH of preferred 6-9.When pH is lower than 5, cause bluring.When pH is higher than 12, undesirable effect appears probably, as the forfeiture of the colour developing ability of urea-urea hydride compounds developer.Water can mix use with water-miscible organic solvent such as methyl alcohol, ethanol etc.
Except above-mentioned essential component, if necessary, various auxiliary agents can be incorporated in the marking composition that adds lustre to that uses among the present invention, for example in order to help composition applying on base material.Various auxiliary agents for example comprise dispersion agent (sodium dioctyl sulfosuccinate for example, Sodium dodecylbenzene sulfonate, lauryl alcohol sulfuric ester sodium salt and fatty acid metal salt), turbidization agent (for example titanium dioxide), defoamer, viscosity modifier, fluorescence dye and tinting material.
The marking composition that adds lustre to of the present invention is printed (applying) be not particularly limited, as long as it needs mark to the base material on it.As base material, for example can mention the predetermined portion of food product containers, wrapping material, electronic unit etc., and goods that will be attached to it (for example label base material).As the label base material, suitably use paper (for example paper and synthetic paper), synthetic resin film, plastics, orange cold foil and synthetic paper, metal-coated membrane, metal, timber etc. according to their purpose.
For example according to the preparation as described below marking composition that adds lustre to.With binding agent dissolving be dispersed in the water or the solvent mainly formed by water in.In coupler, developer, recording sensitivity improving agent etc., component in the solvent that should be dispersed in water or mainly form by water contain dispersion agent as the water of poly-(vinyl alcohol) or aqueous solvent in by use dispersion machine such as ball mill, attritor, common or individual curing such as sand mill, thus prepare one or more dispersions.Normally about 2 μ of the mean particle size of each component after the scatter operation or below 2 μ, preferably approximately 1 μ or below 1 μ.Then, binding agent and dispersion are mixed, to obtain the marking composition that adds lustre to of the present invention.The solids content of the described marking composition that adds lustre to is 20 to 70wt%, preferably approximately 30 to about 65wt%.
The marking composition that adds lustre to can directly be applied on the base material, perhaps it can be applied over carry out surface treatment in advance, prime or the base material of similar processing on.Can be by use suitable spreader such as roller coating machine, the intaglio plate coating machine, miniature intaglio plate coating machine, doctor knife coater, spraying machines etc. are coated with.Can be adjusted to 1-4 μ usually by the thickness of filming (heat sensitive recording layer) that applies and drying obtains.When thickness during, be inadequate with the colour developing of laser radiation, and filming tend to peel off less than 1 μ.On the other hand, when thickness was higher than 4 μ, drying property and label tack tended to reduce.Dry according to coating condition such as change of line speed, and can at room temperature carry out, perhaps undertaken by the heating under the condition that does not cause the heat sensitive recording layer colour developing.
The protective layer of laser labelling goods of the present invention forms by apply transparent limpid coating fluid on heat sensitive recording layer.Transparent coating fluid is the waterborne compositions that contains aqueous binders, water etc.
As the aqueous binders that in the transparent coating fluid of protective layer of the present invention, uses, can mention those that the own known water-soluble or dispersible resin of water that is used for coating or printing ink by use obtains as base-material.This resin has optional being incorporated into wherein so that give the hydrophilic radical (for example carboxyl or amino) of water-soluble or water dispersible.As the described resin of aqueous binders, use second-order transition temperature at 20-80 ℃, the resin in the preferred 35-70 ℃ of scope.When second-order transition temperature is lower than 20 ℃, reductions such as the scuff resistance of protective layer, chemical-resistant, water tolerance.On the other hand, when second-order transition temperature was higher than 80 ℃, protective layer became fragile, variation such as flexibility, and be easy to fracture.Therefore, these two kinds of second-order transition temperatures are undesirable.If necessary, except said components, can be with flow agent, slipperiness imparting agent, defoamer etc. are incorporated in the described transparent coating fluid.
As the aqueous binders that uses in transparent coating fluid, (carbonatoms: 1-24) ester is as major constituent and for example unsaturated carboxylic acid such as vinylformic acid, methacrylic acid, toxilic acid etc. for the alkyl by using acrylic or methacrylic acid; The unsaturated monomer of hydroxyl such as Hydroxyethyl acrylate, Rocryl 410 etc.; Contain amino unsaturated monomer such as acrylamide, Methacrylamide etc.; With other unsaturated monomer such as vinylbenzene, vinyl cyanide, vinyl-acetic ester, any in the vinylchlorid etc. makes alkyl ester and this comonomer copolymerization can obtain acrylic resin.Vibrin can react with the ester that has the polyvalent alcohol of two or more hydroxyls in molecule by the polyprotonic acid (comprising acid anhydrides) that has two or more carboxyls in molecule and obtain.The second-order transition temperature of this aqueous binders can be adjusted to arbitrary temp by type, combination and the ratio that suitable selection constitutes the component of described binding agent.
Prepare described transparent coating fluid in the suitable water by above-mentioned aqueous binders is dissolved or is dispersed in, if necessary, introduce flow agent, slipperiness imparting agent, defoamer etc.The solids content of described transparent coating fluid is preferably 20-70wt%, especially 30-60wt%.
Described transparent coating fluid can print (applying) surface at the dry coating that forms as heat sensitive recording layer.The method of printing (applying) is not special restriction.Apply the enough roller coating machines of energy, intaglio plate coating machine, miniature intaglio plate coating machine, spraying machine waits and carries out.
So the thickness of filming that forms can be adjusted to 3-10 μ usually.When thickness during less than 3 μ, the protection of the heat sensitive recording layer that is provided by described Clear coating is inadequate, and reduction such as chemical-resistant, rub resistance.On the other hand, when thickness was higher than 10 μ, drying property of filming and physicals tended to reduce.The drying of described transparent coating fluid changes according to coating condition such as linear velocity, and can at room temperature carry out, and is perhaps undertaken by the heating under the condition that does not cause the heat sensitive recording layer colour developing.
When the heat sensitive recording layer of the goods that are used for mark that so form with laser beam irradiation, illuminated portion is heated, and makes urea-urea alkane developer and dyestuff former react each other with colour developing, obtains mark.Though to the energy of the laser beam that is used to shine is not special restriction, when considering the disruptive possibility of filming, preferably this energy is 1.4J (joule)/cm
2Or 1.4J/cm
2Below.On the other hand, though the lower limit of the required energy that develops the color is unknown, because there do not have device to produce to be low-yield, even at 0.4J/cm
2Energy under also formed sufficient colour developing.Therefore, the suitable energy region that develops the color with irradiation is 0.4-1.4J/cm
2, 0.45-1.2J/cm especially
2As the laser apparatus that is used to shine, pulsed laser or scan laser are fit to.As for the type of laser apparatus, can use for example gas laser, excimer laser, any in the semiconductor laser.The specific examples of laser apparatus is a carbon dioxide laser, mixed gas laser, YAG laser apparatus, ruby laser etc.
As method, can mention with laser beam and filming by the metal mask irradiation so that the method for filming with laser beam irradiation according to the shape of metal mask perforate with laser beam irradiation desired shape part; With the method that desired shape is input in the computer and films with laser beam irradiation according to desired shape in the mode that so-called one way is drawn.When with the laser beam irradiation heat sensitive recording layer, the illuminated portion temperature increases, and experience causes having the letter or the visual appearance of desired shape clearly by the fusing of the component of adding lustre in the heat sensitive recording layer and the colour developing that mixing causes.Can carry out instantaneous by this colour-change that irradiation causes, because the energy density of laser beam is very high.
By with aforesaid method according to its purpose from paper (for example paper and synthetic paper); the label of suitably selecting in synthetic resin film, plastics, orange cold foil and synthetic paper, metallic sprayed coating, the metal etc. can be produced the label as the laser labelling goods of the present invention with forming heat sensitive recording layer and protective layer on the base material.The label of Huo Deing can be used in all common label fields although it is so, but especially is preferred for the field of food, medicine, toiletry, publication and electrical equipment and electronic unit etc.
By on various ordinary packing materials such as case, wrapping paper and parcel any, forming heat sensitive recording layer and protective layer with aforesaid method; can produce the wrapping material as laser labelling goods of the present invention, these wrapping material can obtain by use the base material of suitably selecting according to its purpose from paper (for example paper and synthetic paper), synthetic resin film, plastics, orange cold foil and synthetic paper, metallic sprayed coating, metal, glass, timber etc.Though described wrapping material can be used in all areas of ordinary packing material, especially be preferred for the field of food, medicine, makeup, publication and electrical equipment and electronic unit etc.
As the container of laser labelling goods of the present invention by on base material such as glass, plastics, metal or analogue, forming heat sensitive recording layer with aforesaid method and protective layer is produced.This container can be used in all bread and cheese field of containers, as drinks and refreshment drink bottle, canning food container, snack food product container, cosmetics containers, medical container, fields such as cosmetic product.
When color former of the present invention was used for the pressure sensitive recording material, recording materials for example can have at U.S. patent No.2505470, disclosed form in 2712507,2730456,2730457 and 3418250 etc.Promptly, can use various forms: be dissolved in by mixture and contain alkylated naphthalene with dyestuff former or dyestuff former such as following form, the alkylation hexichol, the alkylation ditan, the alkylation diarylethane, synthetic oil (for example chlorinated paraffin), vegetables oil, animal oil, in the solvent of one or both in the mineral wet goods or multiple mixture, gained solution is dispersed in the binding agent maybe this solution is incorporated into microcapsule, dispersion is applied on the base material or with microcapsule is applied on the base material with binding agent, the last paper that will so obtain again and be stacked together up and down with the following paper of the dispersion of urea-urea hydride compounds (with aminocompound and/or developer etc.) coating makes its coating surface face with each other and the pressure sensitive recording paper that obtains; The pressure sensitive recording paper that the middle paper that simultaneously is coated with dyestuff former with urea-urea hydride compounds dispersion coating and another side by clamping between paper on above-mentioned and the following paper obtains; By on the same surface of base material, applying above-mentioned urea-urea hydride compounds (with aminocompound and/or developer) dispersion and the above-mentioned automatic type pressure sensitive recording paper that contains the dispersion acquisition of dyestuff former with mixture or with multilayer form; With by each dyestuff former and urea-urea hydride compounds (with aminocompound and/or developer) are made microcapsule, on the same surface of base material, apply the automatic type pressure sensitive recording paper that the mixture of two kinds of microcapsule obtains again.
As the method for producing microcapsule, for example can adopt disclosed condensing method in U.S. patent No.2800457 and 2800458, at JP-B-38-19574, JP-B-42-446, disclosed interfacial polymerization among the JP-B-42-771 etc., at JP-B-36-9168, disclosed in-situ method among the JP-B-51-9079 etc., disclosed fusion dispersion method of cooling and in English Patent No.952807 and 96-5074 etc. at U.S. patent No.311140, disclosed spray-drying process among the English Patent No.930422 etc.
Color former of the present invention is equivalent to the dyestuff former described in each piece in above reference etc. and the composition of developer.
In order to form the pressure sensitive recording layer, each component such as urea-urea hydride compounds can use with the form of solution in solvent or dispersion.Further comprise under the situation of aminocompound and/or developer in the system of adding lustre to, each component can be used with the form of solution in solvent or dispersion, or the composition of urea-urea hydride compounds, aminocompound and optional developer can use with the form of solution in solvent or dispersion.
In being used to form the above-mentioned interfacial polymerization of microcapsule, by using two kinds of monomers, promptly oily monomer and water-soluble monomer form film on the interface.For example, known have wherein the polyprotonic acid muriate as oil phase and multivalence amine as water, on the interface, form the method for polyamide layer; Wherein the polyprotonic acid muriate is used as water as oil phase and polyol, forms the method for polyester film on the interface; Wherein polyvalent isocyanate is used as oil phase and polyhydroxy-alcohol or polyhydroxy phenol as water, forms the method for polyurethane film on the interface; Wherein polyvalent isocyanate is used as water as oil phase and multivalence amine, forms the method for polyureas film on the interface.Therefore, when adopting interfacial polymerization to produce microcapsule, use isocyanate compound in some cases as film forming reactive monomer.
In this case, described isocyanate compound is consumed in being formed for the film of microcapsule, and is directly visual not relevant with colour developing, and to use water-soluble monomer and isocyanate compound jointly be indispensable.In these areas, its use is different from the use according to isocyanate compound of the present invention.
By containing compound, prepare the dispersion of the compound of not making microcapsule as one or more compounds of each component as fine grinding in the aqueous solution of water-soluble polymers, tensio-active agent or analogue with dispersive ability.Urea-urea hydride compounds can disperse with aminocompound and acid developer.
As the base material that in the pressure sensitive recording material, uses, the main paper that uses, but can also use various Woven fabrics except that paper according to its purposes, supatex fabric, synthetic resin film, laminated paper, synthetic paper, tinsel and any by in conjunction with in the composite sheet of two or more acquisitions in them.
As binding agent, can use various binding agents commonly used.Binding agent for example comprises water-soluble binder such as starch, Natvosol, methylcellulose gum, carboxymethyl cellulose, gelatin, casein, poly-(vinyl alcohol), poly-(vinyl alcohol) of modification, poly-(vinylformic acid) sodium, acrylamide-acrylicacid ester copolymer, acrylamide-acrylicacid ester-methacrylic acid ter-polymer, the an alkali metal salt of styrene-maleic anhydride copolymer, an alkali metal salt of ethene-copolymer-maleic anhydride etc.; Latex type water-insoluble binding agent with styrene-butadiene copolymer, acrylonitrile butadiene copolymer, methyl acrylate butadiene copolymer etc.
In recording materials of the present invention, recording layer can contain sterically hindered phenolic compound or UV light absorber.Sterically hindered phenolic compound or UV light absorber for example comprise 1,1,3-three (3 '-cyclohexyl-4 '-hydroxyphenyl) butane, 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 4,4 '-thiobis (3-methyl-6-tert butyl phenol), 1,3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-acrinyl) benzene, 2,2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone, Whitfield's ointment is right-the octyl phenyl ester, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, vinylformic acid ethyl-2-cyano group-3,3 '-diphenyl and four (2,2,6,6-tetramethyl--4-piperidyl)-1,2,3,4-butane tetra-carbonic ester.
The add lustre to method of layer of formation is not special restriction.For example by using coating process such as the free-falling curtain coating method that is fit to, the air knife spread coating, Bariber scraper coating method, Pure scraper coating method, short residence time(SRT) coating method or similar approach apply the coating fluid of the layer that is used to add lustre on base material, the dry again base material of handling like this forms the layer that adds lustre to.The glue spread of coating fluid of layer of being used to add lustre to is not special restriction, presses dry weight basis, is controlled at 1-15g/m usually
2Scope in, preferably approximately 3 is to about 10g/m
2
Thermal response can improve by form the middle layer between heat sensitive recording layer and base material.Under the situation of common thermal recording medium, but for example used the technology of improving developing sensitivity by the material of common use hot melt in the layer that adds lustre to.It is unfavorable improving sensitivity in this way, causes fuzzy because be easy to by heat or friction.Especially in the thermal recording medium that obtains by the urea-urea hydride compounds developer that uses the developing sensitivity excellence, it can promote the generation of bluring.Under the situation of the common thermal recording medium that does not have the print retention, even cause fuzzyly, it also disappears as trace, makes under the situation of recording materials after using standing storage especially, seldom considers fuzzy.Yet, under the situation of the thermal recording medium that obtains by the excellent especially urea-urea hydride compounds developer of the long-term print retention of use, caused following typical problem in some cases: when in case cause when fuzzy, it gets off preservation, therefore store and accumulate during the service recorder material then each, make that the recording materials surface is dirty when recording materials use after standing storage.In this case, by forming the middle layer, but but do not use the material of hot melt or only use the material of a spot of hot melt just can obtain actual developing sensitivity, and can obtain also to accumulate hardly even recording materials use to blur after standing storage to by thermal recording medium hot or the fuzzy tolerance excellent performance that friction causes.
The middle layer mainly is made up of organic or inorganic pigment, hollow particle and aqueous binders such as water-soluble polymers or latex.As organic or inorganic pigment and aqueous binders, can use with heat sensitive recording layer in used identical organic or inorganic pigment and aqueous binders.The method that forms the middle layer is not special restriction.As this method, can adopt the method identical with the method that forms heat sensitive recording layer.The dry-coated amount that is used to form the middle layer is preferably 2.0-15.0g/m
2In this case, the surface p H in the middle layer that forms on the base material is 3-9 preferably, is more preferably 5-9, most preferably is 6-8.
