Classifications

• • 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
  • B41M5/3333—Non-macromolecular compounds
• • 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
  • B41M5/3333—Non-macromolecular compounds
  • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
  • B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides
• • 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
  • B41M5/3333—Non-macromolecular compounds
  • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
  • B41M2205/40—Cover layers; Layers separated from substrate by imaging layer; Protective layers; Layers applied before imaging
• • 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
  • B41M5/323—Organic colour formers, e.g. leuco dyes
  • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
  • B41M5/3275—Fluoran compounds

Definitions

• the present invention relates to a color developer, a heat-sensitive recording material, and a paint for a heat-sensitive recording layer.
• the heat-sensitive recording material provided with the heat-sensitive recording layer on the support is used in various industrial fields.
• the required performance of the printed portion formed by the heat-sensitive recording layer of the heat-sensitive recording material is influenced by, for example, the basic dye, the color developer, the sensitizer, etc., which are the components of the heat-sensitive recording layer, and in particular, the influence of the color developer.
• the color developer synthetic compounds derived from petrochemicals such as phenolic compounds and sulfonylurea compounds have been proposed. Among them, many phenolic compounds have been developed and put into practical use.
• examples of the non-phenolic developer include phenylureidphenyl-benzene such as N- (phenylureidophenyl) benzenesulfonamide compound (Patent Document 1) and 3- (3-phenylureido) phenyl-4-methylbenzenesulfonate. Phenylonate compounds (Patent Document 2) and the like have been proposed.
• N- (phenylureidophenyl) benzenesulfonamide compound described in Patent Document 1 and the 3- (3-phenylureido) phenyl-4-methylbenzenesulfonate described in Patent Document 2 can be used.
• the phenylureidophenyl-benzenesulfonate compound has good printing characteristics and the like, but has low plasticizer resistance, and if a plasticizer coexists, the printed portion may disappear.
• an object of the present invention is to provide a color developer having excellent plasticizer resistance, a heat-sensitive recording material, and a coating material for a heat-sensitive recording layer.
• a color developer for the thermal recording layer It is characterized by containing a compound represented by the following general formula (I) and an N-substituted amino acid derivative represented by the following general formula (II).
• L is an imino group (-NH-) or an oxy group (-O-).
• R 1 , R 2 and R 3 are a hydrogen atom, a halogen atom, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group, an alkenyl group, a fluoroalkyl group and two N ( R4 ) groups, respectively.
• R 4 represents a hydrogen atom, a phenyl group, a benzyl group, or an alkyl group of C1 to C6.
• NHCOR 5 groups in the formula, R 5 represents an alkyl group of C1 to C6),.
• R 1 , R 2 and R 3 may be the same or different from each other.
• each R 1 may be the same or different from each other.
• each R2 may be the same or different from each other.
• each R3 may be the same or different from each other. (R 0 -X) -Y- (Z) ...
• R0 has an alkyl group having an aryl group of C6 to C10, an alkyl group of C1 to C8, an aralkyl group of C7 to C11, an aryl group of C6 to C10, or a substituent of an alkoxy group of C1 to C8.
• Represents an aryl group that may be X is a group attached to the N-terminus of Y and represents -OCO-, -SO 2 NHCO-, -NHCO-, -NHCS-, or -SO 2- .
• Y represents an amino acid residue or a peptide residue
• the OH group of the serine residue, threonine residue, aspartic acid residue, glutamate residue, or tyrosine residue in the Y group is OR 0 group or OR ".
• the SH group of the cysteine residue may be substituted with an SR 0 group or an SR "group
• the NH group of the histidine residue may be substituted with an NR 0 group or an NR'group.
• the two NH groups of the lysine residue or the ornithine residue may be substituted with an NHR 0 group or an NHR'group, where R'represents an amino-protecting group and R'represents a carboxy-protecting group.
• Y is an amino acid residue other than a cystine residue or a peptide residue having no cystine residue
• Z is a group attached to the C-terminus of Y and represents an OH group or an OR "group.
• R 0 , R'and R' may be the same or different from each other. When there are a plurality of R 0s , each R 0 may be the same or different from each other. When there are multiple R's, each R'may be the same or different from each other. When there are multiple Rs, each R "may be the same or different from each other. Two or more groups of R 0 , R'and R'may be bonded to each other to form a ring.
• the heat-sensitive recording material of the present invention is It is a heat-sensitive recording material in which a heat-sensitive recording layer is provided on a support.
• the heat-sensitive recording layer contains a colorless or light-colored basic dye at room temperature and a color developer that can come into contact with the basic dye and develop a color by heating.
• the color developer is the color developer of the present invention.
• the paint for the heat-sensitive recording layer of the present invention is A paint for a heat-sensitive recording layer to be used for forming a heat-sensitive recording layer. It contains a colorless or light-colored basic dye at room temperature and a color developer that can come into contact with the basic dye and develop a color by heating.
• the color developer is the color developer of the present invention.
• the present invention it is possible to provide a color developer having excellent plasticizer resistance, a heat-sensitive recording material, and a coating material for a heat-sensitive recording layer.
• the color developer, the heat-sensitive recording material, and the paint for the heat-sensitive recording layer of the present invention are represented by the general formula (II) as compared with the compound represented by the general formula (I) as the color developer.
• N-substituted amino acid derivatives are used in combination.
• the plasticizer resistance can be further improved without deteriorating various good storage characteristics such as the color development concentration and the whiteness of the compound represented by the general formula (I). ..
• the performance required for the heat-sensitive recording material includes, for example, 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.
• the storage stability of the printed part is the stability when the printed part is placed in an environment of heat or high humidity, the stability when water adheres, the stability when oils or alcohols adhere, or. It means the residual performance of the printed part due to these external factors such as the stability when it adheres to the tanning used for leather products such as wallets and the plasticizer used to bring out the plasticity of synthetic leather and film products. do.
• thermal recording materials are often used for POS cash register paper.
• the POS cash register paper may be stored in a leather or synthetic leather wallet for a long period of time, and the printed portion of the POS cash register paper may be lost by the plasticizer.
• the film products such as wraps used may come into direct contact with the food label paper, and the plasticizer of the film products may cause the printed portion of the food label paper to disappear.
• the plasticizer resistance of the printed portion is one of the most important items in the storage stability of the heat-sensitive recording material.
• the color developer, the heat-sensitive recording material, and the paint for the heat-sensitive recording layer of the present invention are excellent in plasticizer resistance, and are therefore suitable for the above-mentioned applications such as POS cash register paper and food labels. It can be used for a wide range of purposes without being limited to.
• the compound represented by the general formula (I) is excellent in, for example, printing characteristics, heat resistance, moisture heat resistance, water resistance and the like.
• the N-substituted amino acid derivative represented by the general formula (II) is used in combination with the compound represented by the general formula (I).
• the plasticizer resistance can be further improved while maintaining the excellent printing characteristics, heat resistance, moisture heat resistance, water resistance and the like of the compound represented by the general formula (I).
• the compound represented by the general formula (I) is phenylureidophenyl-benzene represented by the general formula (I-2).
• the heat resistance and heat resistance can be further improved by using the N-substituted amino acid derivative represented by the general formula (II) in combination. According to this, for example, it is possible to suppress or prevent the phenomenon that the printed portion disappears due to the problems of moisture resistance and heat resistance.
• a tautomer or a stereoisomer (eg, a geometric isomer, a configuration) is added to a compound (for example, a compound represented by the general formula (I), a compound represented by the general formula (II), etc.).
• a compound for example, a compound represented by the general formula (I), a compound represented by the general formula (II), etc.
• isomers such as locomotive isomers and optical isomers are present, any isomer can be used in the present invention unless otherwise specified.
• the salt can also be used in the present invention unless otherwise specified.
• the salt may be an acid addition salt or a base addition salt.
• the acid forming the acid addition salt may be an inorganic acid or an organic acid
• the base forming the base addition salt may be an inorganic base or an organic base.
• the inorganic acid is not particularly limited, and is, for example, sulfuric acid, phosphoric acid, hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, hypofluoric acid, hypochloric acid, hypobromic acid, and the like.
