EP1010542A1 - Matériau d'enregistrement thermosensible - Google Patents

Matériau d'enregistrement thermosensible Download PDF

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Publication number
EP1010542A1
EP1010542A1 EP99125267A EP99125267A EP1010542A1 EP 1010542 A1 EP1010542 A1 EP 1010542A1 EP 99125267 A EP99125267 A EP 99125267A EP 99125267 A EP99125267 A EP 99125267A EP 1010542 A1 EP1010542 A1 EP 1010542A1
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EP
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Prior art keywords
thermosensitive recording
recording material
roll
thickness
resins
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EP99125267A
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German (de)
English (en)
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EP1010542B1 (fr
Inventor
Hiroshi c/o Ricoh Company Ltd. Goto
Chiaki c/o Ricoh Company Ltd. Uematsu
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Ricoh Co Ltd
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Ricoh Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C3/00—Reproduction or duplicating of printing formes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • 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
    • 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
    • B41M2205/04—Direct thermal recording [DTR]
    • 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
    • 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
    • B41M5/337—Additives; Binders
    • B41M5/3375—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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/41—Base layers supports or substrates

Definitions

  • the present invention relates to a thermosensitive recording material for plate-making use which is useful as a block copy for making a plate for flexography, gravure printing, offset printing, and screen printing.
  • the present invention relates to a thermosensitive recording material useful as a recording material for CAD.
  • thermosensitive recording materials are widely known which utilize a coloring reaction between an electron donating coloring compound (hereinafter sometimes referred to as a coloring agent) and an electron accepting compound (hereinafter sometimes referred to as a color developer).
  • a coloring agent an electron donating coloring compound
  • a color developer an electron accepting compound
  • the use of the thermosensitive recording materials is growing, and needs exist for the thermosensitive recording materials as second original sheets or plans for diazo copying.
  • a block copy film for making a plate useful for flexography, gravure printing, offset printing, and screen printing.
  • thermosensitive recording material having such requisite properties is proposed in Japanese Laid-Open Patent Publication No. 8-118811.
  • this accuracy is sometimes referred to as inter-plate error
  • skew is defined as the length difference (La - Lb) and (Lc - Ld).
  • the dimensional accuracy of recorded images formed in a block copy film depends on the conditions under which the block copy film is prepared and the printing conditions under which the formed block copy film is used for printing.
  • the block copy forming apparatus also has influence on the dimensional accuracy of the block copy film, which are as result-effecting as or more result-effecting than the influence that the film has on the dimensional accuracy.
  • the accuracy of film-feeding and the dimensional accuracy of a heat source such as thermal heads have influence on the dimensional accuracy of the resultant images.
  • the accuracy of film-feeding is influenced by:
  • the sticking phenomenon and the head-dust adhesion caused by fusing-adhesion largely depend on the protective layer (or the overcoat layer) and the recording layer. Even when only the lubricating property of the protective layer is enhanced and the film of the protective layer is hardened, if the recording layer is a layer which softens and is crushed upon application of heat, the recording layer becomes the cause of the sticking phenomenon and the head-dust adhesion caused by fusing-adhesion.
  • thermosensitive recording material which utilizes a color reaction between an electron donating coloring compound and an electron accepting compound and which can solve the problems which have been experienced in the past.
  • an object of the present invention is to provide a thermosensitive recording material which utilizes a color reaction between an electron donating coloring compound and an electron accepting compound and in which high levels of inter-plates accuracy between block copy films for plate-making use and skew can be obtained.
  • thermosensitive recording material characterized in that in a thermosensitive recording material in which a thermosensitive recording layer, which includes as main components an electron donating coloring compound, an electron accepting compound and a binder resin, is formed overlying a substrate, the variation (R) of thickness of the roll-shaped thermosensitive recording material in the lateral direction is not greater than 3 ⁇ m.
  • thermosensitive recording material which is characterized in that in a roll-shaped thermosensitive recording material in which a thermosensitive recording layer, which includes as main components an electron donating coloring compound, an electron accepting compound and a binder resin, is formed overlying a substrate, a difference (inclination) in thickness between the right side and the left side of the roll-shaped thermosensitive recording material in the lateral direction is not greater than 0.7 ⁇ m.
  • thermosensitive recording material of the present invention may have an overcoat layer, which is formed overlying the thermosensitive recording layer and which includes as a main component a resin having almost the same refractive index as the binder resin in the thermosensitive recording layer.
  • the variation (R) of thickness of the roll-shaped substrate in the lateral direction is preferably not greater than 4 ⁇ m, and the difference (inclination) in thickness between the right side and the left side of the roll-shaped substrate in the lateral direction is preferably not greater than 0.6 ⁇ m.
  • thermosensitive recording material of the present invention in which images are recorded upon application of heat or the like, is preferably used as a block copy for making a plate for flexography, gravure printing, offset printing, and screen printing.
  • the inter-plates accuracy requisite for the block copy films for plate-making use is preferably not greater than ⁇ 0.1 mm/A0 size. As described below, the inter-plates accuracy is determined by comparing a block copy film having a print ratio of 70 % with a block copy film having a print ratio of 30 %.
