WO2020218003A1 - Dérivé de n,n'-diarylurée et matériau d'enregistrement thermosensible l'utilisant - Google Patents

Dérivé de n,n'-diarylurée et matériau d'enregistrement thermosensible l'utilisant Download PDF

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WO2020218003A1
WO2020218003A1 PCT/JP2020/015936 JP2020015936W WO2020218003A1 WO 2020218003 A1 WO2020218003 A1 WO 2020218003A1 JP 2020015936 W JP2020015936 W JP 2020015936W WO 2020218003 A1 WO2020218003 A1 WO 2020218003A1
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group
bis
phenyloxysulfonyl
benzene
groups
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PCT/JP2020/015936
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English (en)
Japanese (ja)
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良一 木西
石橋　良三
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三光株式会社
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Priority to JP2021515971A priority Critical patent/JP7176796B2/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/75—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton

Definitions

  • the present invention relates to an N, N'-diarylurea derivative and a heat-sensitive recording material using the same.
  • a colorless or light-colored basic dye and an organic color developer are pulverized and dispersed in fine particles at room temperature, and then the two are mixed, and this is mixed with a sensitizer, a binder, a lubricant, and various other materials.
  • a coating liquid obtained by adding an additive or the like is applied onto a support such as paper, plastic film, or processed paper to form a heat-sensitive recording layer, and the heat energy of a heat-sensitive head, a heat pen, or the like is formed.
  • Color development records can be obtained by adding (dye heat). Such thermal recording materials have already been widely put into practical use.
  • the performance required for the heat-sensitive recording material includes the whiteness of the unprinted portion, the whiteness of the unprinted portion under various environmental conditions, the color density of the printed portion, and the storage stability of the printed portion.
  • various resistance tests such as moist heat resistance, water resistance, light resistance, oil resistance and plasticizer resistance are required.
  • Phenol-based color developing agents such as 1), N-3-[(p-toluenesulfonyl) oxy] phenyl-N'-(p-toluenesulfonyl) -urea (Patent Document 2), N- (2-( Non-phenolic color developers such as 3-phenylureido) phenyl) benzenesulfonamide (Patent Document 3) have been proposed.
  • Patent Document 2 N-3- (p-toluenesulfonyloxy) phenyl-N, which is a non-phenole-based color developer, is not sufficient.
  • Patent Document 2 has improved color development sensitivity and storage stability, it is not sufficient and further improvement is required.
  • N-3- (p-toluenesulfonyloxy) phenyl-N'-(p-toluenesulfonyl) -urea is derived from the toluenesulfonylurea group and toluenesulfonyl chloride derived from the toluenesulfonyl isocineate. It has two functional groups of aromatic sulfonic acid aryl ester groups, and although the aromatic sulfonic acid aryl ester group is stable to water (Non-Patent Document 1), one toluenesulfonylurea group is originally an amino group. Although it has been used as a protective group for such substances, it has the drawback of being easily hydrolyzed by water.
  • N- (2- (3-phenylureido) phenyl) benzenesulfonamide (Patent Document 3) still has a problem in the storage stability of the recording unit, and is not sufficiently satisfactory in terms of the required performance as a heat-sensitive recording material. In particular, further improvement in the storage stability of the printed portion is required. Furthermore, in recent years, environmental hygiene problems such as environmental hormones and mutagenicity have been pointed out for 4,4'-isopropyridene diphenol and 4,4'-bisphenol sulfone. The reality is that there is a demand for non-phenol-based color developers.
  • the present invention has been made in view of the above circumstances, and provides an N, N'-diphenylurea derivative suitable as a color developer for a heat-sensitive recording material, and a heat-sensitive recording material using the same as a color developer. Is what you do.
  • R is an alkyl group of C1 to C12, an alkenyl group of C2 to C12, an alkyloxyalkyl group of C3 to C12, a polyoxyalkylene alkyl group of C3 to C12, an aralkyl group of C7 to C12, and an aryl group of C6 to C14.
  • a and B represent a methyl group.
  • a, b, and c are independently integers of 0 to 4, and n is 0 or 1. However, a + c is an integer of 0 to 5.
  • Z is a saturated or unsaturated C1-C8 aliphatic hydrocarbon or alicyclic.
  • Two hydrogen atoms are removed from C1-C8 aliphatic hydrocarbons or alicyclic hydrocarbons linked by a divalent organic group formed by removing two hydrogen atoms from a hydrocarbon and a linking group containing a hetero element.
  • a divalent organic group formed by removing two hydrogen atoms from a monocyclic aromatic hydrocarbon a divalent organic group formed by removing two hydrogen atoms from a polycyclic aromatic hydrocarbon, and a divalent organic group formed by removing two hydrogen atoms from a polycyclic aromatic hydrocarbon.