• Hypochloroic acid, fluorinated acid, chloric acid, bromine acid, phobic acid, fluoric acid, chloric acid, bromic acid, iodic acid, perfluoric acid, perchloric acid, perbromic acid, periodic acid, etc. Can be mentioned.
• the organic acid is also not particularly limited, and examples thereof include p-toluene sulfonic acid, methane sulfonic acid, oxalic acid, p-bromobenzene sulfonic acid, carbonic acid, succinic acid, citric acid, benzoic acid and acetic acid.
• the inorganic base is not particularly limited, and examples thereof include ammonium hydroxide, alkali metal hydroxides, alkaline earth metal hydroxides, carbonates, hydrogen carbonates, and the like, and more specifically, for example. Examples thereof include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, calcium hydroxide and calcium carbonate.
• the organic base is also not particularly limited, and examples thereof include ethanolamine, triethylamine, tris (hydroxymethyl) aminomethane, and the like.
• the method for producing these salts is also not particularly limited, and for example, they can be produced by appropriately adding an acid or a base as described above to the compound by a known method.
• the chain substituent for example, a hydrocarbon group such as an alkyl group or an unsaturated aliphatic hydrocarbon group
• the chain substituent may be linear or branched unless otherwise specified, and the number of carbon atoms thereof may be high. Although not particularly limited, for example, it may be 1 to 40, 1 to 32, 1 to 24, 1 to 18, 1 to 12, 1 to 6, or 1 to 2 (2 or more in the case of an unsaturated hydrocarbon group). May be.
• the number of ring members (number of atoms constituting the ring) of the cyclic group is not particularly limited, but is, for example, 5 to 32, 5 to 24, 6 It may be ⁇ 18, 6-12, or 6-10.
• any isomer may be used unless otherwise specified.
• the term "naphthyl group” may be a 1-naphthyl group or a 2-naphthyl group.
• the compound represented by the general formula (I) is, for example, N- (phenylureid) represented by the following general formula (I-1). It may be a phenyl) benzenesulfonamide compound.
• R 1 , R 2 and R 3 are a hydrogen atom, a halogen atom, a nitro group, an alkyl group of C1 to C6, a cycloalkyl group of C1 to C6, an alkoxy group of C1 to C6, and a cycloalkyloxy of C1 to C6, respectively.
• Group, alkenyl group of C2 to C6, fluoroalkyl group of C1 to C6, 2 groups of N ( R4 ) (in the formula, R4 represents a hydrogen atom, a phenyl group, a benzyl group, or an alkyl group of C1 to C6.
• NHCOR 5 groups (in the formula, R 5 represents an alkyl group of C1 to C6), a optionally substituted phenyl group, or a optionally substituted benzyl group.
• n1 and n3 independently represent an integer of 1 to 5, respectively.
• n2 represents an integer of 1 to 4, and represents R 1 , R 2 and R 3 may be the same or different from each other.
• each R 1 may be the same or different from each other.
• each R2 may be the same or different from each other.
• each R3 may be the same or different from each other.
• the halogen atom is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the alkyl group of C1 to C6 is not particularly limited, but for example, methyl, ethyl, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, t-butyl.
• examples thereof include a linear or branched alkyl group such as a group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, and an isohexyl group.
• the cycloalkyl group of C1 to C6 is not particularly limited, but for example, cyclopropyl group, cyclobutyl group, 2-methylcyclopropyl group, cyclopropylmethyl group, cyclopentyl group, cyclohexyl. Cyclic cycloalkyl groups such as groups can be mentioned.
• the alkoxy group of C1 to C6 is not particularly limited, but for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, and the like.
• examples thereof include a linear or branched alkoxyl group such as a t-butoxy group, a pentyloxy group, an isopentyloxy group, a neopentyloxy group, a hexyloxy group and an isohexyloxy group.
• the cycloalkyloxy group of C1 to C6 is not particularly limited, but for example, a cyclopropyloxy group, a cyclobutyloxy group, a 2-methylcyclopropyloxy group, or a cyclopropylmethyloxy group.
• examples thereof include a cyclic alkoxyl group such as a group, a cyclopentyloxy group, and a cyclohexyloxy group.
• the alkenyl group of C2 to C6 is not particularly limited, but for example, a vinyl group, an allyl group, an isopropenyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group. , 2-Butenyl group, 3-Butenyl group, 1,3-Butandienyl group, 2-methyl-2-propenyl group and the like.
• the fluoroalkyl group of C1 to C6 is not particularly limited, but for example, a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, or a perfluorohexyl.
• Groups, perfluorocyclohexyl groups and the like can be mentioned.
• the two N (R 4 ) groups are not particularly limited, but for example, R 4 contains an amino group such as a hydrogen atom, a phenyl group, a benzyl group, or a C1 to C6 alkyl group. Can be mentioned.
• the five NHCOR groups are not particularly limited, but for example, a methylcarbonylamino group, an ethylcarbonylamino, a propylcarbonylaminocarbonylamino group, an isopropylcarbonylaminocarbonylamino group, and a butylcarbonylaminocarbonyl.
• Amino group isobutylcarbonylaminocarbonylamino group, sec-butylcarbonylamino group, t-butylcarbonylamino group, pentylcarbonylamino group, isopentylcarbonylamino group, neopentylcarbonylamino group, hexylcarbonylamino group, isohexylcarbonylamino
• Examples thereof include a group, a cyclopropylcarbonylamino group, a cyclobutylcarbonylamino group, a 2-methylcyclopropylcarbonylamino group, a cyclopropylmethylcarbonylamino group, a cyclopentylcarbonylamino group, a cyclohexylcarbonylamino group and the like.
• the substituents of the optionally substituted phenyl group and the optionally substituted benzyl group include the above-mentioned alkyl groups of C1 to C6, alkoxy groups of C1 to C6, and C1.
• ⁇ C6 cycloalkyloxy group, C2 ⁇ C6 alkenyl group, C1 ⁇ C6 fluoroalkyl group, N ( R4 ) 2 groups in the formula, R4 is a hydrogen atom, phenyl group, benzyl group, or C1 ⁇ C6 (Represents the alkyl group of), NHCOR 5 groups and the like can be mentioned.
• the N- (phenylureidophenyl) benzenesulfonamide compound represented by the general formula (I-1) is not particularly limited, and is, for example, 4-methyl-N- [2- (3-phenylureido) phenyl]. Benzene sulfonamide, N- [2- (3-phenylureido) phenyl] benzene sulfonamide and the like can be mentioned.
• the compound represented by the general formula (I) is, for example, phenylureidophenyl-benzene represented by the following general formula (I-2). It may be a sulfonate compound.
• R 1 and R 3 are an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkylcarbonylamino group, an arylcarbonylamino group and an alkylsulfonylamino group, respectively.
• R 1 and R 3 may be the same or different from each other. When there are a plurality of R 1 , each R 1 may be the same or different from each other. When there are a plurality of R3s , each R3 may be the same or different from each other.
• the alkyl group of C1 to C6 is preferable.
• the alkyl group of C1 to C6 is not particularly limited, but for example, methyl, ethyl, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group.
• a linear or branched alkyl group such as a hexyl group and an isohexyl group. In particular, a methyl group is preferable.
• the cycloalkyl group of C1 to C6 is preferable.
• the cycloalkyl group of C1 to C6 is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a 2-methylcyclopropyl group, a cyclopropylmethyl group, a cyclopentyl group, and a cyclohexyl group.
• the alkoxy group of C1 to C6 is preferable.
• the alkoxy group of C1 to C6 is not particularly limited, but for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, a pentyloxy group and an iso. Examples thereof include a linear or branched alkoxy group such as a pentyloxy group, a neopentyloxy group, a hexyloxy group, and an isohexyloxy group.
• the cycloalkyloxy group of C1 to C6 is preferable.
• the cycloalkyloxy group of C1 to C6 is not particularly limited, and for example, a cyclopropyloxy group, a cyclobutyloxy group, a 2-methylcyclopropyloxy group, a cyclopropylmethyloxy group, a cyclopentyloxy group, a cyclohexyloxy group and the like. Cyclic cycloalkyloxy group can be mentioned.
