A heat transfer sheet in which a recorded image having excellent stability in storage and manifesting little variation in sensitivity and resolution can be obtained by adding an additive to a light-heat-conversion layer.

1. Field of the Invention
The present invention relates to a heat transfer sheet and a light-heat-conversion type image forming material used in an image forming method in which an image having high resolution is formed using a laser beam. More particularly, the present invention relates to a heat transfer sheet and a light-heat-conversion type image-forming material in which deterioration of a light-heat-conversion layer due to the passage of time when the heat transfer sheet and the light-heat conversion type image forming material is stored or the like is prevented, and in which a transfer image showing no reduction in image quality is obtained.
2. Description of the Related Art
Conventionally, as a recording material used in a method of formation of transferred images using laser beam, heat transfer sheets are known in which a light-heat-conversion layer containing a light-heat-conversion colorant such as an infrared light absorbing colorant and the like and which light-heat-conversion layer absorbs laser beams and generates heat, and an image formation layer containing a pigment dispersed in components such as heat waxes which melt when heated, binder and the like, are provided in that order on a support. In an image forming method using this sheet, due to heat generated in regions irradiated with laser beam in the light-heat-conversion layer, portions of the image formation layer corresponding to these regions are melted, and transferred onto an image receiving material which has been laminated on the heat transfer sheet, to thereby form transferred images.
However, when a heat transfer sheet is stored, particularly when stored under conditions of high temperature and high humidity, problems occur such as decrease in sensitivity and deterioration of resolution. Further, even if a heat transfer sheet is stored at room temperature, when the period of storage is long, the problem of reduction in recording ability also arises. Further, even if the heat transfer sheet is stored before the formation of a light-heat-conversion layer, that is, even if a coating solution is stored, a problem exists that due to deterioration as a result of the passage of time, a desired optical density can not be obtained, leading to lowering of image quality.
An object of the present invention is to provide a heat transfer sheet and a light-heat-conversion type image forming material which are excellent in stability during storage and in which recorded images showing little variation in sensitivity and resolution can be obtained.
A first embodiment of the present invention is a heat transfer sheet comprising a light-heat-conversion layer which includes an infrared light absorbing colorant and an image formation layer, the layers being provided in that order on a support, wherein said light-heat-conversion layer further includes one or more compounds having at least one functional group selected from a phosphate group, a phosphite group, an acid halide group, a sulfonic halide group, an acid anhydride group and an isocyanate group.
A second embodiment of the present invention is a heat transfer sheet comprising a light-heat-conversion layer which includes an infrared light absorbing colorant and an image formation layer, the layers being provided in that order on a support, wherein said light-heat-conversion layer includes at least one of compounds having an acidic group.
A third embodiment of the present invention is a heat transfer sheet comprising a light-heat-conversion layer which includes an infrared light absorbing colorant and an image formation layer, the layer being provided in that order on a support, wherein said light-heat-conversion layer further includes at least one or more compounds selected from compounds represented by the following general formula (10) and tautomers thereof, and compounds represented by the following general formula (13):
Axe2x80x94Sxe2x80x94Bxe2x80x83xe2x80x83General formula (10)
wherein, A represents an aromatic ring or a heterocyclic ring which may have a substituent; B represents a hydrogen atom, xe2x80x94Sxe2x80x94Axe2x80x2, or xe2x80x94C(xe2x95x90O)R1; Axe2x80x2 represents an aromatic or heterocyclic ring which may have a substituent, and may be the same as said A; R1 represents an alkyl group which may be branched, has 1 to 18 carbon atoms, and may include a functional group,
Sxe2x95x90Dxe2x80x83xe2x80x83General formula (13)
wherein, D represents a 5-membered or 6-membered nitrogen-containing heterocyclic or aromatic ring; said aromatic or heterocyclic ring may have a substituent, and further, the aromatic or heterocyclic ring may be condensed.