  • Z in the formulas (1), (1-1), (2), (3), (4) or (5) can be formed by removing two hydrogen atoms from the monocyclic aromatic hydrocarbon.
  • a divalent organic group a divalent organic group formed by removing two hydrogen atoms from a plurality of aromatic hydrocarbons linked by a single bond, or a plurality of aromatic groups linked by a linking group containing a hetero element.
  • a heat-sensitive recording material provided with a heat-sensitive recording layer on a support containing a colorless or light-colored basic dye at room temperature and a color developer that can come into contact with the dye to develop a color by heating.
  • N, N'-diarylurea derivative of the present invention as a color developer, it is possible to provide a heat-sensitive recording material having a high whiteness in a non-printed portion, showing a good color development density, and a high storage stability in the printed portion.
  • the IR chart of 1,3-bis- (3- [3-phenylureido] phenyloxysulfonyl) benzene (Synthesis Example 1) according to the present invention is shown.
  • 1,3-bis - shows the 1 H-NMR spectrum of (3- [3-phenyl ureido] phenyloxy) benzene (Synthesis Example 1).
  • the FD mass spectrum of 1,3-bis- (3- [3-phenylureido] phenyloxysulfonyl) benzene (Synthesis Example 1) according to the present invention is shown.
  • the IR chart of 1,3-bis- (3- [3- ⁇ m-tolyl ⁇ ureido] phenyloxysulfonyl) benzene (Synthesis Example 2) is shown in the present invention.
  • the IR chart of 1,3-bis- (4- [3- ⁇ m-tolyl ⁇ ureido] phenyloxysulfonyl) benzene (Synthesis Example 3) according to the present invention is shown.
  • the IR chart of 4,4'-bis- (3- [3- ⁇ m-tolyl ⁇ ureido] phenyloxysulfonyl) biphenyl (Synthesis Example 4) according to the present invention is shown.
  • the IR chart of 4,4'-bis- (3- [3- ⁇ m-tolyl ⁇ ureido] phenyloxysulfonyl) diphenyl ether (Synthesis Example 5) according to the present invention is shown.
  • the IR chart of 4,4'-bis- (3- [3-phenylureido] phenyloxysulfonyl) diphenyl ether (Synthesis Example 6) according to the present invention is shown.
  • the IR chart of 4,4'-bis- (3- [3-phenylureido] phenyloxysulfonyl) biphenyl (Synthesis Example 7) according to the present invention is shown.
  • the IR chart of 1,3-bis- (3- [3- ⁇ p-tolyl ⁇ ureido] phenyloxysulfonyl) benzene (Synthesis Example 8) according to the present invention is shown.
  • the IR chart of 1,3-bis- (3- [3- ⁇ 1-naphthyl ⁇ ureido] phenyloxysulfonyl) benzene (Synthesis Example 9) according to the present invention is shown.
  • N, N'-diarylurea derivative The N, N'-diarylurea derivative of the present invention is represented by the general formula (1). Further, the N, N'-diarylurea derivative of the present invention may be represented by the general formulas (2) to (5).
  • Z is a divalent organic group.
  • a divalent organic group formed by removing two hydrogen atoms from a saturated or unsaturated aliphatic hydrocarbon or an alicyclic hydrocarbon, an aliphatic hydrocarbon linked by a linking group containing a hetero element or From a divalent organic group formed by removing two hydrogen atoms from an alicyclic hydrocarbon, a divalent organic group formed by removing two hydrogen atoms from a monocyclic aromatic hydrocarbon, and a polycyclic aromatic hydrocarbon
  • Preferred Z is C1 to C8 such as methylene group, ethylene group, trimethylene group, tetramethylene group, hexamethylene group, octamethylene group, isopropylidene group, cyclohexanediyl group, vinylene group, propenylene group and 1-butenylene group.
  • naphthalene and substituted naphthalene such as naphthalene diyl groups, 2,6-naphthalenedyl groups, 1,8-naphthalenediyl groups, and 2,3-naphthalenediyl groups.
  • Zs are phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,2-phenylene group, biphenyl group, 4,4'-biphenyl group, 3,4'-biphenyl group, 3, From monocyclic or polycyclic aromatic hydrocarbons such as 3'-biphenyl group, oxydiphenyl group, 4,4'-oxydiphenyl group, 3,4'-oxydiphenyl group, 3,3'-oxydiphenyl group, etc.