In addition, in the present invention, if necessary, the rub resistance of gained recording paper can improve by form the protective layer of mainly being made up of water-soluble polymers on heat sensitive recording layer.When the urea of the present invention that uses the excellent and anti-standing storage excellence of print of developing sensitivity-urea hydride compounds developer, often stay scratch because of highly sensitive.Therefore on the other hand, in case the scratch that stays is preserved the unlimited time, store and scratch accumulation during the service recorder material then each.Therefore, when service recorder paper after standing storage, the paper surface can be dirty in some cases.In this case, by forming protective layer, even recording paper uses after standing storage, scratch also is difficult to accumulation.The object lesson of the water-soluble polymers that is contained in the protective layer is the water-soluble polymers binding agent of mentioning in about heat sensitive recording layer above-mentioned.Water-soluble polymers can use with the common water-resisting agent that can make the water-soluble polymers waterproof.The object lesson of water-resisting agent is a formaldehyde, oxalic dialdehyde, chromium alum, melamine, melamine-formaldehyde resin, polyamide resin, polymeric amide-epichlorohydrin resins etc.
In addition, for example, pigment, metallic soap, wax, linking agent etc. are incorporated in the protective layer in order to improve in printing process with the coupling of thermal head and to improve the water tolerance of protective layer.
Pigment comprises zinc oxide, lime carbonate, barium sulfate, titanium dioxide, lithopone, talcum, agalmatolite, kaolin, aluminium hydroxide, silica, amorphous silica etc.The addition of pigment is 0.5-4 a times of total polymer weight, and preferred 0.8-3.5 doubly.Measure when the lower limit of above scope is following when this, pigment can not effectively improve the coupling with thermal head.When this amount is when the upper limit is above, the sensitivity of thermal recording medium obviously reduces, the commercial value of infringement recording materials.
Metallic soap for example comprises the emulsion of higher fatty acid metal-salt such as Zinic stearas, calcium stearate, aluminum stearate etc.Based on the gross weight of protective layer, with 0.5-20wt%, the ratio of preferred 1-10wt% is added metallic soap.Wax for example comprises paraffin, Microcrystalline Wax, carnauba wax, methylol stearylamide, the emulsion of polyethylene wax etc.Based on the gross weight of protective layer, with 1-20wt%, the ratio of preferred 1-10wt% is added.
When on heat sensitive recording layer, forming protective layer, tensio-active agent is joined in the coating fluid that is used to form protective layer, so that obtain uniform coating.Tensio-active agent comprises an alkali metal salt of sulfo-succinic acid, fluorochemical surfactant etc.The specific examples of tensio-active agent is the sodium salt or the ammonium salt of two (2-ethylhexyl) sulfo-succinic acid, two-(n-hexyl) sulfo-succinic acid etc.Usually, any tensio-active agent all is effectively, as long as it is an anionic.Can also be with usual auxiliaries such as filler, but the material of hot melt (lubricant), tensio-active agent, fluorescence dyes etc. are incorporated in the protective layer.But the material of filler hot melt and the specific examples of fluorescence dye are those that mention about above-mentioned heat sensitive recording layer.The dry-coated amount preferably about 0.5 to about 10g/m of protective layer
2, especially about 1 to about 5g/m
2
If necessary, when forming reverse side layer (back coating) on the opposite face of the recording layer of the recording materials of producing by method of the present invention, the gained recording paper will be difficult to curl.Especially under the situation of urea of the present invention-urea hydride compounds developer, the formation of reverse side layer is because following reason but effectively: described developer is better than other developer on dispersing property, obtain the little dispersion of granularity easily, and has highly sensitive, but in the time will being applied on the base material by the coating fluid that mixes described developer and other necessary component preparation, the force of cohesion of binding agent increases because the granularity of developer is little in the time of exsiccant, make recording layer shrink easily, cause curling easily.As the component of the coating fluid that is used for the reverse side layer and the coating process of this coating fluid, can use identical component and method under the situation of protection recording layer.The dry-coated amount of coating fluid is 0.2-10.0g/m preferably
2
Below further describe the present invention with embodiment.
Carry out the analysis of material and the evaluation of physicals in order to following method.
＜infrared spectra 〉
Use is measured by the FTIR-8100M diffuse reflectance spectroscopy that Shimadzu Corp. produces.
＜mass spectrum 〉
The JMS-HX100 that use is produced by JEOL LTD., nitrobenzyl alcohol is measured as source gas as matrix and xenon.
The developing sensitivity of＜temperature-sensitive paper 〉
By using the printing tester produced by Ohkura Denki K.K. and by Kyocera Co., the thermal head KJT-256-8MG optical density meter that Ltd. produces is measured the colorant density under the pulse width of the impressed voltage of 24V and 1.5 milliseconds.
＜plasticizer resistance properties 〉
Remain on thermal recording medium between the vinylchlorid packaging film or in the vinylchlorid folder, from the top it is applied 300g/cm again
2Load.After placing 24 hours under 40 ℃, the colorant density of visually rank printing and non-printing (source recording material surface).When printing density only slightly descended, the print retention was rated as well.
＜thermotolerance 〉
Thermal recording medium was placed 24 hours, again the visually rank print degree of fading under 60 ℃ and 25%RH.When fading extent was low, the print retention was rated as well.
In addition, thermal recording medium was placed 24 hours under 80 ℃ and 25%RH, again the visually rank print degree of fading.When fading extent was low, the print retention was rated as well.The colorant density of visually rank source recording material surface also.When colour developing was slight, the retention of source recording material surface was rated as well.
The colorant density of＜impact paper 〉
To go up paper and following paper and be stacked together up and down, make they coating surface toward each other.Exert pressure from above, on last paper, to obtain the colour developing image.Optical density meter MacbethRD917 measures the colorant density of colour developing image.
＜solvent resistance 〉
Hand cream (Atrix, trade(brand)name are produced by Kao Corp.) is applied on the colour developing image area that obtains in the colorant density assessment thinly, place 7 days at ambient temperature after, the colorant density of visually rank printing.When printing density only slightly descended, the print retention was rated as well.
Embodiment 1
In the 27.8g 2,4 toluene diisocyanate, add 111g toluene, at room temperature the drips of solution of 7.4g aniline in 37g toluene is added to wherein subsequently, allow reaction carry out again other 1 hour through 1 hour as solvent.By the sedimentary white solid of filtered and recycled, use hexane wash, dry in a vacuum then a whole night, obtained the 20g white crystal.Subsequently, the compound that 5g is so obtained is added in the 50mL methyl alcohol, allows be reflected at again and carries out under 60 ℃ 30 minutes, afterwards, uses vaporizer to remove excessive methanol, toluene is added in the resistates to carry out crystallization again.By filtered and recycled gained white crystal, use hexane wash, dry in a vacuum then a whole night, obtained the 5.4g white crystal.The fusing point of these white crystals is 196 ℃.
The analysis to measure result of these white crystals is as follows:
The IR measuring result:
Characteristic peak appears at 1060cm
-1, 1250cm
-1, 1600cm
-1, 1650cm
-1, 1670cm
-1, 1700cm
-1And 3300cm
-1
The structural formula of the main ingredient of this compound is estimated to be the structural formula of above-claimed cpd (S-1).
Next, by the aqueous solution (Gohseran L-3266 with this compound of 2g and 8g 2.5wt% poly-(vinyl alcohol), trade(brand)name, by The Nippon Synthetic Chemical IndustryCo., Ltd. produces) in paint shaker, grind 6 hours together to disperse the former to prepare dispersion.The temperature of the dispersion that directly obtains after the scatter operation is 25 ℃.The diameter of the discrete particles of compound is about 0.6 μ m.
By (by AIMEX Co., LTD. produces at sand mill with poly-(vinyl alcohol) aqueous solution of 130g 8wt% with 70g 3-dibutylamino-6-methyl-7-anilino fluorane; Vessel volume is 400mL) in 2, the revolution of 000rpm grinds down 3 hours to disperse the former to prepare another dispersion.
By (by AIMEX Co., LTD. produces at sand mill with poly-(vinyl alcohol) aqueous solution of 130g 5.4wt% with the sulfobenzide of 70g; Vessel volume is 400mL) in 2, the revolution of 000rpm grinds down 3 hours to disperse the former to prepare another dispersion.
By being mixed with 30g water and use stirrer to stir this mixture, 10g lime carbonate prepares another dispersion.
Obtain coating fluid by stirring in following ratio (dry basis ratio) and mixing above-mentioned dispersion with other component; Dispersion by the above-claimed cpd of drying solid: 30 weight parts, 3-dibutylamino-6-methyl-7-anilino fluorane dispersion by drying solid: 15 weight parts, sulfobenzide dispersion by drying solid: 30 weight parts, divided calcium carbonate prose style free from parallelism by drying solid: 20 weight parts, Zinic stearas dispersion (solids content 16wt%) by drying solid: 10 weight parts and by the 15wt% of drying solid poly-(vinyl alcohol): 7 weight parts.
Be that 10 metering bar coater is applied in coating fluid and has 50g/m with excellent number
2The body paper of Substance on.After drying, carry out the height calendering, to obtain thermal recording medium.The glue spread of coating fluid is 4g/m by dry weight basis
2
The evaluation result of the sensitivity of the thermal recording medium that obtains is good, and its optical density (OD) is 1.2.The assessment result of the thermic colour-change degree (thermotolerance) of source recording material surface is good, and color change is slight.It also is the slight extent that suits the requirements that the thermic of printing fades.These evaluation results are summed up in table 1.
Embodiment 2
To the 40g methyl ethyl ketone of 17g 2,4 toluene diisocyanate interpolation as solvent, subsequently 3.8g methyl alcohol is added drop-wise to wherein, reaction was under agitation carried out 5 hours at 60 ℃.Then, 9.9g 4,4 '-diamino diphenyl sulfone is added to wherein, reaction was under agitation carried out 4 hours at 60 ℃ again.After reaction finishes, with the reaction soln cool to room temperature, pour into again in the 800g acetonitrile, by the sedimentary crystal of filtered and recycled, with hexane wash and dry in a vacuum then a whole night, to obtain 15g compound as white crystal.
The fusing point of white crystal is 169 ℃, and their analysis to measure result is as follows.
The IR measuring result:
Characteristic peak appears at 1220cm
-1, 1550cm
-1, 1590cm
-1, 1660cm
-1, 1740cm
-1And 3300cm
-1
The mass-spectrometer measurement result:
[M+H]
+Under m/z661, detect.
It is the structural formula of above-claimed cpd (S-13) that the structural formula of the major constituent of this compound is inferred.
Produce thermal recording medium in the mode identical with embodiment 1 then, difference is to use the compound of above acquisition to replace synthetic urea-urea hydride compounds in embodiment 1, estimates again.The gained result sums up in table 1.
Embodiment 3
Dissolving 3.46g aniline at room temperature stirs gained solution again in the ethyl acetate of 100mL.(by Nippon Polyurethane Industry Co., Ltd. produced for Coronate L, trade(brand)name with the trimethylolpropane adduct of 10g tolylene diisocyanate through 1 hour time; 75% ethyl acetate solution) drips of solution in the 50mL ethyl acetate is added to wherein, allows reaction carry out again other 30 minutes.Formed crystal reclaims by filtering, and dry in a vacuum again a whole night is to obtain 5.1g white crystal compound.The fusing point of this white crystal is 161 ℃, and their analysis to measure result is as follows.
The IR measuring result:
Characteristic peak appears at 1070cm
-1, 1220cm
-1, 1550cm
-1, 1600cm
-1, 1700cm
-1And 3300cm
-1
The structural formula of the major constituent of this compound is estimated to be the structural formula of above-claimed cpd (S-33).
Then, produce thermal recording medium in the mode identical with embodiment 1, difference is to use the compound of above acquisition to replace synthetic urea-urea hydride compounds among the embodiment 1, estimates again.The result that obtains sums up in table 1.
Embodiment 4
Add 20g methyl ethyl ketone as solvent to the 2,4 toluene diisocyanate of 10.4g, the diluent with 3.7g 4,4 '-diamino diphenyl sulfone and 30g methyl ethyl ketone is added drop-wise to wherein subsequently, reacts and carries out at ambient temperature 20 hours.After reaction finishes, remove methyl ethyl ketone by concentrating, then toluene is added in the resistates, by the sedimentary white solid of filtered and recycled, use hexane wash again, dry in a vacuum then a whole night, the acquisition 8.8g crystalline compound that is white in color.Subsequently, successively 15g phenol is added to 4g with a small amount of dibutyl tin laurate and obtains in the compound, make again to be reflected at and carried out under 50 ℃ 4 hours.After reaction finishes, toluene is added in the reaction soln, by filtering the crystal of collecting precipitation, use hexane wash, drying a whole night in a vacuum then, obtained the 5.2g crystalline urea-urea hydride compounds that is white in color.
Then, will be added in the 10g 2,4 toluene diisocyanate, subsequently 30g phenol will be added to wherein, and make again to be reflected at and carried out under 100 ℃ 3 hours as the 30g toluene of solvent.After reaction finishes, remove toluene by concentrating, again hexane is added in the resistates.By the sedimentary white crystal of filtered and recycled,, obtained the crystalline urea hydride compounds that is white in color of 15g with hexane wash and dry in a vacuum then a whole night.
The structural formula of the major constituent of this compound is estimated to be the structural formula of compound (C-2) hereinafter described.
Next, the above-mentioned urea of 3g-urea hydride compounds and 2g urea hydride compounds are mixed, to obtain urea-urea alkane composition.After this, 2g urea-urea alkane composition is ground 45 minutes disperseing with the methylated cellulose aqueous solution of 8g 2.5wt% in paint shaker, thereby obtained dispersion.
Then, produce thermal recording medium in the mode identical with embodiment 1, difference is to use the dispersion of described composition to replace the dispersion of the compound that obtains among the embodiment 1.The result that obtains is summarised in the table 1.
Embodiment 5
Produce thermal recording medium in the mode identical with embodiment 4, difference is to use by being blended in the urea that synthetic 4.5g urea-urea hydride compounds and 0.5g urea hydride compounds obtain among the embodiment 4-urea alkane composition and replaces urea-urea alkane composition of using among the embodiment 4, estimates again.The result that obtains is summarised in the table 1.
Embodiment 6
Produce thermal recording medium in the mode identical with embodiment 4, difference is not use the urea-urea alkane composition that uses among the embodiment 4, the be white in color crystalline 7.4g urea-urea alkane composition of use to obtain with embodiment 4 same way as, be after the building-up reactions of urea-urea hydride compounds, before interpolation toluene precipitates, the 2.2g sulfobenzide to be added in the reaction system outside the difference, stir the mixture that is obtained, toluene is added in the mixture, by the sedimentary crystal of filtered and recycled, use the hexane wash crystal, then in a vacuum with crystal dry a whole night.Estimate thermal recording medium.The result that obtains is summarised in the table 1.
Embodiment 7
Under 70 ℃, in the 2,4 toluene diisocyanate of 31.5g, dripping the solution of 21.5g 4,4 '-diamino diphenyl sulfone in 60mL MEK under the stirring of 300-500rpm through 4 hours, reaction was carried out other 4 hours, to obtain white viscosity slurry reaction mixture.Then, reaction mixture is cooled to 50 ℃, again the phenol of 17.1g is poured in the reaction mixture, so that after this dissolving, will be added to wherein as the 0.015g triethylamine of catalyzer therein, reaction was carried out 4 hours, to obtain yellow, transparent and adhesive reaction mixture.Remove the solvent of reaction mixture, under reduced pressure concentrate again, after this grind the gained solid, dry in a vacuum then a whole night, obtained urea-urea alkane composition that about 70g is buff powder to solidify.
The fusing point of buff powder is 160-180 ℃.In the IR of powder measures, because the broad peak that overlaps to form of the characteristic peak of urea groups and urea alkyl appears at 1700cm respectively
-1
According to the measuring result of liquid phase chromatography, the content of the urea in urea-urea alkane composition-urea alkane principal constituent is 68%.
Then, produce thermal recording medium in the mode identical with embodiment 1, difference is to use above-mentioned composition to replace synthetic urea-urea hydride compounds among the embodiment 1, estimates then.The result that obtains is summarised in the table 1.