  • the skew is preferably not greater than ⁇ 0.2 mm/A0 size. As described below, the skew is defined as a difference between the left side and the right side of a block copy film.
  • thermosensitive recording material having high levels of inter-plates accuracy and skew
  • the most important factors are the variation (R) of thickness of the recording material in the lateral direction and the difference (inclination) in thickness between the left side and the right side of the recording material in the lateral direction in the present invention.
  • the inter-plates accuracy is determined as follows:
  • skew is determined as follows:
  • the variation (R) of thickness of a roll-shaped recording material (or a roll-shaped substrate) in the lateral direction and the difference of thickness between the left side and right side thereof in the lateral direction are defined as follows:
  • the thickness of a roll-shaped thermosensitive recording material (or a substrate) in the lateral direction is measured with a contact type thickness gauge, Electronic Micrometer K351C manufactured by Anritsu Corp (measuring range of 0.1 ⁇ m), as shown in Fig. 3.
  • the thickness is measured with respect to the measuring points as determined by the following equation 1.
  • the variation (R) of thickness thereof is obtained according to equation 2.
  • the number of measuring points W mm/10 mm wherein W represents the width of the recording material (or the substrate) to be measured in the lateral direction.
  • the measuring conditions are 20 ⁇ 10 °C in temperature and 50 ⁇ 20 %RH in relative humidity.
  • the thickness of a left side part and a right side part of a roll-shaped thermosensitive recording material (or a substrate) in the lateral direction, each of whose length from the left edge and the right edge is 30 % of the width, respectively, is measured with a contact type thickness gauge, Electronic Micrometer K351C (measuring range of 0.1 ⁇ m) manufactured by Anritsu Corp.
  • the thickness is measured with respect to the measuring points as determined by the following equation 3, and the difference of thickness between the left side and the right side is obtained by equation 4.
  • the number of measuring points in the left side part and the right side part 0.3 W mm/10 mm wherein W represents the width of the recording material (or the substrate) to be measured in the lateral direction.
  • the inter-plates accuracy and skew can be dramatically improved by imparting the variation (R) of thickness in the lateral direction of not greater than 3 ⁇ m to the roll-shaped thermosensitive recording material, or by imparting the difference of thickness between the left side and the right side in the lateral direction of not greater than 3 ⁇ m to the roll-shaped thermosensitive recording material, and thereby high level needs in of inter-plates accuracy and skew can be satisfied.
  • thermosensitive recording material mentioned above can be easily manufactured by imparting the variation (R) of thickness in the lateral direction of not greater than 4 ⁇ m to the roll-shaped transparent substrate, or imparting the difference of thickness between the left side and the right side in the lateral direction of not greater than 0.6 ⁇ m to the roll-shaped transparent substrate.
  • Suitable electron donating coloring compounds for use in the present invention include dye precursors, which are colorless or pale-colored themselves, but are not specifically limited.
  • known fluoran compounds can be used as the coloring compounds.
  • Specific examples the fluoran compounds include:
  • fluoran compounds having the following formulas (III) - (VIII) are more preferably used as the coloring agents in the present invention.
  • R1 represents an alkyl group having not greater than 8 carbon atoms
  • R2 represents a hydrogen atom or an alkyl group having not greater than 4 carbon atoms
  • X represents a halogen atom such as fluorine, chlorine, bromine or the like.
  • R3 represents an alkyl group having not greater than 8 carbon atoms
  • R4 represents an alkyl group having not greater than 8 carbon atoms.
  • R5 and R6 independently represent an alkyl group having not greater than 8 carbon atoms; and R7 represents a hydrogen atom, a lower alkyl group or a lower alkoxy group.
  • R8 represents a hydrogen atom;
  • R9 represents an alkyl group having not greater than 8 carbon atoms;
  • R10 represents a hydrogen atom, a lower alkyl group or a lower alkoxy group,
  • R11 represents a hydrogen atom or an alkyl group having not greater than 8 carbon atoms;
  • R12 represents an alkyl group having not greater than 8 carbon atoms, a phenyl group or a substituted phenyl group.
  • R13 represents an alkyl group having not greater than 8 carbon atoms
  • R14 represents a methyl group or an ethyl group
  • R15 represents a hydrogen atom or an alkyl group having not greater than 4 carbon atoms
  • Y and Z independently represent a hydrogen atom, or a halogen atom such as fluorine, chlorine, bromine or the like.
  • R16 represents an alkyl group having not greater than 8 carbon atoms
  • R17 represents a methyl group or an ethyl group
  • R18 represents a hydrogen atom or an alkyl group having not greater than 4 carbon atoms
  • Y and Z independently represent a hydrogen atom, or a halogen atom such as fluorine, chlorine, bromine or the like
  • Ar represents a phenyl group or a benzyl group.
  • fluoran compounds having formula (III) include:
  • coloring agents are used alone or in combination.
  • color developers which make the above-mentioned coloring agents color
  • phenolic compounds include gallic acid compounds, protocatechuic acid compounds, bis(hydroxyphenyl)acetic acid and the like.