• the aryloxy group, arylcarbonyloxy group, arylcarbonylamino group, or arylsulfonylamino group of R 1 and R 3 is not particularly limited, but is not particularly limited, for example, phenyl.
• Examples include groups or naphthyl groups. Examples of the naphthyl group include a 1-naphthyl group and a 2-naphthyl group.
• the alkyl group of the alkylcarbonyloxy group, the alkylcarbonylamino group, or the alkylsulfonylamino group is not particularly limited, but for example, the above-mentioned alkyl groups of C1 to C6 are preferable. In particular, a methyl group is preferable.
• n1 is preferably 0 or 1, more preferably 1.
• n3 is preferably 0 or 1, more preferably 0.
• the substitution position of R1 is preferably the ortho position or the para position, and more preferably the para position.
• the substitution position of R2 is preferably the ortho position or the para position, and more preferably the para position.
• the phenylureidophenyl-benzenesulfonate compound represented by the general formula (I-2) is not particularly limited, and examples thereof include the compounds exemplified below.
• the compound represented by the general formula (I) may be referred to as "color developer (B)".
• color developer (B) represented by the general formula (I) as described above, for example, the N- (phenylureidophenyl) benzenesulfonamide compound represented by the general formula (I-1) and the benzenesulfonamide compound represented by the general formula (I-1), and ,
• the phenylureidophenyl-benzenesulfonate compound represented by the general formula (I-2) can be mentioned.
• the content of the color developer (B) in the heat-sensitive recording layer of the paint for the heat-sensitive recording layer of the present invention or the heat-sensitive recording material of the present invention is not particularly limited, but from the viewpoint of color development concentration, the heat-sensitive recording layer. 30 to 800 parts by mass is preferable, 50 to 500 parts by mass is more preferable, and 100 to 400 parts by mass is further preferable with respect to 100 parts by mass of the basic dye.
• the color-developing agent contains an N-substituted amino acid derivative represented by the following general formula (II) as described above. (R 0 -X) -Y- (Z) ... (II)
• R0 is an alkyl group having an aryl group of C6 to C10, an alkyl group of C1 to C8, an aralkyl group of C7 to C11, and an aryl group of C6 to C10.
• R0 represents an aryl group which may have a substituent of an alkoxy group of C1 to C8.
• alkyl group having an aryl group of C6 to C10 examples include a benzyl group, a phenethyl group, an o-tolylmethyl group, an m-tolylmethyl group, a p-tolylmethyl group, an o-tolylethyl group, an m-tolylethyl group and a p-tolylethyl group. Can be mentioned.
• Examples of the aryl group which may have a substituent of the alkyl group of C1 to C8 include an o-tolyl group, an m-tolyl group, a p-tolyl group, a 1-ethylphenyl group, a 2-ethylphenyl group and a 3-ethyl group.
• Examples of the aryl group which may have a substituent of the aralkyl group of C7 to C11 include a p-benzylbiphenyl group and the like.
• Examples of the aryl group which may have a substituent of the aryl group of C6 to C10 include a biphenyl group and a 3,3'-dimethylbiphenyl group.
• Examples of the aryl group which may have a substituent of the alkoxy group of C1 to C8 include a 6-methoxyphenyl group.
• X is a group attached to the N-terminal of Y, and as described above, -OCO-, -SO 2 NHCO-, -NHCO-, -NHCS-, or -SO 2- Represents (sulfonyl group).
• Y represents an amino acid residue or a peptide residue as described above, and a serine residue, a threonine residue, an aspartic acid residue, a glutamate residue, or a tyrosine residue in the Y group.
• the OH group of the group may be substituted with an OR 0 group or an OR "group, and the SH group of the cysteine residue may be substituted with an SR 0 group or an SR" group, and the NH group of the histidine residue may be substituted.
• the NH 2 group of a lysine residue or an ornithine residue may be substituted with an NHR 0 group or an NHR' group, and R'is amino-protected.
• a group is represented, and R "represents a carboxy-protecting group.
• R'group an amino-protecting group that protects the NH group of histidine residue in the Y group or the NH 2 group of lysine residue or ornithine residue.
• an R0X group is mentioned, and an acyl group and an alkyl group are also mentioned.
• R "group” As a carboxyprotecting group (R "group) that protects an aspartic acid residue or a glutamate residue in a Y group, an alkoxy is used. Examples thereof include a group, an aryloxy group, an amino group, an alkylamino group and an arylamino group. Further, as a protective group of a serine residue, a threonine residue, an OH group of a tyrosine residue, or an SH group of a cysteine residue in a Y group, the above-mentioned carboxy protecting group (R "group) can be mentioned.
• Y is an amino acid residue other than the cystine residue or a peptide residue having no cystine residue.
• Z is a group bonded to the C-terminal of Y as described above, and represents an OH group or an OR "group.
• R 0 , R'and R' may be the same or different from each other.
• each R 0 may be the same or different from each other.
• each R' may be the same or different from each other.
• Two or more groups of R 0 , R'and R' may be bonded to each other to form a ring.
• the method for producing the N-substituted amino acid derivative represented by the general formula (II) is not particularly limited, but an amino acid or an amino acid derivative and a sulfonated product can be obtained by applying a known method such as the Schotten-Baumann reaction. It can be easily produced from an isocyanate compound or the like.
• the amino acids and peptides used as constituents of the N-substituted amino acid derivative represented by the general formula (II) and their esters and amides are not particularly limited, and may be, for example, L-form, and may be D. -It may be a body, or it may be a DL-body.
• the amino acid may be, for example, a natural amino acid, an unnatural amino acid, an ⁇ -amino acid, or a ⁇ -amino acid.
• the ester is not particularly limited, and examples thereof include C1 to C4 alkyl esters, aryl esters, and aralkyl esters.
• the amide is not particularly limited, and is, for example, an amide, an alkyl substituted amide, an aryl substituted amide, or the like.
• amino acids, peptides and their esters and amides used as constituents of the N-substituted amino acid derivative represented by the general formula (II) include glycine, glycine methyl ester, and glycine ethyl ester.
• Ester derivatives such as glycine-tert-butyl ester, glycine phenyl ester, glycine p-cresyl ester, glycine m-cresyl ester, glycine benzyl ester, glycin amide, N'-methyl glycine amide, amide derivative such as glycyl anilide, phenyl Ester derivatives such as glycine, phenylglycine methyl ester, phenylglycine ethyl ester, phenylglycine benzyl ester, ester derivatives such as phenylglycine amide, alanine, alanine methyl ester, alanine ethyl ester, alanine benzyl ester, alanin amide, phenyl alanine, naphthyl alanine.
• Ester derivatives such as phenylalanine methyl ester, phenylalanine ethyl ester, phenylalanine benzyl ester, amide derivatives such as phenylalanine amide, N'-methylphenylalanine amide, phenylalanylanilide, valine, valine methyl ester, valine methyl ester, valine isopropyl ester, Ester derivatives such as valine-tert-butyl ester and valine benzyl ester, o-substituted serine such as valine amide, leucine, leucine methyl ester, isoleucine, serine, o-methylserine, o-benzylserine, serinemethyl ester, serinebenzyl ester and the like.
• Ester derivatives such as methyl ester, ornithine ethyl ester, ornithine benzyl ester, arginine, arginine methyl ester, arginine ethyl ester, histidine, histidine methyl ester, tryptophan, tryptophan methyl ester, tryptophan benzyl ester, tryptophanamide, cysteine, cystine, S- S-substituted cysteines such as methyl cysteine, S-ethyl cysteine, S-benzyl cysteine and S-phenyl cysteine, ester derivatives such as cysteine methyl ester and cysteine benzyl ester, and S-oxidized derivatives such as cysteine sulfoxide and sulfone, methionine and methionine.