  • a divalent organic group formed by removing two hydrogen atoms a divalent organic group formed by removing two hydrogen atoms from a plurality of aromatic hydrocarbons linked by a single bond, and a linking group containing a hetero element. It is a divalent organic group formed by removing two hydrogen atoms from a plurality of aromatic hydrocarbons linked by.
  • C1-C12 alkyl sulfanyl groups such as methyl sulfanyl group and butyl sulfanyl group
  • C6-C14 aryl sulfanyl groups such as phenyl sulfanyl group
  • C1-C12 such as methanesulfonyl group, ethanesulfonyl group, propanesulfonyl group and butanesulfonyl group Alkylsulfonyl groups
  • C7 to C12 aralkylsulfonyl groups such as benzylsulfonyl groups; benzenesulfonyl groups, toluenesulfonyl groups, 2-p-xylenesulfonyl groups, mesitylensulfonyl groups, 2,4,6-triisopropylbenzenesulfonyl groups, C6-C15 arylsulfonyl groups such as 1-naphthal
  • C7 to C12 aralkylsulfonylamino groups such as benzylsulfonylamino groups; C6-C15 arylsulfonylamino groups such as benzenesulfonylamino groups and toluenesulfonylamino groups; acetyl groups, propionyl groups, acryloyl groups, metalloyl groups, benzoyl groups, C2-C10 acyl groups such as toluoil groups and 2-naphthoyl groups; C2-C10 acylamino groups such as acetylamino groups, propionylamino groups, benzoylamino groups and toluoilamino groups; acetyloxycarbonylamino groups and propionyloxycarbonyl (C2-C10 acyl) oxycarbonylamino group such as amino group, benzoyloxycarbonylamino group, toluoil oxycarbon
  • an aromatic ring or a non-aromatic ring may be formed together with the carbon atom to which each R is bonded, and preferably an aromatic ring, for example, a naphthalene ring may be formed together with the aromatic ring to which R is bonded. ..
  • Preferred R is an alkyl group of C1 to C4. Further, when two adjacent Rs are bonded to each other to form an aromatic ring together with the carbon atom to which each R is bonded, a naphthalene ring is preferably formed together with the aromatic ring to which the R is bonded. ..
  • a and B represent methyl groups.
  • N represents 0 or 1, and n is most preferably 0.
  • A, b, c are independently integers from 0 to 4. However, a + c is an integer of 0 to 5. 0 is most preferable for a and b.
  • the c is preferably 0 or 1.
  • N, N'-diarylurea derivative represented by the general formula (1) of the present invention examples include N, N'-diarylurea derivatives represented by the following general formula (1-1).
  • N N'-diarylurea derivative represented by the general formula (1) of the present invention
  • N N represented by the following general formulas (1-2), (1-3) or (1-4).
  • '-Diarylurea derivatives can be mentioned.
  • N, N'-diarylurea derivative of the present invention are given below, but the present invention is not limited thereto.
  • N, N'-diarylurea derivative represented by the general formula (1) of the present invention is based on a urea compound represented by the following formula (7) and a dihalogenated sulfonyl compound represented by the following formula (8). It can be easily obtained by reacting in the presence.
  • the urea compound represented by the formula (7) the urea compound represented by the following formula (7-1) is preferable.
  • Examples of the urea compound represented by the formula (7) or the formula (7-1) include N- (2-hydroxyphenyl) -N'-phenyl-urea and N- (2-hydroxyphenyl) -N'-.
  • (P-Trill) -Urea N- (2-Hydroxyphenyl) -N'-(m-Trill) -Urea, N- (2-Hydroxyphenyl) -N'-(o-Trill) -Urea, N- (2-Hydroxyphenyl) -N'-(4-ethylphenyl) -urea, N- (2-hydroxyphenyl) -N'-benzyl-urea, N- (2-hydroxyphenyl) -N'-(1- Naftyl) -urea, N- (2-hydroxyphenyl) -N'-(2-naphthyl) -urea, N- (2-hydroxyphenyl) -N'-(4
  • N- (3-hydroxyphenyl) -N'-phenyl-urea N- (3-hydroxyphenyl) -N'-(p-tryl) -urea, N- (3-hydroxyphenyl) -N'-(m) -Trill) -Urea, N- (3-Hydroxyphenyl) -N'-(o-Trill) -Urea, N- (3-Hydroxyphenyl) -N'-(4-Ethylphenyl) -Urea, N- ( 3-Hydroxyphenyl) -N'-(4-isopropylphenyl) -urea, N- (3-hydroxyphenyl) -N'-(4-propenylphenyl) -urea, N- (3-hydroxyphenyl) -N' -Benzyl-urea, N- (3-hydroxyphenyl) -N'-( ⁇ -phenethyl) -urea, N- (3-
  • N- (4-hydroxyphenyl) -N'-phenyl-urea N- (4-hydroxyphenyl) -N'-(p-tryl) -urea, N- (4-hydroxyphenyl) -N'-(m) -Trill) -Urea, N- (4-Hydroxyphenyl) -N'-(o-Trill) -Urea, N- (4-Hydroxyphenyl) -N'-benzyl-Urea, N- (4-Hydroxyphenyl) -N'-( ⁇ -Phenyl) -urea, N- (4-hydroxyphenyl) -N'-(1-naphthyl) -urea, N- (4-hydroxyphenyl) -N'-(2-naphthyl)- Examples thereof include urea, N- (4-hydroxyphenyl) -N'-(4-isopropylphenyl) -urea, N- (4-
  • dihalogenated sulfonyl compound represented by the formula (8) examples include 1,2-ethanedisulfonyl chloride, 1,4-butanedisulfonyl chloride, heptane-1,5-disulfonyl chloride, and benzene-1,2.