  • organic phosphoric acid compounds include alkylphosphonic acid compounds, ⁇ -hydroxyalkylphosphonic acid and the like. Among these compounds, organic phosphoric compounds are superior in terms of thermosensitivity of the resultant recording material and background fouling of the resultant recorded images.
  • phosphonic acid compounds having the following formula (I) or (II) are even more preferable.
  • R represents a linear alkyl group having from 16 to 24 carbon atoms.
  • R' represents a linear alkyl group having from 13 to 23 carbon atoms.
  • phosphonic acid compounds represented by the above-mentioned formula (I) include hexadecyl phosphonic acid, octadecyl phosphonic acid, eicosyl phosphonic acid, docosyl phosphonic acid, tetracosyl phosphonic acid and the like.
  • phosphonic acids represented by the above-mentioned formula (II) include ⁇ -hydroxytetradecyl phosphonic acid, ⁇ -hydroxyhexadecyl phosphonic acid, ⁇ -hydroxyoctadecyl phosphonic acid, ⁇ -hydroxyeicosyl phosphonic acid, ⁇ -hydroxytetracosyl phosphonic acid and the like.
  • the color developers are used alone or in combination.
  • the color developer for use in the present invention preferably has an average particle diameter not greater than 10 ⁇ m, and more preferably has an average particle diameter of not greater than 1 ⁇ m and do not include particles having a diameter greater than 1 ⁇ m, to improve the thermosensitivity of the resultant thermosensitive recording material and the resolution of the resultant recorded images.
  • Binder resins for use in the thermosensitive layer are preferably materials which can stably maintain a colored dye material, which is produced by a ring-opening reaction caused by the attack of protons of the color developer on the above-mentioned coloring agent upon application of heat energy and the like, while allowing the color dye material to be in a condition rich with protons.
  • materials which further allow the colored material to be in a condition in which the colored material hardly discolors are preferably used as the binder resin.
  • compounds which include a hydroxy group or a carboxylic acid group and which have a refractive index of from 1.45 to 1.60 at room temperature are preferable as the binder resin.
  • binder resin examples include polyvinyl butyral (1.48 - 1.49), polyvinyl acetal (1.50), epoxy resins (1.55 - 1.61), ethyl cellulose (1.46 - 1.49), cellulose acetate (1.46 - 1.50), cellulose acetate butyrate (1.46 - 1.49), cellulose acetate propionate (1.46 - 1.49), nitro cellulose (1.49 - 1.51), styrene-maleic acid copolymers (1.50 - 1.60) and the like.
  • the parenthesized values mean their refractive index.
  • binder resins when acidic materials are included in binder resins as impurities, or ultraviolet absorbents, antioxidants, anti-aging agents and the like are included in the recording layer, a condition similar to the condition achieved by the above-mentioned binder resins can also be achieved.
  • thermosensitive recording material in the present invention can be improved by including a photo-stabilizer in the thermosensitive recording layer or a protective layer (or an overcoat layer) which is formed on the recording layer.
  • a photo-stabilizer in the thermosensitive recording layer or a protective layer (or an overcoat layer) which is formed on the recording layer.
  • Ultraviolet absorbents, antioxidants, anti-aging agents, quenchers for oxygen in a singlet state, and quenchers for superoxide anions can be used as a photo-stabilizer.
  • ultraviolet absorbents include benzophenone type ultraviolet absorbents such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-oxybenzylbenzophenone, 2-hydroxy-4-chlorobenzophenone, 2-hydroxy-5-chlorobenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-n-heptoxybenzophenone, 2-hydroxy-3,6-dichloro-4-methoxybenzophenone, 2-hydroxy-4-n-heptoxybenzophenone, 2-hydroxy-3,6-dichloro
  • antioxidants and anti-aging agents include 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butyl-4-phenol, styrenated phenol, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-isopropylidenebisphenol, 2,6-bis(2'-hydroxy-3'-t-butyl-5'-methylbenzyl)-4-methylphenol, 4,4'-thiobis-(3-methyl-6-t-butylphenol), tetrakis- ⁇ methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate) ⁇ methane, p-hydroxyphenyl-3-naphthylamine, 2,2,4-trimethyl-1,2-dihydroquinoline, thiobis( ⁇ -naphthol), mercaptobenzothiazole, mercaptobenzimidazole, aldol-2-naphthyl
  • Suitable quenchers for oxygen in a singlet state include carotenes, dyes, amines, phenols, nickel complexes, sulfides and the like.
  • Specific examples of the quenchers for oxygen in a singlet state include 1,4-diazabicyclo(2,2,2)octane, ⁇ -carotene, 1,3-cyclohexadiene, 2-diethylaminomethylfuran, 2-phenylaminomethylfuran, 9-diethylaminomethylanthracene, 5-diethylaminomethyl-6-phenyl-3,4-dihydroxypyran, nickeldimethyldithiocarbamate, nickeldibutyldithiocarbamate, nickel3,5-di-t-butyl-4-hydroxybenzyl-o-ethylphosphonate, nickel3,5-di-butyl-4-hydroxybenzyl-o-butylphosphonate, nickel ⁇ 2,2'-thiobis(4-t-
  • quenchers for superoxide anions complexes of superoxide dismutase with cobalt [III] or nickel [II] and the like, but are not limited thereto in the present invention.