• S-oxidized derivatives such as sulfoxide and methionine sulfone, ester derivatives such as methionine methyl ester and methionine benzyl ester, ester derivatives such as methionine amide, aspartic acid, aspartic acid methyl ester, aspartic acid ethyl ester and aspartic acid benzyl ester, asparagine, Examples thereof include ester derivatives such as glutamic acid, glutamic acid methyl ester, glutamic acid ethyl ester, and glutamic acid benzyl ester, and glutamine. Further, it may be an amino acid such as homoserine, homocysteine, norleucine and a derivative thereof. In addition, C1-C8 aminocarboxylic acids such as ⁇ -alanine, 5-aminovaleric acid, and 7-aminoheptic acid are also selected.
• the peptide is not particularly limited, and is, for example, glycylglycine, glycylglycine methyl ester, glycyl glycine amide, glycyl alanine, glycyl alanine methyl ester, glycyl valine, glycyl leucine, glycyl phenylalanine, glycyl phenylalanine methyl.
• esters examples thereof include esters, glycylphenylalanine amide, glycylproline, alanylalanine, alanylproline, alanylmethionine, alanylmethionine methyl ester, alanylphenylalanine, and glycylglycylglycine.
• the N-substituted amino acid derivative represented by the general formula (II) is, for example, an amino acid, a peptide or a derivative thereof in which an amino group is protected.
• the protecting group is not particularly limited, and may be, for example, a large number of commonly used protecting groups in the fields of amino acid chemistry or peptide synthesis chemistry.
• These functional groups, for example, the sulfonylamino group is derived from arylsulfonyl chloride.
• the urethane group is derived from a chloroformate ester such as chloroformate benzyl ester or a carbonic acid ester such as diphenyl carbonate.
• the (thio) urea group is derived from an iso (thio) cyanate ester such as phenyl iso (thio) cyanate.
• Sulfonylureas are derived from sulfonylureas such as toluenesulfonylisocyanates.
• the compound (X1) forming a sulfonylamino group is not particularly limited, but specifically, for example, benzenesulfonyl chloride, p-toluenesulfonyl chloride, m-toluenesulfonyl chloride, o-toluenesulfonyl chloride, p-chloride.
• chlorides such as methoxybenzene sulfonyl, p-xylene sulfonyl chloride, m-xylene sulfonyl chloride, mesitylen sulfonyl chloride, 1-naphthalene sulfonyl chloride and 2-naphthalene sulfonyl chloride, bromide and iodide.
• the compound (X2) forming a urethane group is not particularly limited, and examples thereof include halogenated formic acid esters such as chloroformic acid benzyl ester and chloroformic acid phenyl ester, and carbonic acid esters such as diphenyl carbonate and dibenzyl carbonate.
• the compound (X3) forming the (thio) urea group is not particularly limited, and is, for example, benzyl isocyanate, phenyl isocyanate, p-tolyl isocyanate, m-tolyl isocyanate, o-tolyl isocyanate, 1-naphthyl isocyanate, 2-.
• the compound (X4) forming a sulfonylurea group is not particularly limited, and examples thereof include benzenesulfonylisocyanate and p-toluenesulfonylisocyanate.
• the N-substituted amino acid derivative obtained by using the compound (X1) forming a sulfonylamino group according to the general formula (II) is not particularly limited, but for example, N-benzenesulfonyl-glycine and N-benzenesulfonyl.
• N-benzenesulfonyl-glycinamide N-benzenesulfonyl-methionine methyl ester
• N-benzenesulfonyl-cysteine-S-benzyl N- (p-toluenesulfonyl) -glycine, N- (p-toluene) Sulfonyl) -alanine, N- (p-toluenesulfonyl) - ⁇ -alanine, N- (p-toluenesulfonyl) -phenylalanine, N- (p-toluenesulfonyl) -phenylalanine methyl ester, N- (p-toluenesulfonyl) -Phenylalanine benzyl ester, N- (p-toluenesulfonyl) -methionine, N
• the N-substituted amino acid derivative obtained by using the compound (X3) forming a urea group according to the general formula (II) is not particularly limited, and is, for example, N-phenylaminocarbonyl-glycine and N-phenylamino.
• N-substituted amino acid derivatives obtained by using the compound (X3) forming a urea group include, for example, N- (m-tolylaminocarbonyl) -phenylalanine-methyl ester and N- (m-tolyl).
• Aminocarbonyl) -phenylalanine-ethyl ester N- (m-tolylaminocarbonyl) -phenylalanine-benzyl ester, N- (phenylaminocarbonyl) -phenylalanine-methyl ester, N- (phenylaminocarbonyl) -phenylalanine-ethyl ester, N- (phenylaminocarbonyl) -phenylalanine-benzyl ester, N- (m-tolylaminocarbonyl) - ⁇ -phenylalaninamide, N, N'-di (m-tolylaminocarbonyl) -lysine, N, N'-di (M-trilaminocarbonyl) -lysine-methyl ester, N, N'-di (m-tolylaminocarbonyl) -ornithine, N, N'-di (m-tolylaminocarbonyl) -orn
• the N-substituted amino acid derivative obtained by using the compound (X3) forming a thiourea group according to the general formula (II) is not particularly limited, but for example, N-phenylaminothiocarbonyl-phenylalanine, N- Phenylaminothiocarbonyl-phenylalanine-methyl ester, N-phenylaminothiocarbonyl-valine-isopropyl ester, N-phenylaminothiocarbonyl-tyrosine-methyl ester, N-phenylaminothiocarbonyl-methionine-methyl ester, N-phenylamino Thiocarbonyl-glycylglycine, N-phenylaminothiocarbonyl-glycylalanine, Nm-tolylaminothiocarbonyl-phenylalanine, Nm-tolylaminothiocarbonyl-phenylalanine-benzyl ester, Nm-tolylamin
• the N-substituted amino acid derivative obtained by using the compound (X2) forming a urethane group according to the general formula (II) is not particularly limited, but for example, N-benzyloxycarbonyl-glycine and N-benzyloxy.
• N-benzyloxycarbonyl-glycine Carbonyl-phenylglycine, N-benzyloxycarbonyl-valine, N-benzyloxycarbonyl-methionine, N-benzyloxycarbonyl-tyrosine, N-benzyloxycarbonyl-hydroxyproline, N-benzyloxycarbonyl-arginine, N-benzyloxy Examples thereof include carbonyl-glycine.
• the N-substituted amino acid derivative obtained by using the compound (X4) forming a sulfonylurea group in the above general formula (II) is not particularly limited, but is not particularly limited, and is, for example, N- (p-toluenesulfonylaminocarbonyl).
• the amino-protecting group (R'group) that protects the NH 2 group of the group or the ornithine residue include an R0X group, and examples thereof include an acyl group and an alkyl group.
• These amino protecting groups (R'groups) can be introduced by known methods.
• the acyl group can be introduced using an acid anhydride.
• the alkyl group can be introduced, for example, by an alkyl halide such as trityl chloride in the presence of an amine or the like.
• the aspartic acid residue or glutamate residue in the Y group of the N-substituted amino acid derivative represented by the general formula (II) is protected.
• the carboxy-protecting group (R "group) include an alkoxy group, an aryloxy group, an amino group, an alkylamino group, an arylamino group and the like, and a serine residue, a threonine residue or a tyrosine residue in the Y group.
• the protective group of the OH group or the SH group of the cysteine residue include the above-mentioned carboxy-protecting group (R "group).
• the N-substituted amino acid derivative preferable as the color developer represented by the general formula (II) is not particularly limited, but for example, N-.
• N-allylsulfonyl-amino acids such as (p-toluenesulfonyl) -glycine, N- (p-toluenesulfonyl) -alanine, N- (p-toluenesulfonyl) - ⁇ -alanine, N-phenylaminocarbonyl-glycine, N -Phenylaminocarbonyl-valine, N- (m-tolylaminocarbonyl) -phenylalanine, N- (phenylaminocarbonyl) -phenylalanine, N- (m-tolylaminocarbonyl) -cysteine-S-benzyl, N- (m-) Trillaminocarbonyl) -methionine, N- (m-tolylaminocarbonyl) -tyrosine, N- (p-tolylaminocarbonyl) -phenylalanine, N- (p
• N- (phenylaminocarbonyl) -methionine N- (m-trillaminocarbonyl) -valine, N- (m-trillaminocarbonyl) -phenylglycine and N- (m-trillaminocarbonyl) -tyrosine Can be mentioned.