  • -Disulfonyl chloride benzene-1,3-disulfonyl chloride, chlorobenzene-2,4-disulfonyl chloride, mecitylene-2,4-disulfonyl chloride, xylene-2,5-disulfonyl chloride, 4,4'- Biphenyldisulfonyl chloride, 1,5-naphthalenedisulfonyl chloride, 4,4'-methylenebis (benzenesulfonyl chloride), 4,4'-thiobis (benzenesulfonyl chloride), 4,4'-oxybis (benzenesulfonyl chloride), Examples thereof include disulfonic acid chlorides such as 4,4'-sulfonylbis (benzenesulfonyl chloride) and 4,4'-diphenyletherdisulfonyl chloride.
  • the heat-sensitive recording material of the present invention is provided with a heat-sensitive recording layer on a support containing a colorless or light-colored basic dye at room temperature and a color developer capable of developing color by contacting the basic dye by heating. It is a heat-sensitive recording material, and the color developer contains the N, N'-diarylurea derivative. Two or more compounds may be used in combination as the color developer, or existing color developers may be used in combination.
  • N-3-[(p-toluenesulfonyl) oxy] phenyl-N'-(p-toluenesulfonyl) -urea (trade name: PF-201), N- [2-( 3-Phenylureide) Phenyl] -benzenesulfonamide (trade name: NKK-1304), N-3-[(p-toluenesulfonyl) oxy] phenyl-N'-(phenyl) -urea and other known non-pheno- Lu Coloring Agent, 4,4'-Isopropyridene Diphenol (BPA), 4,4'-Dihydroxydiphenyl Sulfone (BPS), 4-allyloxy-4'-Hydroxydiphenyl Sulfone (trade name: BPS-MAE) , Bis (3-allyl-4-hydroxyphenyl) sulfone (trade name: TGSA), 4-hydroxy-4'-is
  • the basic dye and the N, N'-diarylurea derivatives represented by the formulas (1) to (5) are pulverized and dispersed into fine particles.
  • a coating liquid obtained by adding a binder, a sensitizer, a filler, a lubricant, and various other additives is prepared, and this is applied onto a support such as paper, plastic film, or processed paper to form the coating liquid. Will be done.
  • Examples of the basic dyes colorless or pale at room temperature used in the heat-sensitive recording layer of the heat-sensitive recording material of the present invention include triphenylmethane-based, fluorene-based, diphenylmethane-based, spiro-based, fluorene-based, and thiazine-based compounds. You can choose from known leuco dyes.
  • Leuco dyes include, for example, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) phthalide, 3- (4-diethylamino-2-ethoxy). Phenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3,3-bis (p-methylaminophenyl) -6-dimethylaminophthalide,
  • a sensitizer can be used as needed, and a conventionally known sensitizer can be used as the sensitizer.
  • sensitizer examples include fatty acid amides such as stearic acid amides, bisstearic acid amides and palmitic acid amides, p-toluenesulfonamides, stearic acids, calcium such as bechenic acid and palmitic acid, and fatty acid metal salts such as zinc or aluminum.
  • fatty acid amides such as stearic acid amides, bisstearic acid amides and palmitic acid amides, p-toluenesulfonamides, stearic acids, calcium such as bechenic acid and palmitic acid, and fatty acid metal salts such as zinc or aluminum.
  • P-benzylbiphenyl, diphenylsulfone, benzyl benzyloxybenzoate, 2-benzyloxynaphthalene, 1,2-bis (p-tolyloxy) ethane, 1,2-bis (phenoxy) ethane, 1,2-bis (3) -Methylphenoxy) ethane, 1,3-bis (phenoxy) propane, dibenzyl oxalate, p-methylbenzyl oxalate, m-terphenyl, 1-hydroxy-2-naphthoic acid and the like can be mentioned.