  • photo-stabilizers are used alone or in combination.
  • Suitable substrates for use in the thermosensitive recording material of the present invention include paper or a plastic film.
  • the substrate is preferably transparent, and preferably has a refractive index of from 1.45 to 1.60 at room temperature.
  • the substrate include polyester films such as polyethyleneterephthalate, polybutyleneterephthalate and the like; cellulose derivative films such as triacetyl cellulose and the like; polyolefin films such as polypropylene, polyethylene and the like; polystyrene films; and transparent substrates in which two or more of these films are laminated.
  • thermosensitive layer it is preferable to form an adhesive layer between the thermosensitive layer and the substrate.
  • Suitable materials for use in the adhesive layer include acrylic resins, saturated polyester resins and the like.
  • resins in which these resins are crosslinked can also be used for the adhesive layer.
  • head-matching properties of the recording material can be improved by forming the following overcoat layer overlying the recording layer.
  • the overcoat layer of the recording material of the present invention is effective for the improvement of resistance to chemicals, resistance to water, abrasion resistance and light resistance as well as for the improvement of head-matching properties (i.e., for the improvement of dimensional accuracy). Therefore it is preferable to form the overcoat layer on the top of the thermosensitive recording material of the present invention.
  • Organic fillers for use in the thermosensitive recording material of the present invention preferably have a spherical shape and a 50 % volume average particle diameter (D 50 ), which is obtained by an accumulated volume distribution of particles, of from 1 to 5 ⁇ m.
  • organic fillers preferably have a linseed oil absorption not less than 50 ml/100 g. Further, organic fillers having lubricating properties such as silicone resins are more preferable.
  • an inorganic filler having a 50 % volume average particle diameter (D 50 ) of not greater than 0.7 ⁇ m with an organic filler having a 50 % volume average particle diameter (D 50 ) of from 1 to 5.
  • the total content of the inorganic filler and the organic filler in the overcoat layer is preferably less than 50 % in a solid weight ratio when cost, head-matching properties and other properties are taken into consideration.
  • organic fillers include the following.
  • MP type, and MX type fillers manufactured by Sohken Chemical Co., Ltd., and Technopolymer MB series.
  • the inorganic fillers include kaolin, calcined kaolin, calcined clay, talc, calcium carbonate, titanium oxide, zinc oxide, silica, colloidal silica, magnesium carbonate, magnesium oxide, aluminum hydroxide, and zinc hydroxide.
  • Resins which have the same refractive index as the binder resin constituting the thermosensitive recording layer, are preferably used as a resin constituting the overcoat layer.
  • the term of the same refractive index means that the refractive index of the resin constituting the overcoat layer is substantially the same as that of the resin constituting the recording layer.
  • the refractive index of a resin in the overcoat layer is within the range of about ⁇ 5 % of that of the resin in the recording layer, the refractive indexes of the resin is considered to be the same in the present invention.
  • the refractive index of the resin in the overcoat layer is preferably from 1.45 to 1.60 at room temperature.
  • Suitable resins for use in the overcoat layer include water-soluble resin, aqueous emulsions, hydrophobic resins, ultraviolet crosslinking resins, electron beam crosslinking resins and resins to which a silicone segment is connected like a block or a graft.
  • water-soluble resins include polyvinyl alcohols, modified polyvinyl alcohols, cellulose derivatives (methyl cellulose, methoxy cellulose, hydroxyethyl cellulose, and the like), casein, gelatin, polyvinyl pyrrolidone, styrene-maleic anhydride copolymers, diisobutylene-maleic anhydride copolymers, polyacrylamide, modified polyacrylamlde, methyl vinyl ether-maleic anhydride copolymers, carboxyl-modified polyethylene, polyvinyl alcohol/acrylamide block copolymers, melamine-formaldehyde resins, urea-formaldehyde resins and the like.
  • aqueous emulsions and the hydrophobic resins include polyvinyl acetate, polyurethanes, styrene/butadiene copolymers, styrene/butadiene/acryl type copolymers, polyacrylic acid, polyacrylic acid esters, vinyl chloride/vinyl acetate copolymers, polybutyl methacrylate, ethylene/vinyl acetate copolymers, and the like. These are used alone or in combination. If desired, a hardener may be added to crosslink the resins.
  • ultraviolet crosslinking resins electron beam crosslinking resins, and resins to which a silicone segment is connected like a block or a graft, which are most preferable as the overcoat layer of the present invention, will be explained in detail.
  • Suitable ultraviolet crosslinking resins for use in the overcoat layer include any known monomers, oligomers or prepolymers, which can induce a polymerization reaction upon application of ultraviolet rays.
  • Specific examples of such monomers, oligomers or prepolymers include (poly)ester acrylate, (poly)urethane acrylate, epoxy acrylate, polybutadiene acrylate, silicone acrylate, melamine acrylate and the like.