• Z is preferably an OH group
• X is preferably a -NHCO- group
• the N-substituted amino acid derivative is N- (m-tolylaminocarbonyl).
• N-substituted amino acid derivatives such as N- (m-tolylaminocarbonyl) -phenylalanine and N- (phenylaminocarbonyl) -phenylalanine represented by the general formula (II) used in the present invention are the present inventors. From the viewpoint of whether amino acids, which are also foods, can be used as heat-sensitive recording materials, we have found that they can be used as color-developing agents. Amino acids do not develop color even when in contact with a basic dye because a basic amino group and an acidic carboxy group coexist in the same molecule and are neutralized in the molecule.
• Patent No. 6726048 has proposed an invention relating to a heat-sensitive recording material using an N-substituted amino acid derivative made from a natural amino acid as a color-developing agent.
• the N-substituted amino acid derivative represented by the general formula (II) is a color developer described in Japanese Patent No. 6726048.
• N-substituted amino acid derivative represented by the general formula (II) may be referred to as a color developer (C).
• the content of the color developer (C) is the heat-sensitive recording layer from the viewpoint of color development concentration and plasticizer resistance. 5 to 400 parts by mass is preferable, 8 to 300 parts by mass is more preferable, and 10 to 200 parts by mass is more preferable with respect to 100 parts by mass of the basic dye.
• the content of the color developer (C) in the heat sensitive recording layer of the color developer of the present invention, the paint for the heat sensitive recording layer of the present invention, or the heat sensitive recording material of the present invention is not particularly limited, but is a plastic resistant agent. From the viewpoint of properties, for example, it may be 1 part by mass or more, more preferably 3 parts by mass or more, more preferably 4 parts by mass or more, and further 5 parts by mass with respect to 100 parts by mass of the developer (B).
• the paint for the heat-sensitive recording layer of the present invention, or the heat-sensitive recording material of the present invention the content of the color-developing agent (C) with respect to 100 parts by mass of the color-developing agent (B).
• the upper limit of the amount is not particularly limited, but is preferably an appropriate amount within a range in which the effect of plasticizer resistance can be obtained. Specifically, for example, it may be 500 parts by mass or less, 450 parts by mass or less, 300 parts by mass or less, 200 parts by mass or less, or 100 parts by mass. It may be as follows. The same applies to the case where the color developer (B) is represented by the general formula (I-1) and the case where the color developer (B) is represented by the general formula (I-2). Is.
• the total content of the color-developing agent (B) and the color-developing agent (C) in the heat-sensitive recording layer of the heat-sensitive recording layer coating material of the present invention or the heat-sensitive recording material of the present invention is not particularly limited, but the color is developed. From the viewpoint of concentration, for example, 1 to 500 parts by mass, 5 to 300 parts by mass, 10 to 200 parts by mass, 10 to 100 parts by mass, and 14 to 100 parts by mass with respect to 100 parts by mass of the basic dye of the heat-sensitive recording layer. , 30 to 100 parts by mass, and for example, 35 to 500 parts by mass, more preferably 40 to 400 parts by mass, and more preferably 60 to 300 parts by mass. The same applies to the case where the color developer (B) is represented by the general formula (I-1) and the case where the color developer (B) is represented by the general formula (I-2). Is.
• the color-developing agent (B) and the color-developing agent (C) do not impair the effect of the present invention. It may be used in combination with a color-developing agent (B) and other color-developing agents other than the color-developing agent (C).
• the other color developer is not particularly limited, but may be, for example, any known or existing color developer. When the other color-developing agent is used, only one type of the other color-developing agent may be used, or two or more types may be used in combination.
• the colorless or light-colored basic dye at room temperature is not particularly limited, and for example, triphenylmethane-based, fluorene-based, diphenylmethane-based, spiro-based, fluorene-based, and thiazine. Examples include system compounds.
• the colorless or light-colored basic dye at room temperature can be selected from, for example, conventionally known leuco dyes.
• the colorless or light-colored basic dye at room temperature is preferably a colorless or light-colored basic dye that is solid at room temperature, and a colorless or light-colored basic dye having a melting point of 60 ° C. or higher is more preferable.
• normal temperature may be, for example, room temperature.
• room temperature or “room temperature” may be, for example, ⁇ 10 ° C. or higher, ⁇ 5 ° C. or higher, 0 ° C. or higher, 5 ° C. or higher, or 10 ° C. or higher, for example, 60 ° C. or lower, 55. It may be °C or less, 50 °C or less, 45 °C or less, 40 °C or less, 35 °C or less, or 30 °C or less.
• the "colorless or light-colored basic dye at room temperature” is, for example, in the temperature range of the "normal temperature” or “room temperature” (for example, ⁇ 10 ° C. to 60 ° C. or 10 ° C. to 30 ° C., etc. It may be a colorless or light-colored basic dye in the temperature range).
• the "colorless or light-colored basic dye that is solid at room temperature” is, for example, the temperature range of the "normal temperature” or "room temperature” (for example, ⁇ 10 ° C. to 60 ° C. or 10 ° C. to 30 ° C.”. It may be a colorless or light-colored basic dye that is solid in a temperature range such as ° C.).
• the "colorless or light-colored basic dye at room temperature” may be any basic dye that can be used for the heat-sensitive recording layer of the heat-sensitive recording material by developing a color by heating.
• a basic dye is not particularly limited, but may be, for example, a general basic dye used in a heat-sensitive recording layer of a heat-sensitive recording material, or, for example, as described above, a conventionally known basic dye. There may be.
• the specific example is also not particularly limited, but is, for example, as described above.
• the "light color” is not particularly limited, but may be, for example, light yellow, light blue, or the like.
• the colorless or light-colored basic dye at room temperature in the heat-sensitive recording material and the paint for the heat-sensitive recording layer of the present invention are as follows, for example.
• the colorless or light-colored basic dye at room temperature is not limited to the following specific examples.
• only one type of basic dye that is colorless or light-colored at room temperature may be used, or two or more types may be used in combination.
• the heat-sensitive recording layer and the paint for the heat-sensitive recording layer of the present invention in the heat-sensitive recording material of the present invention develop color by contacting with a colorless or light-colored basic dye at room temperature and the basic dye by heating. It contains the color developer to be obtained, but may or may not contain any component other than these.
• the optional component examples include a sensitizer.
• the sensitizer is not particularly limited, but for example, a conventionally known sensitizer can be used in combination.
• Specific examples of the sensitizer include fatty acid amides such as stearate amide, bisstearic acid amide, and palmitic acid amide, p-toluenesulfonamide, stearic acid, calcium such as behenic acid and palmitic acid, and zinc.
• fatty acid metal salts such as aluminum, p-benzylbiphenyl, diphenylsulfone, benzylbenzyloxybenzoate, 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, etc. Be done.
• the optional component examples include a storage stabilizer.
• the storage stabilizer is not particularly limited, but for example, a conventionally known storage stabilizer can be used in combination.
• Specific examples of the storage stabilizer include 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), and the like.
• n an integer from 1 to 7.
• the content of the storage stabilizer is not particularly limited, but for example, the content of the color developer (B) and the color developer (C) is 100 parts by mass. 5 to 100 parts by mass is preferable, and 5 to 50 parts by mass is more preferable.
• the optional component examples include an auxiliary agent.
• the auxiliary agent is not particularly limited, and is, for example, a dispersant such as sodium dioctiol succinate, sodium dodecylbenzene sulfonate, sodium lauryl alcohol sulfate, a fatty acid metal salt, zinc stearate, calcium stearate, polyethylene wax, and the like.
• Waxes such as carnauba wax, paraffin wax, ester wax, hydrazide compounds such as adipic acid dihydrazide, glioxal, boric acid, dialdehyde starch, methylol urea, glyoxyphosphate, water resistant agents such as epoxy compounds, antifoaming agents, coloring. Examples include dyes, fluorescent dyes, pigments and the like.
• Examples of the optional component used in the heat-sensitive recording layer of the heat-sensitive recording material of the present invention and the paint for the heat-sensitive recording layer of the present invention include a binder.