Embodiment 8
In the 158.5g 2,4 toluene diisocyanate, add 240g methyl ethyl ketone as solvent, again at 30 ℃, under the stirring of 400rpm, through 8 hours with 4,4 of 107.5g powder type '-diamino diphenyl sulfone joins wherein.After 1 hour, the methyl ethyl ketone of 26g is joined wherein, other 15 hours of restir has obtained white viscosity slurry reaction mixture.Then, the solution of 89.5g phenol in the 15.8g methyl ethyl ketone is poured in this reaction mixture, to be dissolved in wherein, after this, to be added to wherein as the solution of triethylamine in methyl ethyl ketone of catalyzer 9.3g 1wt% through 2 hours, reaction was continued 1 hour.After this, reaction mixture was cooled to 20 ℃ and continuously stirring 3 hours, to obtain to contain the slurry that is deposited in pale yellow crystals wherein.Remove the solvent of slurry, under reduced pressure concentrate again, after this, grind the gained solid, dry in a vacuum then a whole night, obtained the urea that is buff powder-urea alkane composition of 355g to solidify.
The fusing point of buff powder is 130-170 ℃.In the IR of powder measures, because the broad peak that overlaps to form of the characteristic peak of urea groups and urea alkyl appears at 1700cm respectively
-1According to the measuring result of liquid phase chromatography, the content of urea-urea alkane principal constituent in urea-urea alkane composition is 65%.
Then, produce thermal recording medium in the mode identical with embodiment 1, difference is to use above-mentioned composition to replace synthetic urea-urea hydride compounds among the embodiment 1, estimates then.The result that obtains is summarised in the table 1.
Embodiment 9
In the 27.8g 2,4 toluene diisocyanate, add 100g toluene, at room temperature the drips of solution of 7.4g aniline in 37g toluene is added to wherein subsequently, reaction was carried out other 1 hour through 1 hour as solvent.Sedimentary white solid reclaims by filtering, and uses hexane wash, dry in a vacuum then a whole night, has obtained the 20g white crystal.Subsequently, the compound that 5g is obtained like this is added in the methyl alcohol of 50mL, makes to be reflected at again and carries out under 60 ℃ 30 minutes, after this, use vaporizer to remove excessive methanol, dried residue a whole night under vacuum again, obtained the 5.4g crystalline urea-urea alkane composition that is white in color.The fusing point of this white crystal is 196 ℃.In crystalline IR measured, the characteristic peak of urea-urea hydride compounds appeared at 1670cm
-1And 1700cm
-1According to the measuring result of liquid phase chromatography, the content of urea-urea alkane principal constituent in urea-urea alkane composition is 92%.
Then, produce thermal recording medium in the mode identical with embodiment 1, difference is to use above-mentioned composition to replace synthetic urea-urea hydride compounds among the embodiment 1, estimates then.The result that obtains is summarised in the table 1.
Embodiment 10
Add the 40g methyl ethyl ketone as solvent in the 17g 2,4 toluene diisocyanate, subsequently 3.8g methyl alcohol is added drop-wise to wherein, reaction was under agitation carried out under 60 ℃ 5 hours again.Then, 4,4 of 9.9g '-diamino diphenyl sulfone is joined wherein, reaction was under agitation carried out under 60 ℃ 4 hours again.After reaction finishes, use vaporizer to remove methyl ethyl ketone as solvent, dried residue a whole night under vacuum again, obtained the 16g crystalline urea-urea alkane composition that is white in color.The fusing point of this white crystal is 169 ℃.In crystalline IR was analyzed, the characteristic peak of urea-urea hydride compounds appeared at 1660cm
-1And 1740cm
-1According to the result that liquid phase chromatography is measured, the content of urea-urea alkane principal constituent in urea-urea alkane composition is 52%.
Then, produce thermal recording medium in the mode identical with embodiment 1, difference is to use above-mentioned composition to replace synthetic urea-urea hydride compounds among the embodiment 1, estimates then.The result that obtains is summarised in the table 1.
Embodiment 11
Dissolving 27.5g 2,4 toluene diisocyanate was added to the drips of solution of 14.7g aniline in 85mL toluene wherein through 30 minutes under 200rpm stirs at 40 ℃ subsequently in 253mL toluene, and reaction was carried out 30 minutes in addition.Add 18.0g2 in the white slurry of such acquisition, two (4-hydroxyphenyl) propane of 2-, 262mL toluene and 0.42mg are increased to 400rpm as the triethylamine of catalyzer with stirring velocity.In order to prevent the gathering of particle in slurry in the initial reaction of controls reaction speed, in according to the temperature of reaction that progressively raises as follows, react: 60 ℃ following 5 hours, 65 ℃ following 2 hours, following hour of 70 ℃ of following 1 hour and 75 ℃.Then, add the triethylamine of 0.42mg, under 80 ℃, reacted 8 hours again.With the reaction mixture cool to room temperature, the gained white crystal passes through filtered and recycled.Dry in a vacuum white crystal a whole night, obtained the 59g crystalline urea-urea alkane composition that is white in color.The fusing point of these white crystals is 170 ℃.In crystalline IR analyzed, the quant's sign peak of urea-urea alkane appeared at 1720cm
-1According to the measuring result of liquid phase chromatography, the content of urea-urea alkane principal constituent in urea-urea alkane composition is 81%.
Then, produce thermal recording medium in the mode identical with embodiment 1, difference is to use above-mentioned composition to replace synthetic urea-urea hydride compounds among the embodiment 1, estimates then.The result that obtains is summarised in the table 1.
Embodiment 12-23
Produce thermal recording medium in the mode identical with embodiment 8, difference is to use 4,4 '-dichloro diphenylsulfone (embodiment 12), 4,4 '-dihydroxy-diphenyl sulfone (embodiment 13), 2,4 '-dihydroxy-diphenyl sulfone (embodiment 14), 4-(benzyloxy) phenol (embodiment 15), Salicylanlide (embodiment 16), 4,4 '-diamino diphenyl sulfone (embodiment 17), 4,4 '-dichloro benzophenone (embodiment 18), 4,4 '-diaminodiphenyl-methane (embodiment 19), 4,4 '-dimethoxy-benzophenone (embodiment 20), diphenyl carbonate (embodiment 21), 4,4 '-dimethoxy sulfobenzide (embodiment 22) or 4,4 '-diallyl oxygen base sulfobenzide (embodiment 23) replacement sulfobenzide, estimate thermal recording medium then.The result that obtains is summarised in the table 1.
The comparative example 1
Produce thermal recording medium in the mode identical with embodiment 1, difference is to use 2, and two (4-hydroxyphenyl) propane of 2-replace synthetic urea-urea hydride compounds among the embodiment 1, estimate then.The result that obtains is illustrated in the table 1.
The comparative example 2
Add the 5mL methyl ethyl ketone as solvent in the 17.4g 2,4 toluene diisocyanate, subsequently the drips of solution of 3.2g methyl alcohol in the 5mL methyl ethyl ketone is added to wherein, reaction was under agitation at room temperature carried out 2 hours again.Then, at room temperature when stirring, the drips of solution in the methyl ethyl ketone of 7.3g n-butylamine at 100mL is added to wherein, again the gained mixture was stirred 1 hour.Sedimentary crystal reclaims by filtering, and uses hexane wash, dry in a vacuum then a whole night, obtains the 27g crystalline compound that is white in color.The fusing point of this white crystal is 156 ℃, and their analysis to measure result is as follows.
The result that IR measures:
Characteristic peak appears at 1240cm
-1, 1550cm
-1, 1640cm
-1, 1720cm
-1And 3300cm
-1
The supposition structural formula of the major constituent of this compound is the formula (R-1) shown in hereinafter.
Then, produce thermal recording medium in the mode identical with embodiment 1, difference is to use the compound of above acquisition to replace synthetic urea-urea hydride compounds among the embodiment 1, estimates then.The result that obtains is summarised in the table 1.
The comparative example 3
In the 10.0g 2,4 toluene diisocyanate, add 100g toluene.Under 25 ℃, when stirring the gained mixture, the solution of stearic amine in 100mL toluene of 15.5g is added to wherein, make again to be reflected at and carried out under 25 ℃ 22 hours.After reaction finished, sedimentary white solid was used toluene wash by filtered and recycled, dry in a vacuum then a whole night, had obtained the 20.4g white crystal.After this, the compound that 5g is obtained like this is added in the 50mL methyl ethyl ketone.When 80 ℃ are stirred the gained mixture, successively 8.6g is added to wherein the solution and the 5mg catalyzer dibutyl tin laurate of hydroxybenzyl carboxylic acid in the 20mL methyl ethyl ketone, make again to be reflected at 80 ℃ of following continuation 12 hours.After reaction finishes,,,, dry in a vacuum then a whole night, obtained the 5.6g white crystal with the methyl ethyl ketone washing again by the sedimentary crystal of filtered and recycled with the reaction mixture cool to room temperature.
The analysis to measure result of these white crystals is as follows.
The result that IR measures:
Characteristic peak appears at 1220cm
-1, 1520cm
-1, 1630cm
-1, 1710cm
-1, 2900cm
-1And 3300cm
-1
The mass-spectrometer measurement result:
[M+H]
+Detect for 596 times at m/z.
The supposition structural formula of the major constituent of this compound is the formula (R-2) shown in hereinafter.
Produce thermal recording medium in the mode identical with embodiment 1, difference is to use the compound of above acquisition to replace synthetic urea-urea hydride compounds among the embodiment 1, estimates then.The result that obtains is summarised in the table 1.
The comparative example 4
To 100mL two
Add the 3.0g p-aminophenol in the alkane.When 50 ℃ are stirred the gained mixture, through 1 hour with 5.4g tolylsulfonyl based isocyanate at 30mL two
Drips of solution in the alkane is added to wherein, makes to be reflected at 50 ℃ of following continuation 5 hours again.After reaction finished, concentrated reaction solution was poured in the hexane then to carry out crystallization, again by the filtered and recycled precipitated solid, with hexane wash and drying a whole night in a vacuum then, had obtained 4.9g brown crystal.After this, the compound that 2g is obtained like this is added to 50mL two
In the alkane.When 80 ℃ are stirred the gained mixture, successively with 3.8g isocyanic acid stearyl at 10mL two
Solution in the alkane and 2mg catalyzer dibutyl tin laurate add to wherein, make to be reflected at 80 ℃ of following continuation 20 hours again.After reaction finishes, with the reaction mixture cool to room temperature, again by the sedimentary crystal of filtered and recycled, with two
The alkane washing, dry in a vacuum then a whole night, the rose pink crystal of acquisition 2.7g.
These rose pink crystalline analysis to measure results are as follows.
The result that IR measures:
Characteristic peak appears at 1230cm
-1, 1470cm
-1, 1510cm
-1, 1570cm
-1, 1620cm
-1, 1700cm
-1, 2900cm
-1And 3300cm
-1
The structural formula of the major constituent of this compound is a formula (R-3) shown below.
Produce thermal recording medium in the mode identical with embodiment 1, difference is to use the compound of above acquisition to replace synthetic urea-urea hydride compounds among the embodiment 1, estimates then.The result that obtains is summarised in the table 1.
(R-3)
The comparative example 5
In the 10g 2,4 toluene diisocyanate, add 50g toluene, subsequently 30g aniline is added to wherein, make again to be reflected at and carried out under 25 ℃ 3 hours as solvent.After reaction finishes,,, obtained the crystalline compound that is white in color of 17g with hexane wash and dry in a vacuum then a whole night by the sedimentary white solid of filtered and recycled.
The structural formula of the major constituent of this compound is the structural formula of compound (C-1) shown below.
Then, this compound of 2g is ground 45 minutes disperseing with poly-(vinyl alcohol) aqueous solution of 8g 2.5wt% in paint shaker, thereby obtained dispersion.
Then, produce thermal recording medium in the mode identical with embodiment 1, difference is to use this dispersion of described compound to replace the dispersion of the compound that obtains among the embodiment 1, estimates then.The result that obtains is summarised in the table 1.
The comparative example 6
In the 10g 2,4 toluene diisocyanate, add 30g toluene, subsequently 30g phenol is added to wherein, make again to be reflected at 100 ℃ of following reactions 3 hours as solvent.After reaction finishes, remove toluene and hexane is added in the resistates by concentrating, by the sedimentary white solid of filtered and recycled, use hexane wash again, drying a whole night in a vacuum then, obtained the 15g crystalline compound that is white in color.
The structural formula of the major constituent of this compound is the structural formula of compound (C-2) shown below.
Then, compound that 2g obtained poly-(vinyl alcohol) aqueous solution with 8g 2.5wt% was ground in paint shaker 45 minutes, disperseing, thereby obtained dispersion.
Then, produce thermal recording medium in the mode identical with embodiment 1, difference is to use this dispersion of described compound to replace the dispersion of the compound that obtains among the embodiment 1, estimates then.The result that obtains is summarised in the table 1.
The comparative example 7
Produce thermal recording medium in the mode identical with embodiment 1, difference is to use 1, and the 3-diphenyl urea replaces synthetic urea-urea hydride compounds among the embodiment 1, estimates then.The result that obtains is summarised in the table 1.
Table 1
| Embodiment 5 | 1.2? | ◎? | ◎? | ?◎? | ?◎? |
| Embodiment 6 | 1.2? | ○? | ◎? | ?○? | ?○～◎? |
| Embodiment 7 | 1.2? | ◎? | ◎? | ?○? | ?◎? |
| Embodiment 8 | 1.2? | ◎? | ◎? | ?○? | ?◎? |
| Embodiment 9 | 1.2? | △? | ◎? | ?○? | ?○? |
| Embodiment 10 | 1.2? | ◎? | ◎? | ?○? | ?◎? |
| Embodiment 11 | 1.2? | ○? | ◎? | ?○? | ?○～◎? |
| Embodiment 12 | 1.2? | ◎? | ◎? | ?◎? | ?◎? |
| Embodiment 13 | 1.2? | ○? | ◎? | ?◎? | ?○～◎? |
| Embodiment 14 | 1.3? | ○? | ◎? | ?○～◎? | ?○～◎? |
| Embodiment 15 | 1.2? | ◎? | ◎? | ?○? | ?○～◎? |
| Embodiment 16 | 1.2? | ◎? | ◎? | ?◎? | ?◎? |
| Embodiment 17 | 1.1? | ○? | ◎? | ?◎? | ?○～◎? |
| Embodiment 18 | 1.2? | ◎? | ◎? | ?○? | ?○～◎? |
| Embodiment 19 | 1.2? | ○～◎? | ◎? | ?○～◎? | ?○～◎? |
| Embodiment 20 | 1.3? | ○? | ◎? | ?◎? | ?○～◎? |
| Embodiment 21 | 1.2? | ◎? | ◎? | ?◎? | ?◎? |
| Embodiment 22 | 1.2? | ◎? | ◎? | ?◎? | ?◎? |
| Embodiment 23 | 1.2? | ◎? | ◎? | ?◎? | ?◎? |
| The comparative example 1 | 1.3? | ×? | △～○? | ?×? | ?×? |
| The comparative example 2 | 0.3? | ×? | ×? | ?△? | ?×? |
| The comparative example 3 | 0.3? | ×? | △? | ?○? | ?×? |
| The comparative example 4 | 0.4? | ×? | △? | ?○? | ?×? |
| The comparative example 5 | 0.5? | ×? | ×? | ?○? | ?×? |
| The comparative example 6 | 0.4? | ×? | ×? | ?○? | ?×? |
| The comparative example 7 | 0.6? | ×? | ×? | ?△? | ?×? |
1, sensitivity is increased with the increase of optical density (OD) (OD value).
2, plasticizer resistance properties (print retention)
◎～do not have substantially and fade.
Zero～tone slightly changes, and is not fuzzy etc.
△～obviously fade.
The color of *～print completely loses.
3, thermotolerance (print 60 ℃ retention)
◎～do not have fuzzy substantially.
Zero～tone slightly changes, but fuzzy etc.
△～obviously fade.
The color of *～print completely loses.
4, thermotolerance (source recording material surface 80 ℃ retention)
◎～do not have fuzzy substantially.
Zero～printing can be read, but tone slightly changes.
△～printing is owing to fuzzy being difficult to reads.
*～printing is because serious fuzzy and can not read.