  • (Poly)Ester acrylate includes a reaction product in which a polyhydric alcohol such as 1,6-hexane diol, propylene glycol (used as propylene oxide), diethylene glycol and the like is reacted with a polybasic acid such as adipic acid, phthalic anhydride, trimellitic acid and the like, and is then reacted with acrylic acid.
  • a polyhydric alcohol such as 1,6-hexane diol, propylene glycol (used as propylene oxide), diethylene glycol and the like
  • a polybasic acid such as adipic acid, phthalic anhydride, trimellitic acid and the like
  • n is an integer of from 1 to 10.
  • k is an integer of from 1 to 10
  • m is an integer of from 1 to 10
  • n is an integer of from 1 to 10.
  • (Poly)Urethane acrylate is a reaction product of a compound having an isocyanate group such as tolylene diisocyanate (TDI) with an acrylate having a hydroxy group.
  • An example of the structure is shown in (d).
  • HEA represents 2-hydroxyethyl acrylate
  • HDO represents 1,6-hexanediol
  • ADA represents adipic acid.
  • n is an integer of from 1 to 10.
  • Epoxy acrylate is broadly classified into bisphenol A type, novolak type and alicyclic type when classified by their structure.
  • the epoxy group of these epoxy resins is esterificated with acrylic acid in order that that the functional group is changed into an acryloyl group. Specific examples of the structure are shown in (e) - (g).
  • n is an integer of from 1 to 15.
  • n is 0 or an integer of from 1 to 5.
  • R represents -(CH 2 ) n -, and n is an integer of from 1 to 10.
  • Polybutadiene acrylate is a reaction product in which 1,2-polybutadiene having a hydroxy group at its end positions is reacted with an isocyanate, 1,2-mercaptoethanol or the like, and is then further reacted with acrylic acid and the like.
  • An example of the structure is shown in (h).
  • Silicone acrylate is made, for example, by modifying with methacrylic acid a product which is made by condensation reaction (demethanolization reaction) of an organic functional trimethoxy silane with a polysiloxane having a silanol group.
  • condensation reaction demethanolization reaction
  • An example of the structure is shown in (i).
  • n is an integer of from 10 to 14.
  • a solvent is optionally used.
  • a solvent include tetrahydrofuran, methyl ethyl ketone, methyl isophenyl isocyanate and the like.
  • compounds having an acrylic type double bond, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and the like can be used as a solvent.
  • polyester diols which can be obtained in the market, Adeka New Ace Y4-30 (manufactured by Asahi Denka Kogyo) is exemplified.
  • polyether triols which can be obtained in the market, Sannics TP-400, and Sannics GP-3000 (manufactured by Sanyo Chemical Industries Ltd.) are exemplified.
  • the molecular weight of the polyester part in the electron beam crosslinking acryl-modified polyurethane resins is preferably from 2000 to 4000 in order to obtain flexibility and toughness, which are requisite for the heat-resistant overcoat layer.
  • the total molecular weight of the electron beam crosslinking acryl-modified polyurethane resins is preferably from 20000 to 50000 for the same reason mentioned above.
  • crosslinking can be accelerated and hardness of the resultant layer can be enhanced.
  • Silicone modified electron beam crosslinking resins are resins having the following formula: wherein R represents -(CH 2 ) n -, wherein n is 0 or an integer of from 1 to 3; TDI represents 2,4-tolylenediisocyanate; HEM represents 2-hydroxyethyl acrylate; x is an integer of from 50 to 100; and y is an integer of from 3 to 6.
  • the electron beam crosslinking silicone-modified resin is used in an amount of not greater than 30 parts by weight, and preferably from 5 to 20 parts by weight, per 100 parts by weight of the electron beam crosslinking acryl-modified polyurethane resin.
  • an electron beam crosslinking monomer having plural functional groups is preferably combined in the overcoat layer to promote crosslinking during the formation of the layer and to enhance the heat resistance properties of the layer. Since this monomer serves as a crosslinking promotor, an advantage such that a complex and high-density crosslinked structure can be formed can be obtained.
  • Such a monomer examples include trimethylolpropane triacrylate, tetramethylolmetane tetraacrylate, pentaerythritol triacrylate, dipentaerythritol triacrylate and the like.
  • the monomer is added in an amount of not greater than 50 parts by weight, and preferably from 20 to 50 parts by weight, per 100 parts by weight of the electron beam crosslinking acryl-modified polyurethane resin.
  • the addition amount is greater than 50 parts by weight, lubricating effects weaken, resulting in deterioration of slipping properties.
  • the overcoat layer including such a phosphazene resin has excellent heat resistance.
  • the phosphazene resin can be manufactured by ring-opening polymerization of a compound having the following formula.
  • the mechanical strength, hardness and heat resistance of the overcoat layer can be further enhanced by crosslinking the resin upon application of ultraviolet rays, electron beams, heat and the like.
  • silicone segments copolymerized with the resin include organopolysiloxanes which have a siloxane bond and an alkyl group such as a methyl group connected to a silicon atom and which includes a reactive functional group, such as a hydroxy group, a carboxyl group, an epoxy group, an amino group, a mercapto group and the like, at the end position of the molecule or in the molecule of the organopolysiloxanes.