• the binder is not particularly limited, but is, for example, fully saponified polyvinyl alcohol having a polymerization degree of 200 to 1900, partially saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, acetacetyl-modified polyvinyl alcohol, and amide-modified polyvinyl alcohol.
• Sulphonic acid-modified polyvinyl alcohol butyral-modified polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, styrene-maleic anhydride copolymer, styrene-butadiene copolymer and cellulose derivatives such as ethyl cellulose and acetyl cellulose, polyvinyl acetate, poly Examples thereof include acrylamide, polyacrylic acid ester, polyvinyl butyral polystyrene and copolymers thereof, polyamide resin, silicone resin, petroleum resin, terpene resin, ketone resin, and chroman resin. These binders can be used alone or in combination of two or more, and can be used by dissolving them in a solvent, or can be used in a state of being emulsified or dispersed in a paste in water or another medium.
• Examples of the optional component used in the heat-sensitive recording layer of the heat-sensitive recording material of the present invention and the paint for the heat-sensitive recording layer of the present invention include pigments.
• the pigment is not particularly limited, but for example, silica, kaolin, calcined kaolin, silica clay, talc, titanium oxide, zinc oxide, aluminum hydroxide, polystyrene resin, urea-formalin resin, styrene-methacrylic acid copolymer, and the like.
• examples thereof include inorganic or organic pigments such as styrene-butadiene copolymers and hollow plastic pigments.
• the types and amounts of basic dyes, color developers, sensitizers, binders, pigments and other additives used in the heat-sensitive recording layer and the paint for the heat-sensitive recording layer of the present invention in the heat-sensitive recording material of the present invention are as follows.
• the quality is not particularly limited, and for example, it can be appropriately determined according to the quality performance required for the heat-sensitive recording layer.
• the method for producing the paint for the heat-sensitive recording layer of the present invention is not particularly limited, and for example, the developer (B) (the compound represented by the general formula (I)) and the developer (the developer) (the compound represented by the general formula (I)) as the developer are not particularly limited. It can be produced in the same manner as a general heat-sensitive recording layer paint except that C) (N-substituted amino acid derivative represented by the general formula (II)) is used in combination. Specifically, for example, in addition to a colorless or light-colored basic dye at room temperature and a color developer that can develop a color in contact with the basic dye by heating, a binder, a sensitizer, a filler, a lubricant, and the like.
• the paint for the heat-sensitive recording layer of the present invention can be produced by adding other additives and the like.
• the coating material for a heat-sensitive recording layer of the present invention can also be produced, for example, by the production method described in Examples described later.
• the method for forming the heat-sensitive recording layer and the method for producing the heat-sensitive recording material are not particularly limited, except that, for example, the paint for the heat-sensitive recording layer of the present invention is used as the paint for the heat-sensitive recording layer. It may be the same as a general method for forming a heat-sensitive recording layer and a method for producing a heat-sensitive recording material. Specifically, for example, the heat-sensitive recording layer paint (coating liquid) of the present invention manufactured as described above is applied onto a support to form a heat-sensitive recording layer, and the heat-sensitive recording material of the present invention is used. Can be manufactured.
• the support is not particularly limited, but may be, for example, at least one of paper and film. That is, the heat-sensitive recording material of the present invention may be, for example, a heat-sensitive recording paper whose support is paper. Further, the heat-sensitive recording material of the present invention may be, for example, a heat-sensitive recording film in which the support is a film.
• the paper is not particularly limited, and examples thereof include paper, recycled paper, and synthetic paper.
• the film is not particularly limited, and examples thereof include a plastic film, a non-woven fabric, and a metal foil.
• the support of the present invention may be formed of, for example, a single material, or may be a composite sheet in which a plurality of materials are combined.
• the heat-sensitive recording layer and the paint for the heat-sensitive recording layer of the present invention in the heat-sensitive recording material of the present invention preferably contain, for example, 20 to 400 parts by mass of a sensitizer with respect to 100 parts by mass of the basic dye, and are all solid. It is preferable to contain 5 to 50% by mass of the binder in the minute.
• the heat-sensitive recording material of the present invention may or may not contain other optional components other than the support and the heat-sensitive recording layer.
• an overcoat layer made of a polymer substance containing an organic pigment may be provided for the purpose of enhancing the storage stability of the heat-sensitive recording layer.
• an undercoat layer containing an organic pigment, an inorganic pigment, hollow fine particles, or the like is provided as the optional component. Is also good.
• the basic dye, the color developer, the sensitizer and, if necessary, the storage stabilizer used in the heat-sensitive recording layer or the paint for the heat-sensitive recording layer are, for example, a ball mill, an attritor, using water as a dispersion medium. It may be finely dispersed and used so that the average particle size is 2 ⁇ m or less by a stirring and crushing machine such as a sand mill.
• a paint for a heat-sensitive recording layer can be manufactured by mixing and stirring a pigment, a binder, an auxiliary agent, etc., if necessary, in the finely dispersed dispersion liquid.
• the heat-sensitive recording layer coating material thus obtained is applied onto a support and then dried to form a heat-sensitive recording layer on the support to produce the heat-sensitive recording material of the present invention. Can be done.
• the amount of the heat-sensitive recording layer paint applied onto the support is not particularly limited, but for example, the amount of the heat-sensitive recording layer paint applied after drying is preferably 1.5 to 12 g / m 2 . More preferably, it is 7 g / m 2 .
• the support in the heat-sensitive recording material of the present invention for example, paper, recycled paper, synthetic paper, plastic film, non-woven fabric, metal leaf and the like can be used as described above. Further, a composite sheet in which these are combined can also be used as a support.
• the thickness of the support is not particularly limited, and can be appropriately adjusted, for example, depending on the use of the heat-sensitive recording material of the present invention.
• a heat-sensitive recording material that satisfies the required performance as a heat-sensitive recording material such as color density, whiteness, and moisture resistance, heat resistance, water resistance, and plasticizer resistance of a printed portion. can.
• the paint for the heat-sensitive recording layer and the heat-sensitive recording material were manufactured as follows.
• Liquid B (Preparation of color developer (B) dispersion) N- [2- (3-Phenylureido) phenyl] Benzene sulfonamide 20 parts 10% polyvinyl alcohol aqueous solution 20 parts Water 33.3 parts
• Liquid D preparation of sensitizer dispersion
• 1,2-bis (3-methylphenoxy) ethane 15 parts
• polyvinyl alcohol aqueous solution 15 parts water 25 parts
• the dispersions A, B, C and D were pulverized with a sand grinder until the average particle size became 1 ⁇ m or less, and the dispersions were mixed at the following ratios to prepare a coating solution.
• Liquid A basic dye dispersion
• Liquid B color developer (B) dispersion) 55.0 parts
• Liquid C color developer (C) dispersion) 18.3 parts
• D sensensitization
• Agent dispersion 55.0 parts
• the obtained sheet was treated with a super calendar so that the smoothness was 900 to 1200 s, and the heat-sensitive recording material of this example was manufactured (made).
• the smoothness was measured by a method according to JIS P8155: 2010 "Paper and Paperboard-Smoothness Test Method-Oken Method”.
• Thermal recordability test (color development test) The prepared thermal recording material was applied with an applied energy of 0.38 mJ / dot using a thermal recording paper printing tester (TH-PMD manufactured by Okura Electric Co., Ltd.). The print density of the recording unit was measured with a Macbeth reflection densitometer (trade name: RD-914, manufactured by Glutag Macbeth). This was used as a sample (blank).
• Plasticizer resistance test Wrap a wrap film (trade name: High Wrap (registered trademark) KMA, manufactured by Mitsui Kagaku) on a polycarbonate pipe (48 mm ⁇ ) in three layers, place the heat-sensitive recording paper recorded in the heat-sensitive recordability test, and then place it. A wrap film was wrapped three times on top and left for 24 hours in an environment of 20 ° C. and 65% RH, and then the image density and the unprinted portion were measured with a Macbeth reflection densitometer.
• Example 2 The same operation as in Example 1 was performed except that 55.0 parts of B solution and 18.3 parts of C solution of Example 1 were changed to 64.1 parts of B solution and 9.2 parts of C solution.