Embodiment 24
When 60 ℃ are down stirred the 31.5g 2,4 toluene diisocyanate, through 4 hours with 21.5g4,4 '-diamino diphenyl sulfone is added drop-wise to wherein with the 120ml methyl ethyl ketone, make again to be reflected at 60 ℃ of other 2 hours of continuation down.After reaction finishes, with the reaction soln cool to room temperature, then toluene is added to wherein, by the sedimentary white solid of filtered and recycled, use toluene wash again, dry in a vacuum then a whole night, the acquisition 47g crystalline compound that is white in color.Subsequently, 9.5g phenol and 95ml methyl ethyl ketone are added to 30g obtain in the compound, subsequently the 30mg triethylamine is joined wherein, make again to be reflected at and carried out under 25 ℃ 4 hours.After reaction finishes, join toluene in the reaction soln and, use toluene wash by the sedimentary crystal of filtered and recycled, drying a whole night in a vacuum then, obtained the 38.5g crystalline compound that is white in color.These white crystals are carried out IR measure, find that characteristic peak appears at 990cm
-1, 1110cm
-1, 1320cm
-1, 1590cm
-1, 1700cm
-1And 3350cm
-1
Then, by compound that 2g obtains is ground 6 hours to disperse the former to prepare dispersion with poly-(vinyl alcohol) aqueous solution of 8g 2.5wt% in paint shaker.The temperature of the dispersion that directly obtains after the scatter operation is 25 ℃.The diameter of the discrete particles of compound is 0.6 μ m.
By with the 3-dibutylamino-6-methyl-7-anilino fluorane of 70g and the Vltra tears aqueous solution (the Metlose 60SH-03 of 130g 5.4wt%, by Shin-Etsu ChemicalCo., Ltd. produce) (by AIMEX Co., LTD. produces at sand mill together; Vessel volume is 400mL) in 2, the revolution of 000rpm grinds down 3 hours to disperse the former to prepare another dispersion.
By (by AIMEX Co., LTD. produces at sand mill with poly-(vinyl alcohol) aqueous solution of 130g 8wt% with the sulfobenzide of 70g; Vessel volume is 400mL) in 2, the revolution of 000rpm grinds down 3 hours to disperse the former to prepare another dispersion.
By being mixed with 30g water and stir this mixture with stirrer, 10g lime carbonate prepares another dispersion.
Obtain coating fluid by stirring in following ratio (dry basis ratio) and mixing above-mentioned dispersion with other component; Dispersion by the above-claimed cpd of drying solid: 20 weight parts, 3-dibutylamino-6-methyl-7-anilino fluorane dispersion by drying solid: 10 weight parts, sulfobenzide dispersion by drying solid: 25 weight parts, divided calcium carbonate prose style free from parallelism by drying solid: 40 weight parts, Zinic stearas dispersion (solids content 16wt%) by drying solid: 20 weight parts and by the 15wt% of drying solid poly-(vinyl alcohol): 15 weight parts.
Be that coating fluid is applied in Substance is 50g/m for 10 metering bar coater with excellent number
2Body paper on.The glue spread of coating fluid is 5g/m
2(pressing dry weight basis).After drying, carry out the height calendering, to obtain thermal recording medium.
The evaluation result of the sensitivity of the thermal recording medium that obtains is good, and optical density (OD) is 1.3.Print retention by the evaluation of use vinylchlorid packaging film is good.The whiteness of source recording material surface is good, is 82.These evaluation results are summarised in the table 2.
Embodiment 25 and 26
Produce thermal recording medium in the mode identical with embodiment 24, difference is to use 3-diethylin-6-methyl-7-anilino fluorane (embodiment 25) or 3, two (dimethylamino phenyl)-6-dimethylamino benzo [c] furanones (embodiment 26) of 3-replace 3-dibutylamino-6-methyl-7-anilino fluorane, estimate then.The result that obtains is summarised in the table 2.
Embodiment 27-29
Produce thermal recording medium in the mode identical with embodiment 24, difference is to use methylcellulose gum (Metlose M-15, by Shin-Etsu Chemical Co., Ltd. produce) (embodiment 27), Voranol EP 2001 sulfuric ester (Rebenol WX, produce by Kao Corp.) (embodiment 28) or sulfo-succinic acid 2-(ethyl hexyl) ester sodium (Neocol SWC, by Dai-ichi KogyoSeiyaku Co., Ltd. production) (embodiment 29) replace the Vltra tears of use among the embodiment 24, be used to disperse 3-dibutylamino-6-methyl-7-anilino fluorane, estimate thermal recording medium then.The result that obtains is summarised in the table 2.
Embodiment 30
Prepare urea-urea hydride compounds developer dispersion, 3-dibutylamino-6-methyl-7-anilino fluorane dispersion, sulfobenzide dispersion and divided calcium carbonate prose style free from parallelism in the mode identical with embodiment 24.
On the other hand, by with 70g 2, two (4-hydroxyphenyl) propane of 2-with poly-(vinyl alcohol) aqueous solution of 130g 5.4wt% sand mill (by AIMEX Co., LTD. production; Vessel volume is 400mL) in 2, the revolution of 000rpm grinds down 3 hours to disperse the former to prepare dispersion.
Obtain coating fluid by stirring in following ratio (dried component ratio) and mixing above-mentioned dispersion with other component; Dispersion by the urea-urea hydride compounds of drying solid: 10 weight parts, 3-dibutylamino-6-methyl-7-anilino fluorane dispersion by drying solid: 10 weight parts, sulfobenzide dispersion by drying solid: 20 weight parts, by 2 of drying solid, two (4-hydroxyphenyl) propane dispersions of 2-: 10 weight parts, divided calcium carbonate prose style free from parallelism by drying solid: 20 weight parts, Zinic stearas dispersion (solids content 16wt%) by drying solid: 10 weight parts and by poly-(vinyl alcohol) of the 15wt% of drying solid: 10 weight parts.
Produce thermal recording medium in the mode identical with embodiment 24, difference is to use the coating fluid of above acquisition, estimates then.The result that obtains is summarised in the table 2.
Embodiment 31-34
Produce thermal recording medium in mode similarly to Example 30; difference be to use 4-isopropyl phenyl-4 '-hydroxyphenyl sulfone (D-8; trade(brand)name; by Nippon Soda Co.; Ltd. produce) (embodiment 31); two (3-allyl group-4-hydroxyphenyl) sulfone (TG-SA, trade(brand)name is by NipponKayaku Co.; Ltd. produce) (embodiment 32); 2,4 '-dihydroxy-diphenyl sulfone (24BPS, trade(brand)name; by Nicca Chemical Co.; Ltd. produce) (embodiment 33) or mainly by 4,4 '-[oxygen two (ethyleneoxy group-right-phenylene alkylsulfonyl)] diphenol (D-90, trade(brand)name; by Nippon SodaCo.; Ltd. production) mixture of forming (embodiment 34) replaces 2, and two (4-the hydroxyphenyl)-propane of 2-are estimated thermal recording medium then.The result that obtains is summarised in the table 2.
Embodiment 35-64
To produce thermal recording medium with each identical mode of embodiment 30-34, difference is to use betanaphthyl benzylic ether (BON, trade(brand)name, produce by Ueno Fine ChemicalsIndustry Ltd.) (embodiment 35-39), to Benzyldiphenyl (PBBP, trade(brand)name, by Nippon Steel Chemical Co., Ltd. produce) (embodiment 40-44), 1,2-two (-methylphenoxy) ethane (KS-235, trade(brand)name, by SANKOSHA Co., LTD. produces) (embodiment 45-49), oxalic acid two-to methyl-benzyl ester (HS3520, trade(brand)name, by DainipponInk and Chemicals, Inc. produces) (embodiment 50-54), 1,2-hexichol oxygen ylmethyl benzene (PMB-2, trade(brand)name, by Nicca Chemical Co., Ltd. produces) (embodiment 55-59) or meta-terphenyl (mtp, trade(brand)name, by Nippon Steel Chemical Co., Ltd. produces) (embodiment 60-64) replace sulfobenzide, estimates thermal recording medium then.The result that obtains is summarised in the table 2.
Embodiment 65 and 66
Produce thermal recording medium in the mode identical with embodiment 24; difference is to use stearylamide emulsification product (Highmicron G-270; trade(brand)name; by Chukyo Yushi Co.; Ltd. produce) (embodiment 65) and N; N-acetoacetyl-neighbour-chloro aminobenzen (acetoacetico-chloroanilide) (by Mitsuboshi Chemical Co., Ltd. produces) (embodiment 66) replaces sulfobenzide, estimates again.The result that obtains is summarised in the table 2.
Embodiment 67
Produce thermal recording medium in the mode identical with embodiment 30, difference is with Stilbene fluorochrome (Kayahol 3BS, trade(brand)name, by Nippon Kayaku Co., Ltd. production) ratio in 1 weight part/100 weight parts (in drying solid) coating fluid is added in the coating fluid of preparation in embodiment 30, estimates again.The result that obtains is summarised in the table 2.
Embodiment 68
By with 70g 1,1, (by AIMEX Co., LTD. produces 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl)-butane at sand mill with poly-(vinyl alcohol) aqueous solution of 130g5.4wt%; Vessel volume is 400mL) in 2, the revolution of 000rpm grinds down 3 hours to disperse the former to obtain dispersion.
Then, produce thermal recording medium in the mode identical with embodiment 30, difference is with above-mentioned 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl)-butane dispersion is added in the coating fluid of preparation among the embodiment 30 in the ratio of 10 weight parts/100 weight parts (in drying solid) coating fluid, estimates again.The result that obtains is illustrated in the table 2.
Embodiment 69
In the 30g 2,4 toluene diisocyanate, add 30g toluene, subsequently 3.24g phenol is added to wherein, make again to be reflected at and carry out 1 hour 30 minutes under 100 ℃ as solvent.After reaction finishes, remove toluene by concentrating, hexane is added in the resistates, reclaim the white solid precipitation by filtering, use hexane wash, drying a whole night in a vacuum then, obtained the 6.9g crystalline compound that is white in color.Subsequently, will join 5.0g as the 100g toluene of solvent and obtain in the compound, subsequently 3.50g aniline will be added to wherein, and make again to be reflected at and carried out under 25 ℃ 3 hours.Sedimentary crystal reclaims by filtering, and uses hexane wash, dry in a vacuum then a whole night, has obtained the 5.5g crystalline compound that is white in color.These white crystals are carried out IR measure, find that characteristic peak appears at 890cm
-1, 1000cm
-1, 1030cm
-1, 1440cm
-1, 1720cm
-1And 3350cm
-1
Then, produce thermal recording medium in the mode identical with embodiment 68, difference is to use the compound of above acquisition to replace the urea-urea hydride compounds that uses among the embodiment 68, estimates again.The result that obtains is summarised in the table 2.
Embodiment 70-75
Produce thermal recording medium in the mode identical with embodiment 68, difference is to use 1,1,3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane (Adecaarcles DH-43, produce by Asahi Denka Kogyo K.K.) (embodiment 70), 4-benzyloxy-4 '-(2,3-epoxy group(ing)-2-methyl-prop-1-base oxygen base) sulfobenzide (NTZ-95, by Nippon Soda Co., Ltd. produce) (embodiment 71), methylene-bis (2-hydroxyl-3-(benzotriazole-2-yl)-uncle's 5-octyl phenyl) (embodiment 72), 2-(2 '-hydroxyl-5 '-aminomethyl phenyl)-benzotriazole (Adecaarcles DN-13, produce by Asahi Denka Kogyo K.K.) (embodiment 73), 1,3,5-three (2,6-dimethyl-4-the tertiary butyl-3-hydroxybenzyl) isocyanuric acid ester (Adecaarcles DH-48, produce by Asahi DenkaKogyo K.K.) (embodiment 74) or 2,2-methylene-bis (4, the 6-di-tert-butyl-phenyl) sodium phosphate (Adecaarcles F-85 is produced by Asahi Denka Kogyo K.K.) (embodiment 75) replaces 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl)-butane estimates thermal recording medium then.The result that obtains is summarised in the table 2.
The comparative example 8
Produce thermal recording medium in mode similarly to Example 24, difference is to use 2, and two (4-hydroxyphenyl) propane of 2-replace synthetic urea-urea hydride compounds among the embodiment 24, estimate again.The result that obtains is illustrated in the table 2.
Table 2
| ? | The sensitivity of temperature-sensitive paper | Plasticizer resistance properties (print retention) | Whiteness | Total appraisal |
| Embodiment 24 | 1.3? | ◎ | 82? | ◎? |
| Embodiment 25 | 1.3? | ◎ | 81? | ◎? |
| Embodiment 26 | 1.3? | ◎ | 82? | ◎? |
| Embodiment 27 | 1.3? | ◎ | 82? | ◎? |
| Embodiment 28 | 1.3? | ◎ | 82? | ◎? |
| Embodiment 29 | 1.3? | ◎ | 82? | ◎? |
| Embodiment 30 | 1.3? | ○～◎? | 81? | ○? |
| Embodiment 31 | 1.3? | ○～◎? | 81? | ○? |
| Embodiment 32 | 1.3? | ○～◎? | 81? | ○? |
| Embodiment 33 | 1.3? | ○～◎? | 81? | ○? |
| Embodiment 34 | 1.2? | ◎ | 81? | ○? |
| Embodiment 35 | 1.4? | ○～◎? | 82? | ○～◎? |
| Embodiment 36 | 1.4? | ○～◎? | 83? | ○～◎? |
| Embodiment 37 | 1.4? | ○～◎? | 82? | ○～◎? |
| Embodiment 38 | 1.3? | ○～◎? | 82? | ○～◎? |
| Embodiment 39 | 1.2? | ◎ | 82? | ○～◎? |
| Embodiment 40 | 1.3? | ○～◎? | 82? | ○～◎? |
| Embodiment 41 | 1.3? | ○～◎? | 83? | ○～◎? |
| Embodiment 42 | 1.3? | ○～◎? | 82? | ○～◎? |
| Embodiment 43 | 1.3? | ○～◎? | 82? | ○～◎? |
| Embodiment 44 | 1.2? | ◎ | 82? | ○～◎? |
| Embodiment 45 | 1.3? | ○～◎? | 83? | ○～◎? |
| Embodiment 46 | 1.3? | ○～◎? | 83? | ○～◎? |
| Embodiment 47 | 1.3? | ○～◎? | 82? | ○～◎? |
| Embodiment 48 | 1.3? | ○～◎? | 82? | ○～◎? |
| Embodiment 49 | 1.2? | ◎ | 82? | ○～◎? |
| Embodiment 50 | 1.3? | ○～◎? | 83? | ○～◎? |
| Embodiment 51 | 1.4? | ○～◎? | 82? | ○～◎? |
| Embodiment 52 | 1.4? | ○～◎? | 82? | ○～◎? |
| Embodiment 53 | 1.3? | ○～◎? | 82? | ○～◎? |
| Embodiment 54 | 1.2? | ◎? | 82? | ○～◎? |
| Embodiment 55 | 1.3? | ○～◎? | 83? | ○～◎? |
| Embodiment 56 | 1.3? | ○～◎? | 82? | ○～◎? |
| Embodiment 57 | 1.3? | ○～◎? | 82? | ○～◎? |
| Embodiment 58 | 1.3? | ○～◎? | 82? | ○～◎? |
| Embodiment 59 | 1.2? | ◎? | 82? | ○～◎? |
| Embodiment 60 | 1.3? | ○～◎? | 82? | ○～◎? |
| Embodiment 61 | 1.3? | ○～◎? | 82? | ○～◎? |
| Embodiment 62 | 1.3? | ○～◎? | 82? | ○～◎? |
| Embodiment 63 | 1.3? | ○～◎? | 82? | ○～◎? |
| Embodiment 64 | 1.2? | ◎? | 82? | ○～◎? |
| Embodiment 65 | 1.3? | ○～◎? | 83? | ◎? |
| Embodiment 66 | 1.2? | ◎? | 82? | ◎? |
| Embodiment 67 | 1.3? | ○～◎? | 85? | ○～◎? |
| Embodiment 68 | 1.3? | ◎? | 82? | ◎? |
| Embodiment 69 | 1.3? | ◎? | 82? | ◎? |
| Embodiment 70 | 1.3? | ◎? | 82? | ◎? |
| Embodiment 71 | 1.3? | ◎? | 82? | ◎? |
| Embodiment 72 | 1.3? | ○～◎? | 82? | ○～◎? |
| Embodiment 73 | 1.3? | ○～◎? | 82? | ○～◎? |
| Embodiment 74 | 1.3? | ○～◎? | 82? | ○～◎? |
| Embodiment 75 | 1.3? | ○～◎? | 83? | ○～◎? |
| The comparative example 8 | 1.3? | ×? | 78? | ×? |
1, sensitivity is increased with the increase of optical density (OD) (OD value).
2, plasticizer resistance properties (print retention)
◎～do not have substantially and fade.
Zero～tone slightly changes, and is not fuzzy etc.
△～obviously fade.
The color of *～print completely loses.