  • organopolysiloxanes which have a siloxane bond and an alkyl group such as a methyl group connected to a silicon atom and which includes a reactive functional group, such as a hydroxy group, a carboxyl group, an epoxy group, an amino group, a mercapto group and the like, at the end position of the molecule or in the molecule of the organopolysiloxanes.
  • thermoplastic resins such as poly(meth)acrylic acid ester resins, polyvinyl butyral resins, polyvinyl acetoacetal resins, ethyl cellulose, methyl cellulose, acetyl cellulose, hydroxyethyl cellulose, cellulose acetate propionate, polyurethane resins, polyester resins, polyvinyl acetate resins, styrene-acrylate resins, polyolefin resins, polystyrene resins, polyvinyl chloride type resins, polyether resins, polyamide resins, polycarbonate resins, polyethylene resins, polypropylene resins, polyacrylamide resins and the like.
  • thermoplastic resins such as poly(meth)acrylic acid ester resins, polyvinyl butyral resins, polyvinyl acetoacetal resins, ethyl cellulose, methyl cellulose, acetyl cellulose, hydroxyethyl cellulose, cellulose a
  • poly(meth)acrylic acid ester resins polyvinyl butyral resins, polyvinylacetoacetal resins, cellulose acetate propionate, ethyl cellulose and polyurethane resins are preferable because of having good heat resistance and being soluble to solvents.
  • the content of the silicone segment in the silicone-modified resins is preferably from 1 to 30 % by weight to maintain good lubricating properties, which results in prevention of a sticking problem, and good binding properties and adhesion properties, which results in prevention of dust-adhesion on thermal heads.
  • these silicone-modified resins themselves have a good binding ability, the resins can be used alone or as a main component in the overcoat layer.
  • Photostabilizers can also be included in the overcoat layer of the present invention similarly to the thermosensitive recording layer to improve the light resistance of the overcoat layer.
  • the photostabilizers for use in the present invention include ultraviolet absorbents, antioxidants, anti-aging agents, quenchers for oxygen in a singlet state, and quenchers for superoxide anions.
  • the same materials as those for use in the above-mentioned thermosensitive recording layer can also be used in the overcoat layer.
  • thermosensitive recording material of the present invention can be manufactured by coating a thermosensitive recording layer coating liquid on one side or both sides of a transparent substrate and drying the liquid to form a thermosensitive recording layer, and then forming thereon an overcoat layer including a resin as a main component to form an overcoat layer.
  • the thermosensitive recording layer coating liquid can be prepared by any one of the following methods:
  • organic solvent useful for dissolving the binder resins include ethers such as dibutyl ether, isopropyl ether, dioxane, tetrahydrofuran and the like; ketones such as acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl propyl ketone and the like; esters such as ethyl acetate, isopropyl acetate, n-propyl acetate, n-butyl acetate and the like; and aromatic hydrocarbons such as benzene, toluene, xylene and the like. These solvents are used alone or in combination.
  • the method for coating the overcoat layer and coating weight thereof are not particularly limited. However, when the performance of the resultant overcoat layer and economics are taken into consideration, the coating weight is preferably from 1 to 20 ⁇ m in coating thickness, and more preferably from 1 to 10 ⁇ m, to maintain good performance of the overcoat layer as a protective layer, and good performance of the resultant recording material.
  • the overcoat layer is preferably formed on the recording material so that the resultant recording material has good dimensional accuracy by improving the head-matching properties of the recording material when a thermal head is used as a heat source.
  • an antistatic layer is preferably formed on a backside of the recording material to improve antistatic properties of the recording material.
  • the antistatic layer is required to have an antistatic ability such that a surface resistivity thereof is not greater than 10 8 ⁇ / ⁇ . Therefore the materials used for the layer are limited, and it is general to add therein an electroconductive metal oxide. Antistatic agents using an electroconductive metal oxide are generally expensive. However, the electroconductive metal oxides have good antistatic ability even when the coating weight is relatively low because the metal oxide itself has an electroconductive property. In addition, since the coating weight is relatively low, the electroconductive metal oxides hardly deteriorate the transparency of the recording material.
  • electroconductive metal oxides include SnO 2 , In 2 O 3 , ZnO, TiO 2 , MgO, Al 2 O 3 , BaO, MoO 3 and the like, which are used alone, and complex oxides in which these metal oxides are mixed with P, Sb, Sn, Zn and the like, but are not limited thereto. It is preferable for these particulate metal oxides to be as fine as possible, because the finer the metal oxides becomes, the better the transparency of the resultant layer. In the present invention, good transparency can be obtained by imparting the average particle diameter of not greater than 0.2 ⁇ m to the antistatic agent (metal oxide).
  • binder resins for use in combination with these antistatic agents include, for example, water-soluble resins, aqueous emulsions, hydrophobic resins, ultraviolet light crosslinking resins and electron beam crosslinking resins.
  • water-soluble resins include, for example, polyvinyl alcohols, cellulose derivatives, casein, gelatin, styrene-maleic anhydride, carboxy-modified polyethylene resins and the like.