• the paint for the heat-sensitive recording layer of No. 2 and the heat-sensitive recording material of Example 2 were produced. Table 1 shows the results of various tests of the heat-sensitive recording material according to Example 2.
• Example 3 The same operation as in Example 1 was performed except that 55.0 parts of B solution and 18.3 parts of C solution of Example 1 were changed to 69.6 parts of B solution and 3.7 parts of C solution.
• the paint for the heat-sensitive recording layer of No. 3 and the heat-sensitive recording material of Example 3 were produced. Table 1 shows the results of various tests of the heat-sensitive recording material according to Example 3.
• Example 4 The same operation as in Example 1 was performed except that 55.0 parts of B solution and 18.3 parts of C solution of Example 1 were changed to 36.7 parts of B solution and 36.7 parts of C solution.
• the paint for the heat-sensitive recording layer of No. 4 and the heat-sensitive recording material of Example 4 were produced. Table 1 shows the results of various tests of the heat-sensitive recording material according to Example 4.
• Example 5 The same operation as in Example 1 was performed except that 55.0 parts of B solution and 18.3 parts of C solution of Example 1 were changed to 18.3 parts of B solution and 55 parts of C solution. A paint for a heat-sensitive recording layer and a heat-sensitive recording material of Example 5 were produced. Table 1 shows the results of various tests of the heat-sensitive recording material according to Example 5.
• Example 6 The same operation as in Example 1 was performed except that the N- (m-tolylaminocarbonyl) -phenylalanine in the C solution of Example 1 was changed to N- (phenylaminocarbonyl) -phenylalanine, and the heat sensitivity of Example 6 was performed.
• a coating material for a recording layer and a heat-sensitive recording material of Example 6 were prepared. Table 1 shows the results of various tests of the heat-sensitive recording material according to Example 6.
• Example 7 The same operation as in Example 1 was performed except that N- (m-tolylaminocarbonyl) -phenylalanine in Solution C of Example 4 was changed to N- (phenylaminocarbonyl) -phenylalanine, and the heat-sensitive recording of Example 7 was performed. A layer coating material and a heat-sensitive recording material of Example 7 were prepared. Table 1 shows the results of various tests of the heat-sensitive recording material according to Example 7.
• Comparative Example 3 The same operation as in Comparative Example 2 was performed except that the N- (m-tolylaminocarbonyl) -phenylalanine of the solution C of Comparative Example 2 was changed to N- (phenylaminocarbonyl) -phenylalanine, and the heat sensitivity of Comparative Example 3 was performed. A coating material for a recording layer and a heat-sensitive recording material of Comparative Example 3 were produced. Table 1 shows the results of various tests of the heat-sensitive recording material according to Comparative Example 3.
• the heat-sensitive recording materials of Examples 1 to 7 contain, as the color developer (B), an N- (phenylureidophenyl) benzenesulfonamide compound represented by the general formula (I) or the general formula (I-1). Moreover, it was a heat-sensitive recording material provided with a heat-sensitive recording layer containing a color-sensitive agent containing an N-substituted amino acid derivative represented by the general formula (II) as the color-developing agent (C) on a support. As is clear from Table 1, the heat-sensitive recording materials of Examples 1 to 7 are color-developing agents while maintaining the characteristics of the heat-sensitive recording materials in which the heat-sensitive recording layer containing the color developer (B) is provided on the support.
• the plasticizer resistance was superior to that of the heat-sensitive recording material (Comparative Example 1) in which the heat-sensitive recording layer containing (B) alone was provided on the support. Further, the heat-sensitive recording materials of Examples 1 to 7 have higher plasticizer resistance than the heat-sensitive recording materials (Comparative Examples 2 to 3) in which the heat-sensitive recording layer containing the color developer (C) alone is provided on the support. was excellent.
• Liquid B Preparation of color developer (B) dispersion) 3- (3-Phenylureid) Phenyl-4-methylbenzene Sulfonate 20 parts 10% polyvinyl alcohol aqueous solution 20 parts Water 33.3 parts
• Liquid D preparation of sensitizer dispersion
• 1,2-bis (3-methylphenoxy) ethane 15 parts
• polyvinyl alcohol aqueous solution 15 parts water 25 parts
• the dispersions A, B, C and D were pulverized with a sand grinder until the average particle size became 1 ⁇ m or less, and the dispersions were mixed at the following ratios to prepare a coating solution.
• Liquid A basic dye dispersion
• Liquid B color developer (B) dispersion) 55.0 parts
• Liquid C color developer (C) dispersion) 18.3 parts
• D sensensitization
• Agent dispersion 55.0 parts
• a coating material for a heat-sensitive recording layer is manufactured by mixing 100 parts of a solution, a zinc stearate dispersion: (trade name: Hydrin (registered trademark) Z-8-36) 19.4 parts and 20 parts of water. (Prepared).
• the obtained sheet was treated with a super calendar so that the smoothness was 900 to 1200 s, and the heat-sensitive recording material of this example was manufactured (made).
• the smoothness was measured by a method according to JIS P8155: 2010 "Paper and Paperboard-Smoothness Test Method-Oken Method”.
• Example 9 The same operation as in Example 8 was performed except that 55.0 parts of the B solution and 18.3 parts of the C solution of Example 8 were changed to 64.1 parts of the B solution and 9.2 parts of the C solution.
• the paint for the heat-sensitive recording layer of No. 9 and the heat-sensitive recording material of Example 9 were produced. Table 2 shows the results of various tests of the heat-sensitive recording material according to Example 9.
• Example 10 The same operation as in Example 8 was performed except that 55.0 parts of the B solution and 18.3 parts of the C solution of Example 8 were changed to 69.6 parts of the B solution and 3.7 parts of the C solution.
• the paint for the heat-sensitive recording layer of 10 and the heat-sensitive recording material of Example 10 were produced. Table 2 shows the results of various tests of the heat-sensitive recording material according to Example 10.
• Example 11 The same operation as in Example 8 was performed except that 55.0 parts of the B solution and 18.3 parts of the C solution of Example 8 were changed to 36.7 parts of the B solution and 36.7 parts of the C solution.
• the paint for the heat-sensitive recording layer of 11 and the heat-sensitive recording material of Example 11 were produced. Table 2 shows the results of various tests of the heat-sensitive recording material according to Example 11.
• Example 12 The same operation as in Example 8 was performed in Example 12 except that 55.0 parts of B solution and 18.3 parts of C solution of Example 8 were changed to 18.3 parts of B solution and 55 parts of C solution.
• a paint for a heat-sensitive recording layer and a heat-sensitive recording material of Example 12 were produced. Table 2 shows the results of various tests of the heat-sensitive recording material according to Example 12.
• Example 13 The same operation as in Example 8 was performed except that the N- (m-tolylaminocarbonyl) -phenylalanine in the C solution of Example 8 was changed to N- (phenylaminocarbonyl) -phenylalanine, and the heat sensitivity of Example 13 was performed.
• a coating material for a recording layer and a heat-sensitive recording material of Example 13 were produced. Table 2 shows the results of various tests of the heat-sensitive recording material according to Example 13.
• Example 14 The heat-sensitive recording of Example 14 was carried out in the same manner as in Example 8 except that N- (m-tolylaminocarbonyl) -phenylalanine in Solution C of Example 11 was changed to N- (phenylaminocarbonyl) -phenylalanine. A layer coating material and a heat-sensitive recording material of Example 14 were prepared. Table 2 shows the results of various tests of the heat-sensitive recording material according to Example 14.
• Comparative Example 8 The same operation as in Comparative Example 7 was performed except that N- (m-tolylaminocarbonyl) -phenylalanine in Liquid C of Comparative Example 7 was changed to N- (phenylaminocarbonyl) -phenylalanine, and the heat sensitivity of Comparative Example 8 was performed. A coating material for a recording layer and a heat-sensitive recording material of Comparative Example 8 were produced. Table 2 shows the results of various tests of the heat-sensitive recording material according to Comparative Example 8.