  • 1,2-bis (p-tolyloxy) ethane and 1,2-bis (phenoxy) ethane are suitable in terms of sensitivity.
  • the N, N'-diarylurea derivative of the present invention has particularly good oil resistance and can be used as a storage stabilizer for conventionally known color developer.
  • Known color formers include, for example, 4,4'-isopropyridene diphenyl, 4,4'-cyclohexylidenediphenyl, 1,1-bis (4-hydroxyphenyl) -ethane, 1,1-.
  • Bis (4-hydroxyphenyl) -1-phenoxyester 4,4'-dihydroxydiphenyl sulfone, 2,4'-dihydroxydiphenyl sulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, 2,2'-bis (4- (4-Hydroxydiphenyl) phenoxy) diethyl ester, 4-hydroxy-4'-isopropoxydiphenyl sulfone, Np-toluenesulfonyl-N'-3- (p-toluenesulfonyloxy) phenylurea, 4 -Hydroxybenzoic acid benzyl ester, N, N-di-m-chloroph
  • a conventionally known storage stabilizer can be used in combination with the heat-sensitive recording layer of the heat-sensitive recording material of the present invention.
  • 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 4,4'-Bis [(4-methyl-3-phenoxycarbonylaminophenyl) ureido] diphenyl sulfone and the diphenyl sulfone cross-linked compound represented by the general formula (10) are suitable for further improvement of storage stability.
  • n an integer from 1 to 7.
  • an auxiliary agent can be used as needed, and examples of the auxiliary agent include sodium dioctiol succinate, sodium dodecylbenzene sulfonate, and lauryl alcohol sulfate.
  • Dispersants such as sodium ester, fatty acid metal salt, zinc stearate, calcium stearate and higher fatty acid metal salt, higher fatty acid amide such as stearic acid amide, paraffin, polyethylene wax, oxide polyethylene wax, caster wax, ester wax and other waxes , Hydrazide compounds such as adipic acid dihydrazide, water resistant agents such as glioxal, boric acid, dialdehyde starch, methylolurea, glyoxyphosphate, epoxy compounds, antifoaming agents, coloring dyes, fluorescent dyes. , And pigments and the like.
  • the binder used for the heat-sensitive recording layer in the present invention includes starches such as oxidized starch, esterified starch, and etherified starch, methyl cellulosic, carboxymethyl cellulosic, methoxycellulosic, and hydroxyethyl cellulos.
  • -Cells such as resin, casein, gelatin, fully (or partially) saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, silicon-modified polyvinyl alcohol, amide-modified polyvinyl alcohol
  • Polyvinyl alcohols such as sulphonic acid-modified polyvinyl alcohol and butyral-modified polyvinyl alcohol, styrene-maleic anhydride copolymer, styrene-butadiene copolymer resin, vinyl acetate resin, urethane Examples thereof include resins, acrylamide resins, acrylic acid ester resins, vinyl butyral styrol and their copolymer resins, amide resins, silicone resins, petroleum resins, terpene resins, ketone resins, and chroman resins.
  • These binders can be used alone or in combination of two or more, and can be used by being dissolved in
  • Pigments blended in the heat-sensitive recording layer include amorphous silica, amorphous calcium silicate, heavy calcium carbonate, light calcium carbonate, kaolin, calcined kaolin, zelkova soil, talc, titanium dioxide, zinc oxide, and aluminum hydroxide. , Magnesium hydroxide, barium sulfate, colloidal silica, polystyrene powder, nylon powder, urea-formalin resin filler, styrene-methacrylic acid copolymer, styrene-butadiene copolymer, hollow plastic pigment, and other inorganic or organic pigments. And so on.
  • the types and amounts of additives such as basic dyes, color formers, sensitizers, binders, pigments and other auxiliaries used in the heat-sensitive recording layer in the present invention are the quality performance required for the heat-sensitive recording layer. It is decided as appropriate according to.
  • the content of the N, N'-diarylurea derivative represented by the above formulas (1) to (5) as a color developer is the basicity of the heat-sensitive recording layer from the viewpoint of color development concentration. It is preferably 0.3 to 5 parts by mass, and more preferably 0.4 to 3 parts by mass with respect to 1 part by mass of the dye.
  • the sensitizer is suitable for 0.2 to 4 parts by mass with respect to 1 part of the basic dye
  • the binder is suitable for 5 to 50% by mass in the total solid content of the heat-sensitive recording layer.