3, whiteness increases with the increase of its numerical value.When numerical value 80 or 80 when above, whiteness is sufficient in practice.
＜rub resistance 〉
With acutely the rub surface of thermal recording medium of nail, range estimation judges whether cause colour developing at friction portion.When recording materials did not show tangible scratch, it is good that it is rated as rub resistance.
The accumulation of＜scratch 〉
The same part of 20cm length on the recording surface of every kind of thermal recording medium being produced makes to have the cylinder that diameter is the face of 5cm (weight: 2kg) speed with 20cm/sec moves 50 times, makes recording materials at room temperature place for 1 week then.After placing a week, range estimation judges whether printed image can be read.When printed image can fully be read, recording materials were rated as well.
Embodiment 76
Obtain the temperature-sensitive coating fluid in the mode identical with embodiment 24.Then, using excellent number is that 10 metering bar coater is applied in coating fluid and has 50g/m
2The body paper of Substance on.After drying, carry out the height calendering, on base material, to form the temperature-sensitive layer that adds lustre to.The glue spread of coating fluid is 5g/m by dry weight basis
2
Then, by (by AIMEX CO., TLD. produces at sand mill with the sodium hexametaphosphate solution of 60g 0.7% with 40g kaolin; Vessel volume 400ml) 2, the revolution of 000rpm grinds 3 hours down to disperse the former to prepare dispersion in.
By stirring in following ratio (dry basis ratio) and mixing the coating fluid that kaolin dispersion and other component obtain to be used for forming protective layer; Kaolin dispersion by drying solid: 20 weight parts, Zinic stearas dispersion (solids content 16wt%) by drying solid: 10 weight parts, carboxy-modified poly-(vinyl alcohol) aqueous solution by drying solid: 40 weight parts and by the polyacrylamide base epichlorohydrin cross-linked agent aqueous solution of drying solid: 5 weight parts.
Using excellent number is that coating fluid that 5 metering bar coater will be used to form protective layer is applied in temperature-sensitive and adds lustre on the layer.After drying, carry out the height calendering, to obtain thermal recording medium.The glue spread that is used to form the coating fluid of protective layer is 2g/m by dry weight basis
2
The evaluation result of the sensitivity of the thermal recording medium that obtains is good, and optical density (OD) is 1.3.It is good using the print retention of vinylchlorid packaging film evaluation.With acutely the rub surface of thermal recording medium of nail, range estimation judges whether cause colour developing in friction portion, and finding does not have tangible scratch, that is, rub resistance is good.The result who estimates the test of long duration of rub resistance is good, can fully read printed image.These evaluation results are summarised in the table 3.
Embodiment 77 and 78
Produce thermal recording medium in the mode identical with embodiment 76, difference is to use poly-(vinyl alcohol) (embodiment 77) or acrylic copolymer (embodiment 78) replaces carboxy-modified poly-(vinyl alcohol), estimates again.The result that obtains is summarised in the table 3.
Embodiment 79-81
Produce thermal recording medium in the mode identical with embodiment 76, difference is to use aluminium hydroxide (embodiment 79), and crosslinkable poly-(methyl methacrylate) resin (embodiment 80) or silicon-dioxide (embodiment 81) replace kaolin, estimate again.The result that obtains is summarised in the table 3.
Embodiment 82
By stirring in the ratio (dry weight ratio) of 100 weight parts and 12 weight parts respectively and mixing the coating fluid that 33wt% calcined kaolin dispersion and 50wt% phenylethylene/butadiene type latex water dispersion obtain to be used for the middle layer.
Then by stirring in the ratio (dry weight ratio) of 100 weight parts and 7 weight parts respectively and mixing the 20wt% ACRYLIC EMULSION and 10wt% silica fine powder dispersion (Fineseal SP-10) obtains back side coating fluid.
The above-mentioned coating fluid that will be used for the middle layer is with 10g/m
2The amount of (by solid) is applied over body paper (50g/m
2) one side and dry, again with the temperature-sensitive coating fluid of embodiment 76 preparations with 5g/m
2The amount of (by solid) is applied over one side and dry, and after this coating fluid that is used for protective layer that embodiment 76 is prepared is with 2g/m
2The amount of (by solid) is applied over one side and dry.Then, with above-mentioned back side coating fluid with 1g/m
2The amount of (by solid) is applied over uncoated and dry, carries out calendering again to form thermal recording medium, estimates again.The result that obtains is summarised in the table 3.
The comparative example 9
Produce thermal recording medium in the mode identical with embodiment 76, difference is not apply the coating fluid that is used to form protective layer on temperature-sensitive is added lustre to layer, revalues recording materials.The result that obtains is summarised in the table 3.
Table 3
| ? | The sensitivity of temperature-sensitive paper | Plasticizer resistance properties (print retention) | Rub resistance | The accumulation of scratch | Total appraisal |
| Embodiment 76 | 1.3? | ◎? | ◎? | ◎? | ◎? |
| Embodiment 77 | 1.3? | ◎? | ◎? | ◎? | ◎? |
| Embodiment 78 | 1.3? | ◎? | ○～◎? | ◎? | ○～◎? |
| Embodiment 79 | 1.3? | ◎? | ◎? | ◎? | ◎? |
| Embodiment 80 | 1.3? | ◎? | ○～◎? | ◎? | ○～◎? |
| Embodiment 81 | 13? | ◎? | ◎? | ◎? | ◎? |
| Embodiment 82 | 1.4? | ◎? | ◎? | ◎? | ◎? |
| The comparative example 9 | 1.3? | △～○? | ×～△? | ×? | ×? |
1, sensitivity is increased with the increase of optical density (OD) (OD value).
2, plasticizer resistance properties (print retention)
◎～do not have substantially and fade.
Zero～tone slightly changes, and is not fuzzy etc.
△～obviously fade.
The color of *～print completely loses.
3, rub resistance
◎～scratch does not manifest black.
Zero～scratch shows slight color, but not obvious.
△～scratch shows the color of limited extent and is tangible.
*～scratch presents black and is tangible.
4, the accumulation of scratch
◎～obtained good result reads printed image and has no problem.
Zero～scratch shows slight colour developing, but can fully read printed image.
△～scratch colour developing makes that printed image is difficult to read.
*～scratch shows black, makes to read printed image.
Embodiment 83
The aqueous solution (the Gohsenol KL-05 of poly-(vinyl alcohol) by the 2g compound that will in embodiment 24, obtain and 8g 2.5wt%, trade(brand)name, by The Nippon SyntheticChemical Industry Co., Ltd. produces) in paint shaker, grind 6 hours together to disperse the former to prepare dispersion.The temperature of the dispersion that obtains immediately after the scatter operation is that 25 ℃ of pH with dispersion are 8.The diameter of the discrete particles of compound is 0.6 μ m.
By (by AIMEX Co., LTD. produces at sand mill with poly-(vinyl alcohol) aqueous solution of 130g 5.4wt% with 70g 3-dibutylamino-6-methyl-7-anilino fluorane; Vessel volume is 400mL) in 2, the revolution of 000rpm grinds down 3 hours to disperse the former to prepare another dispersion.
By poly-(vinyl alcohol) (Gohsenol KL-05 with 70g sulfobenzide and 130g 5.4wt%, trade(brand)name, by The Nippon Synthetic Chemical Industry Co., Ltd. produces) (by AIMEX Co., LTD. produces the aqueous solution at sand mill together; Vessel volume is 400mL) in 2, the revolution of 000rpm grinds down 3 hours to disperse the former to prepare another dispersion.
By being mixed with 30g water and use stirrer to stir this mixture, 10g lime carbonate prepares another dispersion.
Obtain coating fluid by stirring and mix above-mentioned dispersion with other component in following ratio (doing the matter ratio); Dispersion by the above-claimed cpd of drying solid: 30 weight parts, 3-dibutylamino-6-methyl-7-anilino fluorane dispersion by drying solid: 15 weight parts, sulfobenzide dispersion by drying solid: 30 weight parts, divided calcium carbonate prose style free from parallelism by drying solid: 20 weight parts, Zinic stearas dispersion (solids content 16wt%) by drying solid: 10 weight parts and by the 15wt% of drying solid poly-(vinyl alcohol): 7 weight parts.The pH of coating fluid is 8.2.
Then, with coating fluid with 5g/m
2Amount (by dry weight basis) to be applied over Substance be 50g/m
2The surface of no wood pulp paper and dry, height calendering subsequently is to produce thermal recording medium.The evaluation result of the developing sensitivity of the thermal recording medium that obtains is good, and optical density (OD) is 1.3.It is good using the print retention of vinylchlorid packaging film evaluation, does not occur fading.The result that obtains is summarised in the table 4.
Embodiment 84
By 2g and embodiment 83 used identical urea-urea hydride compounds and the modification of 2g sulfobenzide and 16g 2.5wt% are gathered (vinyl alcohol) (Gohsenol KL-05, trade(brand)name, by TheNippon Synthetic Chemical Industry Co., Ltd. produces) the aqueous solution in paint shaker, grind 6 hours together to disperse the former two to prepare dispersion.
Then, produce thermal recording medium in the mode identical with embodiment 83, difference is to add the above-mentioned prose style free from parallelism that is divided into to replace the dispersion and the sulfobenzide dispersion of the urea-urea hydride compounds of use among the embodiment 83 in the ratio of 60 weight parts (by drying solid), estimates recording materials then.The result that obtains is summarised in the table 4.
Embodiment 85
In the 61g 2,4 toluene diisocyanate, add 450g toluene,, make again to be reflected at and carried out under 5 ℃ 7 hours with after the drips of solution of 26g aniline in 150g toluene be added to wherein in 6 hours as solvent.After reaction finished, sedimentary white solid reclaimed by filtering, and with toluene wash and dry in a vacuum then a whole night, had obtained the white crystal shape compound of 70g.Subsequently, adding the 365g toluene as solvent to 30g obtains in the compound, subsequently with 2 of 12.2g, the triethylamine of two (4-hydroxyphenyl) propane of 2-and 0.3mg is added to wherein, under 60 ℃, stirred 4 hours again, stirred 3 hours down and react under 3 hours the condition of stirring down at 80 ℃ then at 70 ℃.After reaction finished, with the reaction soln cool to room temperature, sedimentary crystal reclaimed by filtering again, with toluene wash and drying a whole night in a vacuum then, had obtained the 42g crystalline compound that is white in color.The IR that carries out these white crystals measures, and finds that characteristic peak appears at 750cm
-1, 840cm
-1, 1020cm
-1, 1500cm
-1, 1600cm
-1, 1720cm
-1And 3320cm
-1
By the aqueous solution (Gohseran L-3266 with the modification poly-(vinyl alcohol) of this compound of 2g and 2g sulfobenzide and 16g 2.5wt%, trade(brand)name, by The Nippon SyntheticChemical Industry Co., Ltd. produces) in paint shaker, grind 6 hours together to disperse the former two to prepare dispersion.
Then, produce thermal recording medium in the mode identical with embodiment 83, difference is the prose style free from parallelism that is divided into of adding above-claimed cpd and sulfobenzide in the ratio of 60 weight parts (by drying solid), replace the dispersion and the sulfobenzide dispersion of the urea-urea hydride compounds of use among the embodiment 83, revalue recording materials.The result that obtains is summarised in the table 4.
Embodiment 86
The aqueous solution (the Gohseran L-3266 that gathers (vinyl alcohol) by the modification of the 2g compound that will be among the embodiment 69 obtains and 2g oxalic acid dimethylbenzyl ester and 16g2.5wt%, trade(brand)name, by The Nippon Synthetic Chemical Industry Co., Ltd. produces) in paint shaker, grind 6 hours together to disperse the former two to prepare dispersion.
Then, produce thermal recording medium in embodiment 83 identical modes, difference is the prose style free from parallelism that is divided into of adding above-claimed cpd and oxalic acid dimethylbenzyl ester in the ratio of 60 weight parts (by drying solid), replace the dispersion and the sulfobenzide dispersion of the urea-urea hydride compounds of use among the embodiment 83, revalue recording materials.The result that obtains is illustrated in the table 4.
Embodiment 87
The aqueous solution (the Metlose SM-15 of the methylcellulose gum by compound that 2g is obtained in embodiment 2 and 8g 2.5wt%, by Shin-Etsu Chemical Co., Ltd. produces) in paint shaker, grind 6 hours together to disperse the former to prepare dispersion.
Produce thermal recording medium in the mode identical with embodiment 83 then, difference is to use the dispersion of above-claimed cpd to replace the dispersion of urea-urea hydride compounds of using among the embodiment 83, estimates recording materials then.The result that obtains is summarised in the table 4.
Embodiment 88-92
Produce thermal recording medium in the mode identical with embodiment 83.(Dispersant 5027 only to be to use the poly carboxylic acid ammonium salt, by Sunnopco Co., Ltd. produce) (embodiment 88), water-soluble low molecular weight multipolymer (Discort N14, by Dai-ichi Kogyo Seiyaku Co., Ltd. produce) (embodiment 89), sulfo-succinic acid 2-(ethyl hexyl) ester sodium (Neocol SWC, by Dai-ichi Kogyo Seiyaku Co., Ltd. produce) (embodiment 90), Vltra tears (Metlose 60SH-03, by Shin-Etsu Chemical Co., Ltd. produces) (embodiment 91), or condensation sodium naphthalene sulfonate (Roma D, by Sunnopco Co., Ltd. produce) (embodiment 92) replace in embodiment 83, being used as the dispersion agent of urea-urea hydride compounds poly-(vinyl alcohol) (Gohsenol KL-05, trade(brand)name is by The Nippon Synthetic Chemical IndustryCo., Ltd. produce), revalue thermal recording medium.The result that obtains is summarised in the table 4.
Embodiment 93-98
Produce thermal recording medium in the mode identical with embodiment 83, only be to use methylcellulose gum (Metlose SM-15, by Shin-Etsu Chemical Co., Ltd. produce) (embodiment 93), water-soluble low molecular weight multipolymer (Discort N14, by Dai-ichi Kogyo Seiyaku Co., Ltd. produce) (embodiment 94), sulfo-succinic acid 2-(ethyl hexyl) ester sodium (Neocol SWC, by Dai-ichi Kogyo Seiyaku Co., Ltd. produce) (embodiment 95), Vltra tears (Metlose 60SH-03, by Shin-Etsu Chemical Co., Ltd. produce) (embodiment 96), condensation sodium naphthalene sulfonate (Roma D, by Sunnopco Co., Ltd. production) (Dispersant 5027 for (embodiment 97) or poly carboxylic acid ammonium salt, by Sunnopco Co., Ltd. production) (embodiment 98) replacement is used as poly-(vinyl alcohol) (GohsenolKL-05 of the dispersion agent of sulfobenzide in embodiment 83, by The Nippon Synthetic Chemical Industry Co., Ltd. produce), revalue thermal recording medium.The result that obtains is summarised in the table 4.
Embodiment 99-101
Produce thermal recording medium in the mode identical with embodiment 87, only be to use methylcellulose gum (Metlose SM-15, by Shin-Etsu Chemical Co., Ltd. produce) (embodiment 99), Vltra tears (Metlose 60SH-03, by Shin-Etsu Chemical Co, Ltd. produce) (embodiment 100), modification gathers (vinyl alcohol) (Gohseran L-3266, by The Nippon Synthetic Chemical Industry Co., Ltd. production) (embodiment 101) replacement is used as poly-(vinyl alcohol) (GohsenolKL-05 of the dispersion agent of sulfobenzide in embodiment 87, by The Nippon Synthetic Chemical Industry Co., Ltd. produce), revalue thermal recording medium.The result that obtains is summarised in the table 4.
Embodiment 102
Produce thermal recording medium in the mode identical with embodiment 99, only be to use modification to gather (vinyl alcohol) (Gohseran L-3266, by The Nippon Synthetic ChemicalIndustry Co., Ltd. production) replacement is used as methylcellulose gum (the Metlose SM-15 of the dispersion agent of urea-urea hydride compounds in embodiment 99, by Shin-Etsu Chemical Co., Ltd. produce), revalue recording materials.The result that obtains is summarised in the table 4.
Embodiment 103 and 104
Produce thermal recording medium in the mode identical with embodiment 89, difference is to use methylcellulose gum (Metlose SM-15, by Shin-Etsu Chemical Co., Ltd. produce) (embodiment 103) or Vltra tears (Metlose 60SH-03, by Shin-EtsuChemical Co., Ltd. production) (embodiment 104) replacement is used as poly-(vinyl alcohol) (Gohsenol KL-05 of the dispersion agent of sulfobenzide in embodiment 89, by The Nippon SyntheticChemical Industry Co., Ltd. produce), revalue thermal recording medium.The result that obtains is summarised in the table 4.