• Comparative Example 10 For the heat-sensitive recording layer of Comparative Example 10, the same operation as in Comparative Example 6 was performed except that 3- (3-phenylureido) phenyl-4-methylbenzenesulfonate of Liquid B of Comparative Example 6 was changed to bisphenol S. A paint and a heat-sensitive recording material of Comparative Example 10 were prepared. Table 2 shows the results of various tests of the heat-sensitive recording material according to Comparative Example 10.
• the heat-sensitive recording materials of Examples 8 to 14 are 3- (3-phenylureido) phenyl, which is a kind of compound represented by the general formula (I) or the general formula (I-2) as the color developer (B).
• a heat-sensitive recording layer containing -4-methylbenzenesulfonate and a color developer containing an N-substituted amino acid derivative represented by the general formula (II) as the color developer (C) is provided on the support. It was a heat-sensitive recording material.
• the heat-sensitive recording materials of Examples 8 to 14 are color-developing agents while maintaining the characteristics of the heat-sensitive recording material in which the heat-sensitive recording layer containing the color developer (B) is provided on the support.
• the plasticizer resistance was superior to that of the heat-sensitive recording material (Comparative Example 6) in which the heat-sensitive recording layer containing (B) alone was provided on the support. Further, the heat-sensitive recording materials of Examples 8 to 14 have higher plasticizer resistance than the heat-sensitive recording materials (Comparative Examples 7 to 8) in which the heat-sensitive recording layer containing the color developer (C) alone is provided on the support. was excellent.
• a color developer for the thermal recording layer A color developer comprising a compound represented by the following general formula (I) and an N-substituted amino acid derivative represented by the following general formula (II).
• L is an imino group (-NH-) or an oxy group (-O-).
• R 1 , R 2 and R 3 are a hydrogen atom, a halogen atom, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group, an alkenyl group, a fluoroalkyl group and two N ( R4 ) groups, respectively.
• R 4 represents a hydrogen atom, a phenyl group, a benzyl group, or an alkyl group of C1 to C6.
• NHCOR 5 groups in the formula, R 5 represents an alkyl group of C1 to C6),.
• Substitutable phenyl group optionally substituted benzyl group, aryloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylcarbonylamino group, arylcarbonylamino group, alkylsulfonylamino group, or aryl Represents a sulfonylamino group n1, n2 and n3 each independently represent an integer of 0 to 5.
• R 1 , R 2 and R 3 may be the same or different from each other. When there are a plurality of R 1 , each R 1 may be the same or different from each other. When there are a plurality of R2s , each R2 may be the same or different from each other.
• each R3 may be the same or different from each other.
• R0 has an alkyl group having an aryl group of C6 to C10, an alkyl group of C1 to C8, an aralkyl group of C7 to C11, an aryl group of C6 to C10, or a substituent of an alkoxy group of C1 to C8.
• Represents an aryl group that may be X is a group attached to the N-terminus of Y and represents -OCO-, -SO 2 NHCO-, -NHCO-, -NHCS-, or -SO 2- .
• Y represents an amino acid residue or a peptide residue, and the OH group of the serine residue, threonine residue, aspartic acid residue, glutamate residue, or tyrosine residue in the Y group is OR 0 group or OR ".
• the SH group of the cysteine residue may be substituted with an SR 0 group or an SR "group, and the NH group of the histidine residue may be substituted with an NR 0 group or an NR'group.
• the two NH groups of the lysine residue or the ornithine residue may be substituted with an NHR 0 group or an NHR'group, where R'represents an amino-protecting group and R'represents a carboxy-protecting group.
• R' represents an amino-protecting group
• Y is an amino acid residue other than a cystine residue or a peptide residue having no cystine residue
• Z is a group attached to the C-terminus of Y and represents an OH group or an OR "group.
• R 0 , R'and R' may be the same or different from each other. When there are a plurality of R 0s , each R 0 may be the same or different from each other.
• each R' may be the same or different from each other.
• Two or more groups of R 0 , R'and R' may be bonded to each other to form a ring.
• Appendix 2 The description in Appendix 1, wherein the content of the N-substituted amino acid derivative represented by the general formula (II) is 1 part by mass or more with respect to 100 parts by mass of the compound represented by the general formula (I). Color developer.
• alkenyl group of C2 to C6, fluoroalkyl group of C1 to C6, 2 groups of N R4
• R4 represents a hydrogen atom, a phenyl group, a benzyl group, or an alkyl group of C1 to C6.
• NHCOR 5 groups in the formula, R 5 represents an alkyl group of C1 to C6), a optionally substituted phenyl group, or a optionally substituted benzyl group.
• n1 and n3 independently represent an integer of 1 to 5, respectively.
• n2 represents an integer of 1 to 4, and represents R 1 , R 2 and R 3 may be the same or different from each other.
• each R 1 When there are a plurality of R 1 , each R 1 may be the same or different from each other. When there are a plurality of R2s , each R2 may be the same or different from each other. When there are a plurality of R3s , each R3 may be the same or different from each other.
• Appendix 4 The manifestation according to Appendix 3, wherein the N- (phenylureidophenyl) benzenesulfonamide compound represented by the general formula (I-1) is N- [2- (3-phenylureido) phenyl] benzenesulfonamide. Coloring agent.
• R 1 and R 3 are an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkylcarbonylamino group, an arylcarbonylamino group and an alkylsulfonylamino group, respectively.
• R 1 and R 3 may be the same or different from each other. When there are a plurality of R 1 , each R 1 may be the same or different from each other.
• each R3 may be the same or different from each other.
• Appendix 7 The color developer according to Appendix 6, wherein the phenylureidophenyl-benzenesulfonate compound represented by the general formula (I-2) is 3- (3-phenylureido) phenyl-4-methylbenzenesulfonate.
• Appendix 8) The content of the N-substituted amino acid derivative represented by the general formula (II) is 1 to 500 parts by mass with respect to 100 parts by mass of the compound represented by the general formula (I-2). Or the color developer according to 7.
• the N-substituted amino acid derivative represented by the general formula (II) is N- (m-tolylaminocarbonyl) -phenylalanine or N- (phenylaminocarbonyl) -phenylalanine, according to any one of Supplementary note 1 to 8.
• Color developer. It is a heat-sensitive recording material in which a heat-sensitive recording layer is provided on a support.
• the heat-sensitive recording layer contains a colorless or light-colored basic dye at room temperature and a color developer that can come into contact with the basic dye and develop a color by heating.
• a heat-sensitive recording material, wherein the color-developing agent is the color-developing agent according to any one of Supplementary note 1 to 9.
• Appendix 11 The heat-sensitive recording material according to Appendix 10, wherein the support is at least one of paper and film.
• Appendix 12 A paint for a heat-sensitive recording layer to be used for forming a heat-sensitive recording layer. It contains a colorless or light-colored basic dye at room temperature and a color developer that can come into contact with the basic dye and develop a color by heating.
• a paint for a heat-sensitive recording layer, wherein the color-developing agent is the color-developing agent according to any one of Supplementary note 1 to 9.
• (Appendix 13) 12 is described in Appendix 12, wherein the content of the N-substituted amino acid derivative represented by the general formula (II) is 3 parts by mass or more with respect to 100 parts by mass of the compound represented by the general formula (I). Paint for heat-sensitive recording layer. (Appendix 14) The paint for a heat-sensitive recording layer according to Appendix 12 or 13, which is a paint for a heat-sensitive recording layer to be used for forming the heat-sensitive recording layer in the heat-sensitive recording material according to Appendix 10 or 11.
• the present invention it is possible to provide a color developer having excellent plasticizer resistance, a heat-sensitive recording material, and a coating material for a heat-sensitive recording layer.
• the color developer, the heat-sensitive recording material, and the paint for the heat-sensitive recording layer of the present invention for example, the color density, whiteness, and various good storage characteristics of the compound represented by the general formula (I) are deteriorated. It is also possible to further improve the plasticizer resistance without using it.
• the use of the color developer, the heat-sensitive recording material and the paint for the heat-sensitive recording layer of the present invention is not particularly limited, and for example, it can be widely used in the same applications as the general color developer, the heat-sensitive recording material and the paint for the heat-sensitive recording layer. And the industrial applicability is great.

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