A fourth embodiment of the present invention is a light-heat-conversion type image formation material comprising a heat transfer sheet and an image receiving material, wherein said heat transfer sheet comprises a light-heat-conversion layer which includes an infrared light absorbing colorant and an image formation layer, the layers being provided in that order on a support, wherein said light-heat-conversion layer further includes one or more compounds having at least one functional group selected from a phosphate group, a phosphite group, an acid halide group, a sulfonic halide group, an acid anhydride group and an isocyanate group.
A fifth embodiment of the present invention is a light-heat-conversion type image formation material comprising a heat transfer sheet and an image receiving material, wherein said heat transfer sheet comprises a light-heat-conversion layer which includes an infrared light absorbing colorant and an image formation layer, the layers being provided in that order on a support, wherein said light-heat-conversion layer further includes at least one of compounds having an acidic group.
A sixth embodiment of the present invention is a light-heat-conversion type image formation material comprising a heat transfer sheet and an image receiving material, wherein said heat transfer sheet comprises a light-heat-conversion layer which includes an infrared light absorbing colorant and an image formation layer, the layers being provided in that order on a support, in which said light-heat-conversion layer further includes at least one or more compounds selected from compounds represented by the following general formula (10) and tautomers thereof and compounds represented by the following general formula (13):
Axe2x80x94Sxe2x80x94Bxe2x80x83xe2x80x83General formula (10)
wherein, A represents an aromatic ring or heterocyclic ring which may each have a substituent; B represents a hydrogen atom, xe2x80x94Sxe2x80x94Axe2x80x2, or xe2x80x94C(xe2x95x90O)R1; Axe2x80x2 represents an aromatic ring or heterocyclic ring which may each have a substituent, and may be the same as said A; and R1 represents an alkyl group which may be branched, has 1 to 18 carbon atoms, and may include a functional group,
Sxe2x95x90Dxe2x80x83xe2x80x83General formula (13)
wherein, D represents a 5-membered or 6-membered nitrogen-containing heterocyclic or aromatic ring; said aromatic or heterocyclic ring may have a substituent, and further, the aromatic or heterocyclic ring may be condensed.
According to the present invention, decomposition of an infrared light absorbing colorant with the lapse of time when the heat transfer sheet and the light-heat-conversion type image forming material is stored or the like, can be suppressed by adding an additive to a light-heat-conversion layer.
A heat transfer sheet and a light-heat-conversion type image forming material of the present invention will be illustrated in detail below.
Heat Transfer Sheet
A heat transfer sheet of the present invention comprises a light-heat-conversion layer containing an infrared light absorbing colorant and an image formation layer, disposed in that order on a support, the light-heat-conversion layer further contains at least one compound from any one of the groups which include a) compounds having at least one functional group selected from a phosphate group, a phosphite group, an acid halide group, a sulfonic halide group, an acid anhydride group and an isocyanate group, b) compounds having an acidic group, c) compounds represented by the following general formula (10), and tautomers thereof, and compounds represented by the following general formula (13).
xe2x80x83Axe2x80x94Sxe2x80x94Bxe2x80x83xe2x80x83General formula (10)
In the formula, A represents an aromatic ring or a heterocyclic ring which may each have a substituent; B represents a hydrogen atom, xe2x80x94Sxe2x80x94Axe2x80x2, or xe2x80x94C(xe2x95x90O)R1; Axe2x80x2 represents an aromatic ring or heterocyclic ring which may each have a substituent, and may be the same as said A; R1 represents an alkyl group which may be branched, has 1 to 18 carbon atoms, and may include a functional group,
Sxe2x95x90Dxe2x80x83xe2x80x83General formula (13)
In the formula, D represents a 5-membered or 6-membered nitrogen-containing heterocyclic or aromatic ring; said aromatic or heterocyclic ring may have a substituent, and further, the aromatic or heterocyclic ring may be condensed.
 less than Support greater than
The support used in the present invention may be any one having dimensional stability and showing heat tolerance at the time of image formation. Specific examples include: synthetic resin materials such as polyethylene terephthalate (PET), polyethylene-2,6-naphthalene, polycarbonate, polyethylene polyvinyl chloride, polyvinylidene chloride, polystyrene, styrene-acrylonitrile copolymer and the like. Of these, biaxially oriented polyethylene terephthalate is preferable in view of mechanical strength and dimensional stability with respect to heat.