  • the support paper, recycled paper, synthetic paper, plastic film, non-woven fabric, metal foil and the like can be used. In addition, a composite sheet that combines these can also be used.
  • an overcoat layer made of a polymer substance containing an organic pigment may be provided for the purpose of improving storage stability.
  • an undercoat layer containing organic pigments, inorganic pigments, hollow fine particles, foamed particles and the like may be provided for the purpose of preventing the adhesion of debris to the thermal head, improving the print image quality and improving the sensitivity.
  • the basic dyes, color formers, sensitizers and, if necessary, storage stabilizers used in the heat-sensitive recording layer in the present invention are averaged by a stirring pulverizer such as a ball mill, an attritor, or a sand mill using water as a dispersion medium. It is finely dispersed and used so that the particle size is 2 ⁇ m or less.
  • a heat-sensitive recording layer coating material is prepared by mixing and stirring a pigment, a binder, an auxiliary agent, and the like, if necessary, with the finely dispersed dispersion liquid.
  • the amount of the heat-sensitive recording layer coating material thus obtained after drying is about 1.0 to 20 g / m 2 , preferably about 1.5 to 12 g / m 2 , and more preferably 2.0 to 7.
  • the heat-sensitive recording layer is formed by applying it on the support and drying it so as to be about 0 g / m 2 , particularly preferably about 3 to 7 g / m 2 .
  • the coating method for forming the heat-sensitive layer is not particularly limited, and for example, air knife coating, burr bar coating, pure blade coating, rod blade coating, curtain coating, die coating, slide velvet coating, offset gravure coating. It can be coated by an appropriate coating method such as 5-roll coating.
  • the thermal recording layer coating material prepared in this manner may be directly applied onto the support to laminate the thermal recording layer on the support, or an undercoat layer may be first formed on the support. , A thermal recording layer may be formed on the formed undercoat layer.
  • the composition of the undercoat layer may be appropriately selected depending on the intended purpose, but generally includes a binder, a pigment and the like.
  • a resin such as that used for the thermal recording layer can be used. That is, starches such as oxidized starch, esterified starch, and etherified polyvinyl alcohol, cellulose resins such as methyl cellulose, carboxy cellulose, methoxycellulos, methoxy cellulose, and hydroxyethyl cellulose, casein, gelatin, and completely (or partially) saponified polyvinyl alcohol.
  • Examples of the inorganic pigment contained in the undercoat layer include metal oxides such as aluminum hydroxide, magnesium hydroxide, barium sulfate, aluminum silicate and calcium carbonate, metal compounds such as metal hydroxides, sulfates and carbonates, and amorphous materials.
  • Examples thereof include inorganic white pigments such as silica, calcined kaolin, and talc. Of these, calcined kaolin is preferably used because it has excellent color development sensitivity and dregs absorption.
  • the particle size of the inorganic pigment is preferably about 0.5 to 3.0 ⁇ m.
  • spherical resin particles (so-called solid resin particles), hollow particles, resin particles having through holes, and a part of hollow resin particles are obtained by cutting them with a modified surface. Examples thereof include resins having such openings. Hollow resin is preferably used to increase the recording concentration.
  • the ratio of the inorganic pigment to the organic pigment used is the mass ratio. It is preferably about 90:10 to 30:70, and more preferably 70:30 to 50:50.
  • a foam resin can be used.
  • the undercoat layer is generally obtained by mixing and stirring at least one selected from inorganic pigments and organic pigments and a binder using water as a dispersion medium, and the amount of the undercoat layer paint applied on the support after drying is 1 to 20 g. It is formed by coating and drying so as to be about / m 2 , preferably about 5 to 15 g / m 2 .
  • the amount of the binder and the pigment used is preferably about 5 to 40% by mass of the binder and about 10 to 95% by mass of the pigment with respect to the total solid content of the undercoat layer.
  • various auxiliary agents such as lubricants such as zinc stearate, calcium stearate and paraffin wax, fluorescent dyes, coloring dyes, surfactants and cross-linking agents can be added to the paint for the undercoat layer, if necessary.
  • the undercoat layer may be one layer, and in some cases, two or more layers may be provided.
  • a protective layer containing a binder having a film-forming property as a main component may be provided on the heat-sensitive recording layer.
  • the coating material for a protective layer is prepared by mixing and stirring a binder component, a pigment, and, if necessary, an auxiliary agent, using water as a medium, for example.
  • the binder, pigment, and auxiliary agent used for the protective layer those used in the above-mentioned heat-sensitive recording layer are used.
  • a glossy layer may be provided on the protective layer.