Embodiment 105 and 106
Produce thermal recording medium according to the mode identical with embodiment 91, difference is to use methylcellulose gum (Metlose SM-15, by Shin-Etsu Chemical Co., Ltd. produce) (embodiment 105) or Vltra tears (Metlose 60SH-03, by Shin-EtsuChemical Co., Ltd. production) (embodiment 106) replacement is used as poly-(vinyl alcohol) (Gohsenol KL-05 of the dispersion agent of sulfobenzide in embodiment 91, by The Nippon SyntheticChemical Industry Co., Ltd. produce), revalue thermal recording medium.The result that obtains is summarised in the table 4.
Embodiment 107 and 108
Produce thermal recording medium according to the mode identical with embodiment 104, different Vltra tears (the Metlose 60SH-03 that are to use, by Shin-Etsu Chemical Co., Ltd. produce) (embodiment 107) or Vltra tears (Metlose 60SH-03, by Shin-EtsuChemical Co., Ltd. produce) and sulfo-succinic acid 2-(ethyl hexyl) ester sodium (Neocol SWC, by Dai-ichi Kogyo Seiyaku Co., Ltd. produce) (weight ratio: mixed dispersant 1/1) (embodiment 108) replacement is used as poly-(vinyl alcohol) of the dispersion agent of 3-dibutylamino-6-methyl-7-anilino fluorane in embodiment 104, revalue thermal recording medium.The result that obtains is summarised in the table 4.
The comparative example 10
According to producing thermal recording medium with the same mode of embodiment 83, different is to use 2, and two (4-hydroxyphenyl) propane of 2-replace urea-urea hydride compounds of using among the embodiment 83, estimate again.The result that obtains is summarised in the table 4.
Comparative example 11 and 12
To disperse in the mode identical with the used identical urea-urea hydride compounds of embodiment 83 with embodiment 83, different is to change jitter time, measure dispersions obtained mean particle size again, recording the result is 0.04 μ m (comparative example 11) and 6.5 μ m (comparative example 12).Produce the thermal photography sheet material according to the mode identical with embodiment 83, different each above-mentioned dispersion that are to use are estimated again.The result that obtains is summarised in the table 4.
The comparative example 13
To disperse in the mode identical with the used identical urea-urea hydride compounds of embodiment 83, and just in the scatter operation process, keep dispersion temperature at 65 ℃ with embodiment 83.Except the dispersion of using such acquisition,, estimate again according to producing the thermal photography sheet material with the same mode of embodiment 83.Gained is the result be summarised in the table 4.
The comparative example 14
To disperse in the mode identical with embodiment 83 with the used identical urea-urea hydride compounds of embodiment 83, the pH that just will be used for the dispersion medium of scatter operation transfers to 4.Except the dispersion of using such acquisition, produce the thermal photography sheet material according to the mode identical with embodiment 83, estimate again.Gained is the result be summarised in the table 4.
The comparative example 15
To disperse in the mode identical with embodiment 83 with the used identical urea-urea hydride compounds of embodiment 83, the pH that just will be used for the dispersion medium of scatter operation transfers to 11.Except the dispersion of using such acquisition, produce the thermal photography sheet material according to the mode identical with embodiment 83, estimate again.Gained is the result be summarised in the table 4.
The comparative example 16
The pH of the coating fluid that will prepare in embodiment 83 with 1N sulfuric acid transfers to 4.0.Except the coating fluid that uses such adjusting, produce the thermal photography sheet material according to the mode identical with embodiment 83, estimate again.Gained is the result be summarised in the table 4.
The comparative example 17
The pH of the coating fluid that will prepare in embodiment 83 with 1N sodium hydroxide transfers to 12.5.Except the coating fluid that uses such adjusting, produce the thermal photography sheet material according to the mode identical with embodiment 83, estimate again.Gained is the result be summarised in the table 4.
Table 4
| ? | The sensitivity of temperature-sensitive paper | Plasticizer resistance properties (print retention) | Plasticizer resistance properties (retention of source recording material surface) | Total appraisal |
| Embodiment 83 | 1.3? | ◎? | ○～◎? | ○～◎? |
| Embodiment 84 | 1.4? | ◎? | ○～◎? | ○～◎? |
| Embodiment 85 | 1.3? | ○～◎? | ◎? | ○～◎? |
| Embodiment 86 | 1.3? | ○? | ◎? | ○～◎? |
| Embodiment 87 | 1.3? | ○～◎? | ◎? | ○～◎? |
| Embodiment 88 | 1.3? | ◎? | ◎? | ◎? |
| Embodiment 89 | 1.3? | ◎? | ◎? | ◎? |
| Embodiment 90 | 1.2? | ◎? | ◎? | ◎? |
| Embodiment 91 | 1.3? | ◎? | ○～◎? | ○～◎? |
| Embodiment 92 | 1.2? | ◎? | ○～◎? | ○～◎? |
| Embodiment 93 | 1.3? | ◎? | ◎? | ◎? |
| Embodiment 94 | 1.3? | ◎? | ◎? | ◎? |
| Embodiment 95 | 1.3? | ◎? | ◎? | ◎? |
| Embodiment 96 | 1.3? | ◎? | ○～◎? | ○～◎? |
| Embodiment 97 | 1.3? | ◎? | ○～◎? | ○～◎? |
| Embodiment 98 | 1.3? | ◎? | ○～◎? | ○～◎? |
| Embodiment 99 | 1.3? | ◎? | ◎? | ◎? |
| Embodiment 100 | 1.3? | ◎? | ◎? | ◎? |
| Embodiment 101 | 1.4? | ◎? | ◎? | ◎? |
| Embodiment 102 | 1.4? | ◎? | ◎? | ◎? |
| Embodiment 103 | 1.3? | ◎? | ◎? | ◎? |
| Embodiment 104 | 1.3? | ◎? | ◎? | ◎? |
| Embodiment 105 | 1.3? | ◎? | ◎? | ◎? |
| Embodiment 106 | 1.3? | ◎? | ◎? | ◎? |
| Embodiment 107 | 1.3? | ◎? | ◎? | ◎? |
| Embodiment 108 | 1.4? | ◎? | ◎? | ◎? |
| The comparative example 10 | 1.3? | ×? | ○? | ×? |
| The comparative example 11 | 1.3? | ○? | ×? | ×? |
| The comparative example 12 | 0.7? | △? | ○? | ×? |
| The comparative example 13 | 0.8? | △? | △? | ×? |
| The comparative example 14 | 1.0? | △? | ×? | ×? |
| The comparative example 15 | 0.8? | △? | △? | ×? |
| The comparative example 16 | 1.1? | △? | ×? | ×? |
| The comparative example 17 | 0.9? | ×? | △? | ×? |
1, sensitivity is increased with the increase of optical density (OD) (OD value).
2, plasticizer resistance properties (print retention)
◎～do not have substantially and fade.
Zero～tone slightly changes, and is not fuzzy etc.
△～obviously fade.
The color of *～print completely loses.
3, plasticizer resistance properties (retention of source recording material surface)
◎～source recording material surface does not almost have painted.
Zero～source recording material surface has very slight painted, though trickle tonal variation is arranged.
△～source recording material surface is obviously painted.
*～source recording material surface is seriously painted, makes to be difficult to readable print.
Embodiment 109
With among the embodiment 83 preparation coating fluid with 5g/m
2Amount (by dry weight basis) to be applied over surface p H be on 3.2 the no wood pulp paper, dry again, height calendering subsequently is to produce thermal recording medium.Developing sensitivity evaluation result to the thermal recording medium that obtained is good, and optical density (OD) is 1.3.It is good using the print retention of vinylchlorid packaging film evaluation, does not occur fading.The retention of source recording material surface is good, and the surface does not almost have painted.Gained is the result be summarised in the table 5.
Embodiment 110 and 111
Producing thermal recording medium with the same mode of embodiment 109, different be to use surface p H be 5 no wood pulp paper (embodiment 110) or surface p H be 6.8 no wood pulp paper (embodiment 111) to replace surperficial pH be 3.2 no wood pulp papers, estimate again.Gained is the result be summarised in the table 5.
Comparative example 18 and 19
Produce thermal recording medium in the mode identical with embodiment 109, only be to use surface p H be 2.8 no wood pulp paper (comparative example 18) or surface p H be 9.5 no wood pulp paper (comparative example 19) to replace surperficial pH be 3.2 no wood pulp paper, estimate again.Gained is the result be summarised in the table 5.
Table 5
| ? | The sensitivity of temperature-sensitive paper | Plasticizer resistance properties (print retention) | Plasticizer resistance properties (retention of source recording material surface) | Total appraisal |
| Embodiment 109 | 1.3? | ◎? | ○～◎? | ○～◎? |
| Embodiment 110 | 1.3? | ◎? | ◎? | ◎? |
| Embodiment 111 | 1.3? | ◎? | ◎? | ◎? |
| The comparative example 18 | 1.3? | △? | ×? | ×? |
| The comparative example 19 | 1.0? | △? | △? | ×? |
1, sensitivity is increased with the increase of optical density (OD) (OD value).
2, plasticizer resistance properties (print retention)
◎～do not have substantially and fade.
Zero～tone slightly changes, and is not fuzzy etc.
△～obviously fade.
The color of *～print completely loses.
3, plasticizer resistance properties (retention of source recording material surface)
◎～source recording material surface does not almost have painted.
Zero～source recording material surface has very slight painted, though trickle tonal variation is arranged.
△～source recording material surface is obviously painted.
*～source recording material surface is seriously painted, makes to be difficult to readable print.
Embodiment 112
A) be used for the preparation of the coating fluid of magnetic recording layer
By with 100 weight part barium ferrite (coercive forces: 2,700), 25 weight part sodium polyacrylates (the 20wt% aqueous solution), 100 weight parts gather (vinylidene chloride) (49wt% dispersion), 15 weight part carbon blacks (36wt% dispersion), the 10 weight part paraffin (by the 20wt% dispersion of using methylcellulose gum to obtain) and the water of 100 weight parts disperse to prepare in 10 hours the coating fluid that is used for magnetic recording layer in ball mill.
B) be used for the preparation of the coating fluid of heat sensitive recording layer
Obtain to be used for the coating fluid of heat sensitive recording layer according to the mode identical with embodiment 24.
Then, will be at A) in the coating fluid that is used for magnetic recording layer of preparation with 30g/m
2It is 150g/m that the amount of (by dry weight basis) is applied over Substance
2The one side of no wood pulp paper, dry again, to obtain magnetic recording layer.Then, will be at B) in the coating fluid that is used for heat sensitive recording layer of preparation with 6g/m
2Amount (by dry weight basis) be applied over another side into the base material of above-mentioned magnetic recording layer, dry again, height calendering subsequently is to obtain the heat-sensitive magnetic recording material.
The evaluation result of the developing sensitivity of the heat sensitive recording layer of the heat-sensitive magnetic recording material that is obtained is good, and optical density (OD) reaches 1.3.It is good using the print retention of vinylchlorid packaging film evaluation, does not occur fading.Gained is the result be summarised in the table 6.
Embodiment 113
C) be used for the preparation of the coating fluid of protective layer
With the Zinic stearas of 20 weight parts, the 5wt% methylated cellulose aqueous solution of 20 weight parts and 60 weight parts waters mix, and disperse 2 hours in sand mill then.Then, with carboxy-modified poly-(vinyl alcohol) aqueous solution of the 10wt% of 20 weight parts, 1.5 weight part silicas, the 12.5wt% polyamide-based Epicholorohydrin aqueous solution of 6.5 weight parts and 15.0 weight parts waters mix, and disperse 2 hours in sand mill then.
Subsequently, with the Zinic stearas dispersion of the above acquisition of 0.7 weight part, the water of the silica dispersion of the above acquisition of 45.0 weight parts and 11.3 weight parts mixes, and is used for the coating fluid of protective layer with preparation.Produce the heat-sensitive magnetic recording material according to the mode identical with embodiment 112, just by on the heat sensitive recording layer of the heat-sensitive magnetic recording material of embodiment 112 with 3g/m
2Amount (by dry weight basis) apply the above-mentioned coating fluid that is used for protective layer, subsequent drying forms protective layer, revalues the heat-sensitive magnetic recording material.Gained is the result be summarised in the table 6.
Embodiment 114
D) be used for the preparation of the coating fluid in middle layer
The coating fluid that is used for the middle layer that preparation is made up of 40% latex of copolymer in cinnamic acrylic ester of the dispersion of the polystyrene minuteness particle of 80 weight parts (by drying solid) 48% and 20 weight parts (by drying solid).
Produce the heat-sensitive magnetic recording material in the mode identical with embodiment 113, different is between the heat sensitive recording layer of the heat-sensitive magnetic recording material of embodiment 113 and base material with 8g/m
2The amount of (by dry weight basis) applies above-mentioned coating fluid, and subsequent drying forms the middle layer, revalues the heat-sensitive magnetic recording material.Gained is the result be summarised in the table 6.
The comparative example 20
Produce the thermal photography sheet material according to the mode identical with embodiment 112, only be to use 2, two (4-hydroxyphenyl) propane of 2-replace urea-urea hydride compounds of using among the embodiment 112, estimate again.Gained is the result be summarised in the table 6.
Table 6
| ? | The sensitivity of temperature-sensitive paper | Plasticizer resistance properties (print retention) | Total appraisal |
| Embodiment 112 | 1.3? | ◎? | ◎? |
| Embodiment 113 | 1.2? | ◎? | ◎? |
| Embodiment 114 | 1.3? | ◎? | ◎? |
| The comparative example 20 | 1.3? | ×? | ×? |
1, sensitivity is increased with the increase of optical density (OD) (OD value).
2, plasticizer resistance properties (print retention)
◎～do not have substantially and fade.
Zero～tone slightly changes, and is not fuzzy etc.
△～obviously fade.
The color of *～print completely loses.
Embodiment 115
A) be used for the preparation of the coating fluid of heat sensitive recording layer
Obtain to be used for the coating fluid of heat sensitive recording layer in the mode identical with embodiment 24.
Will be at A) in the coating fluid that is used for heat sensitive recording layer of preparation with 7g/m
2Amount (by dry weight basis) to be applied over Substance be 150g/m
2The surface of no wood pulp paper on, dry again, carry out the height calendering subsequently, to produce the sheet material that scribbles heat sensitive recording layer.
B) production of release sheet
Use the intaglio plate coating machine, the releasing agent that will be made up of the oily dimethyl siloxane is with 1g/m
2Amount to be applied over Substance be 40g/m
2Body paper on, to form adherent layer.Then, will be by 100 weight part chlorinated rubbers, the binder layer that 20 weight part ester gums and 120 weight part dibutyl phthalates are formed is with 10g/m
2Amount be applied on the adherent layer.
C) be used for the production of the label of thermal photography
Will be at above A) in the sheet material that scribbles heat sensitive recording layer produced non-coated surface and at above B) in the surface that scribbles binder layer of release sheet of production stick together, make them face with each other, thereby produce the label that is used for thermal photography.
The developing sensitivity evaluation result of the label that is used for thermal photography that is obtained is good, and optical density (OD) has reached 1.3.It is good using the print retention of vinylchlorid packaging film evaluation, does not occur fading.Gained is the result be summarised in the table 7.
Embodiment 116
D) be used for the preparation of the coating fluid of back coating
Mix with 50 weight part kaolin by styrene-maleic acid copolymer and to prepare the coating fluid that is used for back coating 100 weight parts.According to producing the label that is used for thermal photography, just with 1g/m with the same mode of embodiment 115
2Amount (by dry weight basis) above-mentioned coating fluid is applied over the reverse side that scribbles heat sensitive recording layer of the label that is used for thermal photography of embodiment 115, subsequent drying forms back coating, revalues label.Gained is the result be summarised in the table 7.
Embodiment 117
E) be used for the preparation of the coating fluid in middle layer
The coating fluid that is used for the middle layer that preparation is made up of 40% latex of copolymer in cinnamic acrylic ester of the dispersion of the polystyrene minuteness particle of 80 weight parts (by drying solid) 48% and 20 weight parts (by drying solid).
Produce the label that is used for thermal photography in the mode identical with embodiment 116, just by between the heat sensitive recording layer of the label that is used for thermal photography of embodiment 116 and base material with 8g/m
2Amount (by dry weight basis) apply above-mentioned coating fluid, subsequent drying forms the middle layer, revalues label.Gained is the result be summarised in the table 7.