When images are formed by irradiation with laser beam from the support side, it is preferable that this support is transparent. Further, when images are formed by irradiation with laser beam from the image formation layer side, it is not particularly necessary that this support is transparent.
The support may have cushioning property, to improve close adhesion with an image receiving material. In this case, materials having low elastic modulus, or materials having rubber elasticity are advantageously used. Specific examples thereof include elastomers such as natural rubber, acrylate rubber, butyl rubber, nitrile rubber, butadiene rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, urethane rubber, silicone rubber, acrylic rubber, fluororubber, neoprene rubber, chlorosulfonated polyethylene, epichlorohydrine, EPDM, urethane elastomer and the like, and resins having small elastic modulus among some polyethylenes, polypropylenes, polybutadienes, polybutenes, ABS resins having high impact-resistance, polyurethanes, ABS resins, acetates, cellulose acetates, amide resins, polytetrafluoroethylenes, nitrocelluloses, polystyrenes, epoxy resins, phenol-formaldehyde resins, polyesters, acrylic resins having impact resistance, styrene-butadiene copolymers, ethylene-vinyl acetate copolymers, acrylonitrile-butadiene copolymers, vinyl chloride-vinyl acetate copolymers, polyvinyl acetates, vinyl chloride resins containing a plasticizer, vinylidene chloride resins, polyvinyl chlorides, polyvinylidene chlorides and the like. The materials having low elastic modulus and materials having rubber elasticity may also be compounded in a base material of a support. Further, shape memory resins such as styrene-based hybrid polymers including polynorbornene or polybutadiene unit with a polystyrene unit may also be used.
The thickness of a support is not particularly restricted, and usually from 2 to 300 xcexcm, and preferably from 5 to 200 xcexcm. The thickness of a support having cushioning property is determined depending on various factors such as the kind of a resin or elastomer used, suction force at the time of close adhesion, particle size of a matting agent, amount of a matting agent used, and the like, but is usually from 10 to 100 xcexcm.
Further, a back coat layer for imparting functions such as stability when the sheet is conveyed, heat resistance, antistatic property and the like may also be provided on the side of a support opposite to the side on which a light-heat-conversion layer is mounted. The back coat layer is formed by applying on the surface of a support a coating solution for a back coat layer prepared by dissolving a resin such as nitrocellulose and the like in a solvent or a coating solution for a back coat layer obtained by dissolving or dispersing a binder resin and fine particles of 20 to 30 xcexcm in a solvent.
 less than Cushioning Layer greater than
A cushioning layer can be provided between a support and a light-heat-conversion layer. When dimensional stability is required, or a material having low elastic modulus is used, it is more preferable to provide a cushioning layer on a support having no cushioning property than to impart cushioning property to a support. Examples of the material of the cushioning layer, are the same as those for forming a support having cushioning property.
It is preferable that the thickness of a cushioning layer is usually from 10 to 100 xcexcm. However, the thickness is not limited to this range, and it is preferable to appropriately determine the thickness in view of various factors such as the kind of a resin or elastomer used, suction force at the time of close adhesion, particle size of a matting agent, amount of a matting agent used, and the like.
For forming a cushioning layer, components of the cushioning layer dissolved in various solvents or dispersed in the form of latex can be applied by a coating means such as a blade coater, roll coater, bar coater, curtain coater, gravure coater and the like, or according to an extrusion lamination method and the like.
By providing a cushioning layer, close adhesion is improved, however, the time necessary for superposing the sheet and the image receiving material under vacuum conditions does not change significantly. Rather, pressure reduction which is too rapid induces generation of an air bubbles. Further, for sufficiently securing close adhesion and reducing time necessary for vacuum adhesion simultaneously, it is preferable to roughen a heat transfer sheet.
For roughening a heat transfer sheet, there are listed a method in which the surface of a cushioning layer is previously subjected to roughening treatment and then a light-heat-conversion layer and an image formation layer are provided, a method in which a matting agent is contained in the surface of a heat transfer sheet, and other methods. The extent of roughening is preferably determined depending on elasticity and film thickness of a cushioning layer, pressuring force (vacuum degree), and surface roughness of a heat transfer sheet, particle size and amount added of a matting agent.