  • the glossy layer include a method of applying a coating liquid containing an electron beam or an ultraviolet curable compound as a main component and then irradiating with an electron beam or ultraviolet rays to cure the glossy layer, a method of using an ultrafine core-shell acrylic resin, and the like. Be done.
  • an antistatic layer may be provided on the back surface side of the support.
  • the paint for forming the undercoat layer, the protective layer, the glossy layer, etc. is the same as the heat-sensitive recording layer, such as pure blade coating, rod blade coating, cartridge coating, offset gravure coating, etc. It can be coated by the appropriate coating method of, and each layer is formed by drying.
  • thermal recording materials After forming each layer, various known treatment techniques in the field of manufacturing thermal recording materials such as super calender treatment may be appropriately added.
  • FIG. 1 shows an IR chart.
  • FIG. 2 shows the 1 H-NMR spectrum.
  • FIG. 3 shows the FD mass spectrum.
  • Solution C preparation of sensitizer dispersion
  • 1,2-Bis (m-trilloxy) ethane 15 parts 10% polyvinyl alcohol aqueous solution 15 parts water 25 parts
  • Aluminum hydroxide (trade name: Heidilite H-42) 27 parts, amorphous silica (trade name: Mizukasil P-527) 10 parts, 10% solution of oxidized starch 100 parts, zinc stearate dispersion: (trade name) : Hydrin Z-8-36) 19.4 parts and 50 parts of water were mixed to prepare a heat-sensitive recording paint.
  • thermal recording material As a support, an undercoat paint is applied to high-quality paper (acid paper) having a basis weight of 53 g so that the mass per area after drying is 6 g / m 2, and then the paint for a heat-sensitive recording layer is applied. The coating was applied and dried so that the mass per area after drying was 3.8 g / m 2 .
  • This sheet was treated with a super calendar so that the smoothness (JISP8155: 2010) was 900 to 1200 s to prepare a thermal recording material.
  • Oil resistance test-1 The test piece was immersed in salad oil for 10 minutes in a heat-sensitive recording material recorded at an applied energy of 0.38 mJ / dot in a heat-sensitive recordability test, and then the oil of the test piece was wiped off, and the image density was measured with a Macbeth reflection densitometer.
  • Oil resistance test-2 The test piece was immersed in salad oil for 3 hours in a heat-sensitive recording material recorded at an applied energy of 0.38 mJ / dot in a heat-sensitive recordability test, and then the oil of the test piece was wiped off, and the image density was measured with a Macbeth reflection densitometer.
  • the results of various tests of the thermal recording material according to this example are as shown in Table 1.
  • Example 2 1,3-Bis- (3- [3-phenylureido] phenyloxysulfonyl) benzene (Synthesis Example 1) of Solution B of Example 1 was added to 1,3-bis- (3- [3- ⁇ m-trill ⁇ ). Ureido] Phenyloxysulfonyl) Benzene (Synthesis Example 2) was replaced with the same operation as in Example 1.
  • Table 1 The results of various tests of the heat-sensitive recording material according to this example are as shown in Table 1.
  • Example 3 1,3-Bis- (3- [3-phenylureido] phenyloxysulfonyl) benzene (Synthesis Example 1) of Solution B of Example 1 was added to 1,3-bis- (4- [3- ⁇ m-trill ⁇ ). Ureid] Phenyloxysulfonyl) Benzene (Synthesis Example 3) was replaced with the same operation as in Example 1.
  • Table 1 The results of various tests of the heat-sensitive recording material according to this example are as shown in Table 1.
  • Example 4 1,3-Bis- (3- [3-phenylureido] phenyloxysulfonyl) benzene (Synthesis Example 1) of Solution B of Example 1 was added to 4,4'-bis- (3- [3- ⁇ m-trill). ⁇ Ureido] Phenyloxysulfonyl) Biphenyl (Synthesis Example 4) was replaced with the same operation as in Example 1. The results of various tests of the heat-sensitive recording material according to this example are as shown in Table 1.
  • Example 5 1,3-Bis- (3- [3-phenylureido] phenyloxysulfonyl) benzene (Synthesis Example 1) of Solution B of Example 1 was added to 4,4'-bis- (3- [3- ⁇ m-trill). ⁇ Ureido] Phenyloxysulfonyl) The same operation as in Example 1 was carried out except for the replacement with diphenyl ether (Synthesis Example 5). The results of various tests of the heat-sensitive recording material according to this example are as shown in Table 1.
  • Example 6 1,3-Bis- (3- [3-phenylureido] phenyloxysulfonyl) benzene (Synthesis Example 1) of Solution B of Example 1 was added to 4,4'-bis- (3- [3-phenylureido] phenyl. The same operation as in Example 1 was carried out except that the oxysulfonyl) diphenyl ether (Synthesis Example 6) was replaced.