  • aqueous emulsions and the hydrophobic resins include, for example, polyvinyl acetate, polyurethane, vinyl chloride/vinyl acetate copolymers, polyesters, polybutyl acrylate, polyvinyl butyral, polyvinyl acetal, ethylene/vinyl acetate copolymers and the like. These are used alone or in combination, and if necessary a hardener may be added therein to crosslink the resins.
  • Suitable ultraviolet crosslinking resins for use in the antistatic layer include any known monomers, oligomers or prepolymers, which crosslink while inducing a polymerizing reaction upon application of ultraviolet rays.
  • Electron beam crosslinking resins for use in the antistatic layer are also not particularly limited to specific resins, but resins including as a main component an electron beam crosslinking resin having a branched molecular structure having 5 or more functional groups and a polyester skeleton are especially preferable as the electron beam crosslinking resin in the present invention.
  • the addition amount of the metal oxide is from 0.05 to 1 part by weight, and preferably from 0.2 to 0.8 parts by weight, per 1 part by weight of the binder resin.
  • thermosensitive recording material of the present invention Images are recorded in the transparent thermosensitive recording material of the present invention using a thermal pen, a thermal head, laser heating, thermal etching using light, and the like, which depend on the use of the images. However, in practice, it is preferable to form images using a thermal head.
  • the following components were dispersed in a bead mill such that the average particle diameter of the octadecyl phosphonic acid was 0.3 ⁇ m, to prepare a recording layer coating liquid.
  • liquids A and B were uniformly dispersed such that the average particle diameter of the solid components was about 0.4 ⁇ m, to prepare liquids A and B.
  • liquids A, B and C were mixed to prepare an overcoat layer coating liquid.
  • thermosensitive recording material Preparation of thermosensitive recording material
  • the antistatic layer coating liquid was coated with a wire bar on one side of a roll-shaped polyester film having a thickness of 75 ⁇ m, Merinex 705 manufactured by E.I. Du Pont de Nemours and Co., which had a variation (R) of thickness in the lateral direction of 2.0 ⁇ m and a difference in thickness between the left side and the right side in the lateral direction of 0.1 ⁇ m, and dried to form an antistatic layer having a thickness of 0.3 ⁇ m.
  • the recording layer coating liquid was coated with a wire bar, and dried to form a thermosensitive recording layer having a thickness of about 13.5 ⁇ m.
  • an overcoat layer coating liquid was coated with a wire bar on the recording layer and dried, and an ultraviolet lamp irradiated the coated overcoat layer with ultraviolet light of 80 W/cm to form a crosslinked overcoat layer having a thickness of about 3.0 ⁇ m.
  • thermosensitive recording material of Example 1 was prepared.
  • the variation (R) of thickness of the thermosensitive recording material in the lateral direction was 2.3 ⁇ m and the difference in thickness between the left side and the right side in the lateral direction was 0.3 ⁇ m.
  • Example 1 The procedure performed in Example 1 was repeated except that a polyester film, Merinex 705 manufactured by E.I. Du Pont de Nemours and Co., which had a thickness of 75 ⁇ m and which had a variation (R) of thickness in the lateral direction of 3.2 ⁇ m and a difference in thickness of the left side and the right side in the lateral direction of 0.9 ⁇ m, was used.
  • a polyester film Merinex 705 manufactured by E.I. Du Pont de Nemours and Co., which had a thickness of 75 ⁇ m and which had a variation (R) of thickness in the lateral direction of 3.2 ⁇ m and a difference in thickness of the left side and the right side in the lateral direction of 0.9 ⁇ m, was used.
  • the variation (R) of thickness of the resultant thermosensitive recording material in the lateral direction was 2.9 ⁇ m and the difference in thickness between the left side and the right side in the lateral direction was 0.1 ⁇ m.
  • Example 1 The procedure performed in Example 1 was repeated except that a polyester film, Merinex 705 manufactured by E.I. Du Pont de Nemours and Co., which had a thickness of 75 ⁇ m and which had a variation (R) of thickness in the lateral direction of 4.2 ⁇ m and a difference in thickness of the left side and the right side in the lateral direction of 0.5 ⁇ m, was used.
  • a polyester film Merinex 705 manufactured by E.I. Du Pont de Nemours and Co., which had a thickness of 75 ⁇ m and which had a variation (R) of thickness in the lateral direction of 4.2 ⁇ m and a difference in thickness of the left side and the right side in the lateral direction of 0.5 ⁇ m, was used.
  • the variation (R) of thickness of the resultant thermosensitive recording material in the lateral direction was 4.4 ⁇ m and the difference in thickness between the left side and the right side in the lateral direction was 0.4 ⁇ m.
  • Example 1 The procedure performed in Example 1 was repeated except that a polyester film, Merinex 705 manufactured by E.I. Du Pont de Nemours and Co., which had a thickness of 75 ⁇ m and which had a variation (R) of thickness in the lateral direction of 4.4 ⁇ m and a difference in thickness of the left side and the right side in the lateral direction of 1.1 ⁇ m, was used.