Embodiment 118
F) be used for the preparation of the coating fluid of protective layer
With 20 weight part Zinic stearass, the methylated cellulose aqueous solution of 20 weight part 5wt% and 60 weight parts waters mix, and disperse then to reach 2 hours in sand mill.Then with carboxy-modified poly-(vinyl alcohol) aqueous solution of the 10wt% of 20 weight parts, 1.5 weight part silicas, the 12.5wt% polyamide-based Epicholorohydrin aqueous solution of 6.5 weight parts and 15.0 weight parts waters mix, and disperse 2 hours in sand mill then.
Subsequently, with the Zinic stearas dispersion that obtains more than 0.7 weight part, the water of the silica dispersion of the above acquisition of 45.0 weight parts and 11.3 weight parts mixes, and is used for the coating fluid of protective layer with preparation.Produce the label that is used for thermal photography in the mode identical with embodiment 117, just by on the heat sensitive recording layer of the label that is used for thermal photography of embodiment 117 with 3g/m
2Amount (by dry weight basis) apply above-mentioned coating fluid, subsequent drying forms protective layer, estimates label again.Gained is the result be summarised in the table 7.
The comparative example 21
Produce the thermal photography sheet material in the mode identical with embodiment 115, only be to use 2, two (4-hydroxyphenyl) propane of 2-replace urea-urea hydride compounds of using among the embodiment 115, estimate again.Gained is the result be summarised in the table 7.
Table 7
| ? | The sensitivity of temperature-sensitive paper | Plasticizer resistance properties (print retention) | Total appraisal |
| Embodiment 115 | 1.3? | ○～◎? | ○～◎? |
| Embodiment 116 | 1.3? | ○～◎? | ○～◎? |
| Embodiment 117 | 1.4? | ○～◎? | ◎? |
| Embodiment 118 | 1.3? | ◎? | ◎? |
| The comparative example 21 | 1.3? | ×? | ×? |
1, sensitivity is increased with the increase of optical density (OD) (OD value).
2, plasticizer resistance properties (print retention)
◎～do not have substantially and fade.
Zero～tone slightly changes, but not fuzzy etc.
△～obviously fade.
The color of *～print completely loses.
Embodiment 119
The following temperature-sensitive that is used for is added lustre to that to be applied over thickness be being purchased of 75 μ m poly-(ethylene glycol terephthalate) film (Lumilar E for the coating of layer and the coating that is used for the middle layer, trade(brand)name, TorayIndustries, Inc.) on the face, make and on base material, form following multilayer in the following order: cyan colour developing heat sensitive recording layer, middle layer, magenta colour developing heat sensitive recording layer, the middle layer, yellow colour developing heat sensitive recording layer and middle layer.Apply by the scraper coating method, make that each heat sensitive recording layer and each middle layer are respectively 6.5g/m in dried glue spread
2And 2.0g/m
2Thereby, obtain the polychrome thermal recording medium.
The preparation of the coating of cyan colour developing heat sensitive recording layer
Liquid A (but dye dispersion of temperature-sensitive colour developing)
With 20 weight parts 3, two (to dimethylamino phenyl)-6-dimethylamino benzo [c] furanones of 3-, 10% poly-(vinyl alcohol) aqueous solution and 10 weight parts waters of 20 weight parts mix, then at sand mill (by AIMEX CO., LTD. produce) in disperse and grind, have the dispersion of the mean particle size of 0.7 μ m with preparation.
Liquid B (developer dispersion)
With the synthetic urea of the mode identical-urea hydride compounds with embodiment 24, and by this compound of 30g is ground 3 hours to disperse the former to prepare dispersion with (vinyl alcohol) aqueous solution that gathers of 120g 2.5wt% in sand mill.The temperature of the dispersion that obtains immediately after the scatter operation is 25 ℃.The diameter of the discrete particles of compound is 0.6 μ m.
By liquid A with 30 weight parts, the liquid B of 120 weight parts, 60% calcium carbonate slurry of 52 weight parts, 10% poly-(vinyl alcohol) aqueous solution of 40 weight parts, SBR latex (L-1537, the trade(brand)name of 28 weight parts, ASAHI Chemical Industry, Co., Ltd.; Solids content 50%), (by ChukyoYushi Co., Ltd. produces the stearylamide of 11 weight parts for Celozol A-877, trade(brand)name; Solids content 26.5%) and 82 weight parts waters mix and prepare the add lustre to coating of layer of the temperature-sensitive that is used for cyan colour developing.
Be used for the preparation of the coating of pinkish red colour developing heat sensitive recording layer
Liquid A (but temperature-sensitive ingrain dye(stuff) dispersion)
(2-(2 with the phosphofluoric acid 4-N-of 20 weight parts; 4-two tert-pentyl phenoxy groups) piperazinyl phenyl diazonium salt butyryl radicals); 10% poly-(vinyl alcohol) aqueous solution and 10 weight parts waters of 20 weight parts mix; in sand mill, disperse then and grind, have the dispersion of the mean particle size of 0.7 μ m with preparation.
Liquid B (coupler dispersion)
With the 1-of 50 weight parts (2 '-octyl phenyl)-3-methyl-5-pyrazolone, 1 of 50 weight parts, 2,3-triphenyl guanidine, 10% poly-(vinyl alcohol) aqueous solution and 25 weight parts waters of 50 weight parts mix, in sand mill, disperse then and grind, have the dispersion of the mean particle size of 1.0 μ m with preparation.
By liquid A with 30 weight parts, the liquid B of 90 weight parts, 60% calcium carbonate slurry of 52 weight parts, 10% poly-(vinyl alcohol) aqueous solution of 40 weight parts, SBR latex (L-1537, the trade(brand)name of 28 weight parts, ASAHI Chemical Industry, Co., Ltd.; Solids content 50%), (by ChukyoYushi Co., Ltd. produces the stearylamide of 11 weight parts for Celozol A-877, trade(brand)name; Solids content 26.5%) and 82 weight parts waters mix and prepare the add lustre to coating of layer of the temperature-sensitive that is used for magenta colour developing.
Be used for the preparation of the coating of the yellow heat sensitive recording layer that develops the color
Liquid A (but dye dispersion of temperature-sensitive colour developing)
Phosphofluoric acid 2 with 20 weight parts, 5-dibutoxy-4-tolyl thio phenyl phenyl diazonium salt, 10% poly-(vinyl alcohol) aqueous solution of 20 weight parts and the water of 10 weight parts mix, and disperse in sand mill then and grind, and have the dispersion of the mean particle size of 0.7 μ m with preparation.
Liquid B (coupler dispersion)
(3-(2 with the 2-chloro-5-of 50 weight parts, 4-two tert-pentyls) Acetanilide phenoxy propyl amino), 1 of 50 weight parts, 2,3-triphenyl guanidine, 10% poly-(vinyl alcohol) aqueous solution and 25 weight parts waters of 50 weight parts mix, and disperse in sand mill then and grinding, have the dispersion of the mean particle size of 1.0 μ m with preparation.
By liquid A with 30 weight parts, the liquid B of 90 weight parts, 60% calcium carbonate slurry of 52 weight parts, 10% poly-(vinyl alcohol) aqueous solution of 40 weight parts, SBR latex (L-1537, the trade(brand)name of 28 weight parts, ASAHI Chemical Industry, Co., Ltd.; Solids content 50%), (by ChukyoYushi Co., Ltd. produces the stearylamide of 11 weight parts for Celozol A-877, trade(brand)name; Solids content 26.5%) and 82 weight parts waters mix and prepare the add lustre to coating of layer of the temperature-sensitive that is used for yellow colour developing.
Coating (the solids content: preparation 15%) that is used for the middle layer
By with 60% kaolin of 42 weight parts (mean particle size: dispersion 0.6 μ m), carboxyl acid modified poly-(vinyl alcohol) aqueous solution of 200 weight parts (Gohsenol T-330, by The NipponSynthetic Chemical Industry Co., Ltd. produces; Solids content 10%), (by Nippon Shokubai Co., Ltd. produces 100 parts by weight of acrylic acid emulsions for SC-2250, trade(brand)name; Solids content 40%), 33 weight part dihydroxymethyl urea solutions (produced by ShowaDenko K.K. by J-001, trade(brand)name; Solids content 30%), (by Chukyo Yushi Co., Ltd. produces 40% Zinic stearas dispersion of 13 weight parts for Highmicron F-930, trade(brand)name; Mean particle size 0.9 μ m), the water-ground limestone of 70 weight parts (NS-1000, trade(brand)name, by Nitto FunkaKogyo Co., Ltd. produces), (EM 90 for 25 weight part urea alkane acrylic ester emulsions, trade(brand)name is produced by Arakawa Chemical Industries Ltd.; Solids content 40%), and the polysiloxane of 5 weight parts (SM 7025, trade(brand)name, and by Dow Coming Toray Silicone Co., Ltd. produces; Solids content 33%) and the water of 40 weight parts mix and prepare the coating that is used for the middle layer.
Embodiment 120
The production example of two look thermal recording mediums is below described.
(A) be used for high temperature add lustre to the layer leuco dye: 3-(4 '-dibutylamino-2 '-hydroxyphenyl)-3-(5 '-anilino-4 '-methyl-2 '-p-methoxy-phenyl) benzo [c] furanone.
(B) be used for low temperature add lustre to the layer leuco dye: 3-diethylin-7-chlorine fluorane.
(C) synthetic urea-urea hydride compounds among developer: the embodiment 19.
(D) sensitizing agent: sulfobenzide.
With each above-mentioned organic compound (A)-(D) of 40g and 10% poly-(vinyl alcohol) solution (polymerization degree 500 of 40g, and saponification deg 90%) and 20g water mix, again each of the composition that will obtain like this at vertical grinding machine (by AIMEX CO., LTD. disperse the sand mill of Sheng Chaning), make that granularity is 1 μ m, thereby prepared as the dispersion that corresponds respectively to the liquid (A)-(D) of compound (A)-(D).
On the other hand, (Brilliant 15, and by Shiraishi IndustrialCo., Ltd. produces with the light calcium carbonate of 40g; Mean particle size 0.15 μ m) and 0.7% sodium hexametaphosphate solution of 60g mix, resulting composition disperses in the Cowles dispersion machine again.
Individually, 21% Zinic stearas dispersion is as lubricant dispersion, and promptly liquid (F) prepares, and 10% poly-(vinyl alcohol) (NM11, by The Nippon Synthetic ChemicalIndustry Co., Ltd. produces) prepare as binder liq (G).
Be used for the preparation of the coating fluid (I) of high temperature colour developing heat-sensitive layer
By blend aforesaid liquid (A), (C), (D) and (G) and make them be: (A): (C): (E) in dried weight ratio: (G)=20: 40: 25: 15, prepare the coating fluid that is used for high temperature colour developing heat-sensitive layer.
The formation of high temperature colour developing heat-sensitive layer
Is 60g/m with the Mayer rod at Substance
2No wood pulp paper (neutralized paper) go up with 8g/m
2Amount (by dry weight basis) apply the above-mentioned coating fluid (I) that is used for high temperature colour developing heat-sensitive layer and form high temperature colour developing heat-sensitive layer.
Be used for the preparation of the coating fluid (II) of cryogenic displaying color heat-sensitive layer
By blend aforesaid liquid (B), (C), (D), (E), (F) and (G) and make them be: (B): (C): (D): (E): (F): (G)=10: 20: 20: prepare the coating fluid that is used for the cryogenic displaying color heat-sensitive layer at 20: 10: 10 in dried weight ratio.
The production of two look thermal recording mediums
The coating fluid (II) that will be used for the cryogenic displaying color heat-sensitive layer is with 5g/m
2Amount (by dry weight basis) be applied over above-mentioned high temperature colour developing heat-sensitive layer.Then, be adjusted to 150 seconds by carry out the Bekk smoothness (JIS-P8119) that smooth handles the thermal photography surface with supercalender, thereby obtained two look thermal recording mediums.
The comparative example 22
Produce the polychrome thermal recording medium in the mode identical with embodiment 119, only be to use 2, two (4-hydroxyphenyl) propane of 2-replace synthetic urea-urea hydride compounds in embodiment 119, estimate again.Gained is the result be summarised in the table 8.
The comparative example 23
Produce two look thermal recording mediums in the mode identical with embodiment 120, only be to use 2, two (4-hydroxyphenyl) propane of 2-replace synthetic urea-urea hydride compounds in embodiment 120, estimate again.Gained is the result be summarised in the table 8.
The evaluation of polychrome thermal recording medium
Use is purchased thermal printer (NC-1, trade(brand)name, by Fuji Photo Film Co., Ltd. produces) to embodiment 119 and 120 and comparative example 22 and 23 in the polychrome thermal recording medium that obtains print, estimate the quality of image and the retention of image in order to method down.
The quality of＜image 〉
For 5 each recording materials, the sharpness of image is judged in range estimation, contrast gradient, the even property of density unevenness and other or the like, again by following 5 grade evaluations they; Zero: good, zero～△: good slightly, △: medium, △～*: some is poor, *: poor.
＜visual retention 〉
Remain on each recording materials between the vinylchlorid packaging film or in the vinylchlorid folder, apply 300g/m again from above
2Load.After placing 24 hours under 40 ℃, the colorant density of visually rank printing and non-printing (source recording material surface).When print density only slightly reduced, visual retention was rated as well.
The gained result is as shown in table 8.That is, embodiment 119 and 120 recording materials are good on image quality, and have showed excellent visual retention, and the recording materials of comparative example 22 and 23 are inferior to the recording materials of embodiment 119 and 120.
Table 8
| ? | Image quality | The image retention | Total appraisal |
| Embodiment 119 | ○? | ◎ | ◎? |
| Embodiment 120 | ○? | ◎ | ◎? |
| The comparative example 22 | △? | △～X? | ×? |
| The comparative example 23 | ×? | × | ×? |
1, image quality
Zero～good.
△～medium.
*～poor.
2, print retention
◎～colour-fast substantially.
Zero～slight tonal variation, but not fuzzy etc.
△～obviously fade.
*～print color completely loses.
Embodiment 121
With the synthetic urea of the mode identical-urea hydride compounds, and, this compound of 2g in paint shaker, grinds 6 hours to disperse the former to prepare dispersion by being gathered (vinyl alcohol) aqueous solution with the 2.5wt% of 8g with embodiment 24.The temperature of the dispersion that directly obtains after the scatter operation is 25 ℃.The diameter of the discrete particles of compound is 0.6 μ m.
(by AIMEX Co., LTD. produces at sand mill with poly-(vinyl alcohol) aqueous solution of the 5.4wt% of 130g by the 3-dibutylamino-6-methyl-7-anilino fluorane with 70g; Vessel volume is 400mL) in 2, the revolution of 000rpm grinds down 3 hours to disperse the former to prepare another dispersion.
(by AIMEX Co., LTD. produces at sand mill with poly-(vinyl alcohol) aqueous solution of the 5.4wt% of 130g by the sulfobenzide with 70g; Vessel volume is 400mL) in 2, the revolution of 000rpm grinds down 3 hours to disperse the former to prepare another dispersion.
By being mixed with 30g water and stir this mixture with stirrer, 10g lime carbonate prepares another dispersion.
On the other hand, by using mixture 2 hours that sand mill handles 60 weight part aluminium hydroxides and poly-(vinyl alcohol) aqueous solution of 40 weight part 12.5wt%, make that its mean particle size is that about 1 μ m prepares the aluminium hydroxide dispersion to disperse aluminium hydroxide.
Obtain coating fluid by stirring in following ratio (dry basis ratio) and mixing above-mentioned dispersion with other component; Dispersion by the above-claimed cpd of drying solid: 20 weight parts, 3-dibutylamino-6-methyl-7-anilino fluorane dispersion by drying solid: 10 weight parts, sulfobenzide dispersion by drying solid: 25 weight parts, divided calcium carbonate prose style free from parallelism by drying solid: 40 weight parts, aluminium hydroxide dispersion by drying solid: 13 weight parts, Zinic stearas dispersion (solids content 16wt%) by drying solid: 20 weight parts and by the 15wt% of drying solid poly-(vinyl alcohol): 15 weight parts.
Subsequently, use intaglio plate coating machine (200 orders; The intaglio plate degree of depth 20 μ) this coating fluid that will be used for heat sensitive recording layer with the speed of 50m/min is applied over aluminium-foil paper.The aluminium-foil paper of Chu Liing is the heat sensitive recording layer of 2 μ 80 ℃ of 3 seconds of drying to obtain thickness like this.Then, the use roll coater will be by acrylic resin (mainly by methyl methacrylate units, 2-EHA unit and styrene units form also have about 40 ℃ second-order transition temperature) the transparent coating fluid formed of aqueous dispersion on the coating surface of aluminium-foil paper, be applied to the thickness of 8 μ, again 80 ℃ of 10 seconds of drying, to obtain according to the metallized paper that is used for laser labelling of the present invention.