  • Table 1 The results of various tests of the heat-sensitive recording material according to this example are as shown in Table 1.
  • Example 7 1,3-Bis- (3- [3-phenylureido] phenyloxysulfonyl) benzene (Synthesis Example 1) of Solution B of Example 1 was added to 4,4'-bis- (3- [3-phenylureido] phenyl. The same operation as in Example 1 was carried out except that the mixture was replaced with oxysulfonyl) biphenyl (Synthesis Example 7). The results of various tests of the heat-sensitive recording material according to this example are as shown in Table 1.
  • Example 8 1,3-Bis- (3- [3-phenylureido] phenyloxysulfonyl) benzene (Synthesis Example 1) of Solution B of Example 1 was added to 1,3-bis- (3- [3- ⁇ p-trill ⁇ ). Ureido] Phenyloxysulfonyl) Benzene (Synthesis Example 8) was replaced with the same operation as in Example 1.
  • Example 9 1,3-Bis- (3- [3-phenylureido] phenyloxysulfonyl) benzene (Synthesis Example 1) of Solution B of Example 1 was added to 1,3-bis- (3- [3- ⁇ 1-naphthyl ⁇ ). Ureido] Phenyloxysulfonyl) Benzene (Synthesis Example 9) was replaced with the same operation as in Example 1.
  • the heat-sensitive recording material produced from the N, N'-diarylurea derivative of the present invention has high whiteness in the non-printed portion, exhibits a good color density, and moisture resistance in the printed portion. It was also good in all the storage stability tests of heat resistance, heat resistance, light resistance, water resistance, and oil resistance.
  • the heat-sensitive recording material produced from the N, N'-diarylurea derivative of the present invention is not printed because the color developer used is the N, N'-diarylurea derivative represented by the general formula (1).
  • the whiteness of the part is high, it shows a good color density, and good storage stability is obtained in all the storage stability tests, and its industrial applicability as an alternative to the conventional thermal recording material is extremely promising.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Abstract

L'invention concerne : un dérivé de N,N'-diarylurée représenté par la formule générale (1) (dans la formule (1), Z est un groupe organique divalent ; R est un groupe alkyle, un groupe alcényle, un groupe alkyloxyalkyle, un groupe aralkyle, un groupe aryle, un groupe alkylsulfanyle, un groupe aralkylsulfanyle, un groupe arylsulfanyle, un groupe alkylsulfonyle, un groupe aralkylsulfonyle, un groupe arylsulfonyle, un groupe aralkylsulfonylamino, un groupe arylsulfonylamino, un groupe acyle, ou similaire ; une pluralité de fractions R peuvent se lier les unes aux autres pour former un cycle ; A et B sont des groupes méthyle ; a, b et c sont chacun indépendamment un nombre entier compris entre 0 et 4 ; et n vaut 0 ou1) ; et un matériau d'enregistrement thermosensible qui présente une blancheur élevée dans des parties non imprimées, a une bonne densité de coloration et qui est obtenu à l'aide du N,N'-diarylurée, qui répond aux performances requises d'un matériau d'enregistrement thermosensible ayant une grande aptitude au stockage de la partie imprimée, en tant que développeur de couleur.
PCT/JP2020/015936 2019-04-26 2020-04-09 Dérivé de n,n'-diarylurée et matériau d'enregistrement thermosensible l'utilisant WO2020218003A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09510457A (ja) * 1994-03-14 1997-10-21 イーライ・リリー・アンド・カンパニー カルバニリド抗コクシジウム剤
JP2010053128A (ja) * 2008-07-30 2010-03-11 Nippon Paper Industries Co Ltd フェノールスルホン酸エステル、顕色剤及び感熱記録材料
JP2019043005A (ja) * 2017-08-31 2019-03-22 三光株式会社 感熱記録材料
JP2019048411A (ja) * 2017-09-08 2019-03-28 三光株式会社 ジフェニルメタン誘導体を用いた感熱記録材料

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09510457A (ja) * 1994-03-14 1997-10-21 イーライ・リリー・アンド・カンパニー カルバニリド抗コクシジウム剤
JP2010053128A (ja) * 2008-07-30 2010-03-11 Nippon Paper Industries Co Ltd フェノールスルホン酸エステル、顕色剤及び感熱記録材料
JP2019043005A (ja) * 2017-08-31 2019-03-22 三光株式会社 感熱記録材料
JP2019048411A (ja) * 2017-09-08 2019-03-28 三光株式会社 ジフェニルメタン誘導体を用いた感熱記録材料

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