  • a polyester film Merinex 705 manufactured by E.I. Du Pont de Nemours and Co., which had a thickness of 75 ⁇ m and which had a variation (R) of thickness in the lateral direction of 4.4 ⁇ m and a difference in thickness of the left side and the right side in the lateral direction of 1.1 ⁇ m, was used.
  • the variation (R) of thickness of the resultant thermosensitive recording material in the lateral direction was 4.5 ⁇ m and the difference in thickness between the left side and the right side in the lateral direction was 1.3 ⁇ m.
  • Example 1 The procedure performed in Example 1 was repeated except that a polyester film, Merinex 705 manufactured by E.I. Du Pont de Nemours and Co., which had a thickness of 75 ⁇ m and which had a variation (R) of thickness in the lateral direction of 3.4 ⁇ m and a difference in thickness of the left side and the right side in the lateral direction of 0.8 ⁇ m, was used.
  • a polyester film Merinex 705 manufactured by E.I. Du Pont de Nemours and Co., which had a thickness of 75 ⁇ m and which had a variation (R) of thickness in the lateral direction of 3.4 ⁇ m and a difference in thickness of the left side and the right side in the lateral direction of 0.8 ⁇ m, was used.
  • the variation (R) of thickness of the resultant thermosensitive recording material in the lateral direction was 3.6 ⁇ m and the difference in thickness between the left side and the right side in the lateral direction was 0.9 ⁇ m.
  • thermosensitive recording materials prepared in Examples 1 to 5 and the transparent substrate thereof were evaluated as follows:
  • the variation (R) of thickness and difference in thickness of each recording material and its transparent substrate were measured by the method mentioned before using a contact type thickness gauge, Electron Micrometer K351C manufactured by Anritsu Corp.
  • thermosensitive recording materials 1 to 5 prepared in the following examples using a large-size plotter for exclusive use as a trace station, TPE910 manufactured-by Ricoh Co., Ltd.
  • the method for measuring dimensional feeding accuracy and skew were mentioned before.
  • thermosensitive recording material of the present invention for block copy use has high levels of inter-plates accuracy and skew, which are requisite for block copy films used for making plates for flexography, gravure printing, offset printing and screen printing, can be obtained. Therefore the thermosensitive recording material of the present invention is useful as block copies.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Thermotherapy And Cooling Therapy Devices (AREA)
EP99125267A 1998-12-18 1999-12-17 Matériau d'enregistrement thermosensible Expired - Lifetime EP1010542B1 (fr)

Applications Claiming Priority (2)

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JP36106398 1998-12-18
JP36106398 1998-12-18

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AT (1) ATE249342T1 (fr)
DE (1) DE69911155T2 (fr)
ES (1) ES2205689T3 (fr)
PT (1) PT1010542E (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5933180A (ja) * 1982-08-18 1984-02-22 Oji Paper Co Ltd 感熱記録紙の製造法
JPS61274987A (ja) * 1985-05-31 1986-12-05 Fuji Photo Film Co Ltd 感熱記録紙
EP0343687A2 (fr) * 1988-05-27 1989-11-29 Mitsubishi Paper Mills, Ltd. Papier d'enregistrement thermosensible
JPH06143805A (ja) * 1992-11-04 1994-05-24 Oji Yuka Synthetic Paper Co Ltd 感熱記録紙
JPH0776168A (ja) * 1993-06-18 1995-03-20 Ricoh Co Ltd 透明感熱記録媒体
EP0688680A1 (fr) * 1994-06-09 1995-12-27 Ricoh Company, Ltd Elément transparent pour enregistrement thermique

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5933180A (ja) * 1982-08-18 1984-02-22 Oji Paper Co Ltd 感熱記録紙の製造法
JPS61274987A (ja) * 1985-05-31 1986-12-05 Fuji Photo Film Co Ltd 感熱記録紙
EP0343687A2 (fr) * 1988-05-27 1989-11-29 Mitsubishi Paper Mills, Ltd. Papier d'enregistrement thermosensible
JPH06143805A (ja) * 1992-11-04 1994-05-24 Oji Yuka Synthetic Paper Co Ltd 感熱記録紙
JPH0776168A (ja) * 1993-06-18 1995-03-20 Ricoh Co Ltd 透明感熱記録媒体
EP0688680A1 (fr) * 1994-06-09 1995-12-27 Ricoh Company, Ltd Elément transparent pour enregistrement thermique

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 008, no. 132 (M - 303) 20 June 1984 (1984-06-20) *
PATENT ABSTRACTS OF JAPAN vol. 011, no. 135 (M - 585) 28 April 1987 (1987-04-28) *
PATENT ABSTRACTS OF JAPAN vol. 018, no. 453 (M - 1662) 24 August 1994 (1994-08-24) *
PATENT ABSTRACTS OF JAPAN vol. 1995, no. 06 31 July 1995 (1995-07-31) *

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DE69911155T2 (de) 2004-06-09
ES2205689T3 (es) 2004-05-01
ATE249342T1 (de) 2003-09-15
EP1010542B1 (fr) 2003-09-10
DE69911155D1 (de) 2003-10-16
PT1010542E (pt) 2003-12-31

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