The laser beam irradiation of metallized paper from carbon dioxide laser.It is good can obtaining clearly mark and color developing.Carry out the plasticizer resistance properties test between the packaging film by metallized paper is remained on, found that plasticizer resistance properties is good, does not cause fading of printing.Gained is the result be summarised in the table 9.
Embodiment 122
With mode synthetic urea-urea hydride compounds same, in paint shaker, grind 6 hours to disperse the former to prepare dispersion by (vinyl alcohol) aqueous solution that gathers with this compound of 2g and 8g 2.5wt% with embodiment 85.
Then, produce the metallized paper that is used for laser labelling in the mode identical with embodiment 121, the different dispersions that is to use above-claimed cpd replaces the dispersion of the compound of acquisition among the embodiment 121, and uses sulfobenzide to replace aluminium hydroxide, estimates again.Gained is the result be summarised in the table 9.
The comparative example 24
Produce the orange cold foil that is used for laser labelling in the mode identical with embodiment 121, different is to use 2, and two (4-hydroxyphenyl) propane of 2-replace synthetic urea-urea hydride compounds among the embodiment 121, estimate again.The result that obtains is summarised in the table 9.
＜developing sensitivity 〉
Use laser beam from carbon dioxide laser (Unimark, by USHIO INC. produce) with 0.6J/cm
2The masterplate irradiation of dosage through figure occurring be used for the goods of laser labelling.When obtaining clear marking and colour developing density when high, developing sensitivity is rated as well.
＜plasticizer resistance properties 〉
Three vinylchlorid packaging films are placed each upper and lower surface of the mark goods that are used for laser labelling, make the gained assembly at 300kg/cm
2Load under placed 24 hours at 40 ℃.After placement, the color density of visually rank printing.When printing density only slightly reduced, the print retention was rated as well.
Table 9
| ? | Marking sensitivity | Plasticizer resistance properties (print retention) | Total appraisal |
| Embodiment 121 | ◎ | ◎? | ◎? |
| Embodiment 122 | ○～◎? | ◎? | ◎? |
| The comparative example 24 | ○ | ×? | ×? |
1, marking sensitivity
◎～good color developing.Can obtain clear marking.
Some is insufficient in zero～colour developing, but does not have relevant visibility problem.
*～low color developing and unclear print.
2, plasticizer resistance properties (print retention)
◎～do not have substantially and fade.
Zero～tone slightly changes, but not fuzzy etc.
The color of *～print completely loses.
Embodiment 123
(1) the upward production of paper
Will be by at the NISSEKI of 80 weight parts HISOL N-296 (a kind of oil, trade(brand)name is produced by Nippon Sekiyu Kagaku K.K.) in dissolving 2.5 weight parts 3-diethylin-7-chlorine fluorane preparation solution 100 weight parts pass through styrene-maleic anhydride copolymer is dissolved emulsification in 5% aqueous solution of pH4.0 of preparation with small amounts of sodium hydroxide.On the other hand, when with sodium hydroxide with 10 weight part melamines, the mixture of 25 weight parts, 37% formalin and 65 weight parts waters is adjusted to pH9.0 and at 60 ℃ down during heating, mixture became transparent and obtained melamine-formaldehyde precondensate after 15 minutes.This precondensate is added in the emulsion of above acquisition, again keep mixture in 60 ℃ with gained mixture continuously stirring 4 hours, be cooled to room temperature then.The solids content of gained dispersion of microcapsules is 45%.
The dispersion of microcapsules that so obtains is applied on the paper, dry again, to obtain paper.
(2) preparation of paper down
Gather (vinyl alcohol) aqueous solution by 2wt% and in paint shaker, grind 45 minutes at ambient temperature to disperse the former to prepare dispersion with embodiment 7 same way as synthetic compositions and 45g with 15g.
Mix and use stirrer to stir the mixture with the water of 90g by lime carbonate and prepare another dispersion 60g.
By mixing and stir the dispersion of 40 weight part above-mentioned compositions, poly-(vinyl alcohol) aqueous solution of the 10wt% of 125 weight part divided calcium carbonate prose style free from parallelisms and 120 weight parts prepares coating fluid.
Be that coating fluid is applied over Substance is 40g/m for 10 scraper spreader with excellent number
2Body paper on to obtain down paper.
The result of colorant density evaluation is good, and optical density (OD) is 0.7.
The result who uses hand cream to estimate solvent resistance is good, and printing can be read.Gained is the result be summarised in the table 10.
The comparative example 25
Produce the pressure sensitive recording material in the mode identical with embodiment 123, difference is to use activated clay to replace urea-urea hydride compounds of using among the embodiment 123 as developer, estimates again.Gained is the result be summarised in the table 10.
Table 10
| ? | The colorant density of impact paper | Solvent resistance (hand cream) |
| Embodiment 123 | 1.3 | ◎ |
| The comparative example 25 | 0.9 | × |
1, sensitivity is increased with the increase of optical density (OD) (OD value).
2, solvent resistance (hand cream)
◎～do not have substantially and fade.
Zero～tone slightly changes, but not fuzzy etc.
△～obviously fade.
The color of *～print completely loses.
Industrial applicability
The application of special urea-urea hydride compounds is so that might be to provide at a low price the recording materials of color former and visual retention and developing sensitivity excellence.
Claims (4)
1. urea-urea hydride compounds is characterized in that with following formula (d) expression:
Wherein R is selected from methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, cyclopentyl, tert-pentyl, the 2-amyl group, hexyl, the 3-hexyl, cyclohexyl, cyclohexyl methyl, 4-methyl-2-amyl group, heptyl, different heptyl, octyl group, 2-ethyl-1-hexyl, nonyl, different nonyl, decyl, octadecyl, benzyl, methoxy ethyl, ethoxyethyl group, the propoxy-ethyl, the isopropoxy ethyl, butoxyethyl group, the isobutoxy ethyl, the hexyloxy ethyl, the phenoxy group ethyl, methoxyethoxyethyl, the ethoxy ethoxy ethyl, the propoxy-ethoxyethyl group, the isopropoxy ethoxyethyl group, the butoxy ethoxyethyl group, the isobutoxy ethoxyethyl group, the hexyloxy ethoxyethyl group, the phenoxy group ethoxyethyl group, the methoxyl group sec.-propyl, the oxyethyl group sec.-propyl, the propoxy-sec.-propyl, the isopropoxy sec.-propyl, the butoxy sec.-propyl, the isobutoxy sec.-propyl, the phenoxy group sec.-propyl, methoxyl group isopropoxy sec.-propyl, oxyethyl group isopropoxy sec.-propyl, propoxy-isopropoxy sec.-propyl, isopropoxy isopropoxy sec.-propyl, the aliphatic cpd residue of butoxy isopropoxy sec.-propyl or isobutoxy isopropoxy sec.-propyl, the hydrogen atom of each phenyl ring can be by the aromatic substance residue, aliphatic cpd residue or heterogeneous ring compound residue replace
Wherein the aliphatic cpd residue is meant the residue by the carbon atom keyed jointing of the part of the aliphatic hydrocrbon in the residue,
The aromatic substance residue be meant by the residue of the carbon atom keyed jointing of the aromatic ring in the residue and
The heterogeneous ring compound residue is meant by forming the residue of heterocyclic carbon atom keyed jointing in the residue.
2. urea-urea hydride compounds, it is characterized in that with following formula (e) or (f) expression, described urea-urea hydride compounds have at least one urea alkyl and at least one urea groups and urea alkyl and urea groups total no more than 10 and be no less than 4, this compound has 5, molecular weight below 000 or 5,000:
Wherein R is selected from methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, cyclopentyl, tert-pentyl, the 2-amyl group, hexyl, the 3-hexyl, cyclohexyl, cyclohexyl methyl, 4-methyl-2-amyl group, heptyl, different heptyl, octyl group, 2-ethyl-1-hexyl, nonyl, different nonyl, decyl, octadecyl, benzyl, methoxy ethyl, ethoxyethyl group, the propoxy-ethyl, the isopropoxy ethyl, butoxyethyl group, the isobutoxy ethyl, the hexyloxy ethyl, the phenoxy group ethyl, methoxyethoxyethyl, the ethoxy ethoxy ethyl, the propoxy-ethoxyethyl group, the isopropoxy ethoxyethyl group, the butoxy ethoxyethyl group, the isobutoxy ethoxyethyl group, the hexyloxy ethoxyethyl group, the phenoxy group ethoxyethyl group, the methoxyl group sec.-propyl, the oxyethyl group sec.-propyl, the propoxy-sec.-propyl, the isopropoxy sec.-propyl, the butoxy sec.-propyl, the isobutoxy sec.-propyl, the phenoxy group sec.-propyl, methoxyl group isopropoxy sec.-propyl, oxyethyl group isopropoxy sec.-propyl, propoxy-isopropoxy sec.-propyl, isopropoxy isopropoxy sec.-propyl, the aliphatic cpd residue of butoxy isopropoxy sec.-propyl or isobutoxy isopropoxy sec.-propyl, Y is the aromatic substance residue, heterogeneous ring compound residue or aliphatic cpd residue, α
1Be to be different from Y and to have divalent above aromatics, heterocycle or aliphatic cpd residue, n is the integer more than 2; Or
Z wherein
1With Y be aromatic substance residue or heterogeneous ring compound residue independently, β
1Be to have the above aliphatic cpd residue of divalent, n is the integer more than 2,
Wherein the aliphatic cpd residue is meant the residue by the carbon atom keyed jointing of the part of the aliphatic hydrocrbon in the residue,
The aromatic substance residue be meant by the residue of the carbon atom keyed jointing of the aromatic ring in the residue and
The heterogeneous ring compound residue is meant by forming the residue of heterocyclic carbon atom keyed jointing in the residue.
3. urea-urea hydride compounds is characterized in that with following formula (g) or (h) expression:
Wherein the hydrogen atom of each phenyl ring can be replaced β by aromatic substance residue, aliphatic cpd residue or heterogeneous ring compound residue
1Be to have the above aliphatic cpd residue of divalent, n is the integer more than 2; Or
Wherein R is selected from methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, cyclopentyl, tert-pentyl, the 2-amyl group, hexyl, the 3-hexyl, cyclohexyl, cyclohexyl methyl, 4-methyl-2-amyl group, heptyl, different heptyl, octyl group, 2-ethyl-1-hexyl, nonyl, different nonyl, decyl, octadecyl, benzyl, methoxy ethyl, ethoxyethyl group, the propoxy-ethyl, the isopropoxy ethyl, butoxyethyl group, the isobutoxy ethyl, the hexyloxy ethyl, the phenoxy group ethyl, methoxyethoxyethyl, the ethoxy ethoxy ethyl, the propoxy-ethoxyethyl group, the isopropoxy ethoxyethyl group, the butoxy ethoxyethyl group, the isobutoxy ethoxyethyl group, the hexyloxy ethoxyethyl group, the phenoxy group ethoxyethyl group, the methoxyl group sec.-propyl, the oxyethyl group sec.-propyl, the propoxy-sec.-propyl, the isopropoxy sec.-propyl, the butoxy sec.-propyl, the isobutoxy sec.-propyl, the phenoxy group sec.-propyl, methoxyl group isopropoxy sec.-propyl, oxyethyl group isopropoxy sec.-propyl, propoxy-isopropoxy sec.-propyl, isopropoxy isopropoxy sec.-propyl, the aliphatic cpd residue of butoxy isopropoxy sec.-propyl or isobutoxy isopropoxy sec.-propyl, the hydrogen atom of each phenyl ring can be by the aromatic substance residue, aliphatic cpd residue or heterogeneous ring compound residue replace, γ
1Be to be selected from-SO
2-,-O-,-(S)
n-,-(CH
2)
n-,-CO-,-CONH-,-NH-,-CH (COOR
1)-,-C (CF
3)
2-,-CR
2R
3-and with the group in any group of formula (a) expression or do not exist:
R
1, R
2And R
3Each is alkyl naturally, and n is 1 or 2,
Wherein the aliphatic cpd residue is meant the residue by the carbon atom keyed jointing of the part of the aliphatic hydrocrbon in the residue,
The aromatic substance residue be meant by the residue of the carbon atom keyed jointing of the aromatic ring in the residue and
The heterogeneous ring compound residue is meant by forming the residue of heterocyclic carbon atom keyed jointing in the residue.
4. urea-urea hydride compounds, wherein said urea-urea hydride compounds by following general formula (S-1), (S-13) and the arbitrary general formula (S-33) represent:
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| JP2000057693 | 2000-03-02 | ||
| JP2000057538 | 2000-03-02 | ||
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| JP57538/2000 | 2000-03-02 | ||
| JP58861/2000 | 2000-03-03 | ||
| JP2000058249 | 2000-03-03 | ||
| JP2000058861A JP2001246859A (en) | 2000-03-03 | 2000-03-03 | Heat-sensitive recording label |
| JP58594/2000 | 2000-03-03 | ||
| JP58468/2000 | 2000-03-03 | ||
| JP58770/2000 | 2000-03-03 | ||
| JP59216/2000 | 2000-03-03 | ||
| JP58249/2000 | 2000-03-03 | ||
| JP59298/2000 | 2000-03-03 | ||
| JP58823/2000 | 2000-03-03 | ||
| JP2000058594A JP2001246856A (en) | 2000-03-03 | 2000-03-03 | Heat-sensitive recording sheet |
| JP58279/2000 | 2000-03-03 | ||
| JP58891/2000 | 2000-03-03 | ||
| JP59047/2000 | 2000-03-03 | ||
| JP2000058770A JP2001246857A (en) | 2000-03-03 | 2000-03-03 | Multicolor heat-sensitive recording material |
| JP2000058468A JP2001246855A (en) | 2000-03-03 | 2000-03-03 | Recording sheet |
| JP2000058891A JP2001246860A (en) | 2000-03-03 | 2000-03-03 | Coloring marking agent, marking method and marking article |
| JP2000058279A JP2001246854A (en) | 2000-03-03 | 2000-03-03 | Recording material |
| JP2000058823A JP2001246858A (en) | 2000-03-03 | 2000-03-03 | Heat-sensitive magnetic recording material |
| JP267467/2000 | 2000-09-04 | ||
| JP267302/2000 | 2000-09-04 |
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| TWI499625B (en) * | 2013-12-27 | 2015-09-11 | Fdc Lees Chemical Industry Co Ltd | The organic materials used to improve the weather resistance stabilizers and through which the modified polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0160402A2 (en) * | 1984-03-30 | 1985-11-06 | Minnesota Mining And Manufacturing Company | Fluorochemicals and fibrous substrates treated therewith |
| WO1990006975A1 (en) * | 1988-12-21 | 1990-06-28 | Battelle Memorial Institute | Non-tin-based, low toxicity anti-fouling agents |
| WO1992020747A1 (en) * | 1991-05-17 | 1992-11-26 | Battelle Memorial Institute | Marine compositions bearing preferentially concentrated domains of non-tin, organo anti-fouling agents |
| WO1999051692A1 (en) * | 1998-04-03 | 1999-10-14 | Grace Gmbh | Matting agents based on coated silicon dioxide |
| WO2000014058A1 (en) * | 1998-09-04 | 2000-03-16 | Asahi Kasei Kabushiki Kaisha | Novel color-developing compound and recording material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0160402A2 (en) * | 1984-03-30 | 1985-11-06 | Minnesota Mining And Manufacturing Company | Fluorochemicals and fibrous substrates treated therewith |
| WO1990006975A1 (en) * | 1988-12-21 | 1990-06-28 | Battelle Memorial Institute | Non-tin-based, low toxicity anti-fouling agents |
| WO1992020747A1 (en) * | 1991-05-17 | 1992-11-26 | Battelle Memorial Institute | Marine compositions bearing preferentially concentrated domains of non-tin, organo anti-fouling agents |
| WO1999051692A1 (en) * | 1998-04-03 | 1999-10-14 | Grace Gmbh | Matting agents based on coated silicon dioxide |
| WO2000014058A1 (en) * | 1998-09-04 | 2000-03-16 | Asahi Kasei Kabushiki Kaisha | Novel color-developing compound and recording material |
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| JP昭45-2594B 1970.01.28 |
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