In roughening of the surface of a cushioning layer, the surface roughness Ra is preferably in the range from 0.3 to 10 xcexcm, though it varies depending on the material of which a cushioning layer is formed. The range is also approximately the same for roughening the surface of a heat transfer sheet.
 less than Light-Heat-Conversion Layer greater than
(Infrared Light Absorbing Colorant)
In a light-heat-conversion layer, an infrared light absorbing colorant is used as a light-heat-conversion substance. The infrared light absorbing colorants which can be used include an indolenine colorants and derivative thereof, a polymethine colorant and derivatives thereof, a phthalocyanine colorant and derivatives thereof, a naphthalocyanine colorant and derivatives thereof, a squalirium colorant and derivatives thereof, cyanine dyes, nitroso compounds and metal complex salts thereof, thiol nickel salts, a triallylmethane colorant and derivatives thereof, an immonium colorant and derivatives thereof, a naphthoquinone colorant and derivatives thereof, an anthraquinone colorant and derivatives thereof, an anthracene colorant and derivatives thereof, an azulene colorant and derivatives thereof, and the like. Specifically, the examples include groups of compounds described in Japanese Patent Application Laid-Open (JP-A) Nos. 62-87388, 63-264395, 63-319191,64-33547, 1-160683,1-280750, 1-293342,2-2064,2-2074, 3-26593, 3-30991, 3-30992, 3-34891, 3-36093, 3-36094, 3-36095, 3-42281, 3-63185, 3-97589, 3-97590, 3-97591, 3-103476, 3-124488, 3-132391, 4-140191, 4-161382, 4-169289, 4-169290, 4-173290, 4-173291, 5-32058, 5-201140, 5-221164, 5-338358, 6-24143, 6-32069, 6-115263, 6-210987, 6-255271, 6-309695, 7-101171, 7-149049, 7-172059, 7-195830, 9-58143, 9-80763, 10-207065, 10-268512, 11-95026, and 11-302610. The infrared light absorbing colorant used in the present invention are preferably those containing a methine group, and particularly, an indolenine colorant and derivatives thereof are preferable. Further, it is preferable that a light-heat-conversion layer contains two or more infrared light absorbing pigments.
(Additives)
A heat transfer sheet of the present invention may contain, as an additive in a light-heat-conversion layer,at least one of the compounds included in any one group selected from a) compounds having at least one functional group selected from a phosphate group, a phosphite group, an acid halide group, a sulfonic halide group, an acid anhydride group and an isocyanate group, b) compounds having an acidic group, c) compounds represented by the following general formula (10), and tautomers thereof, and compounds represented by the following general formula (13).
xe2x80x83Axe2x80x94Sxe2x80x94Bxe2x80x83xe2x80x83General formula (10)
In the formula, A represents an aromatic ring or a heterocyclic ring which may have a substituent; B represents a hydrogen atom, xe2x80x94Sxe2x80x94Axe2x80x2, or xe2x80x94C(xe2x95x90O)R1; Axe2x80x2 represents an aromatic ring or heterocyclic ring which may have a substituent, and may be the same as said A; R1 represents an alkyl group which may be branched, has 1 to 18 carbon atoms, and may include a functional group,
Sxe2x95x90Dxe2x80x83xe2x80x83General formula 13
In the formula, D represents a 5-membered or 6-membered nitrogen-containing heterocyclic or aromatic ring; said aromatic or heterocyclic ring may have a substituent, and further, the aromatic or heterocyclic ring may be condensed.
A heat transfer sheet or a coating solution thereof manifests, in general, reduction in recording abilities such as reduction in sensitivity, deterioration of resolution, and the like with the lapse of time when stored and the like. Particularly, this is remarkable under conditions of high temperature and high humidity. This is believed to be derived from decomposition of an infrared light absorbing colorant contained in a light-heat-conversion layer. Further, even if a heat transfer sheet is stored at room temperature, when the storage period is long, an infrared light absorbing colorant may sometimes be decomposed by the effect of the remaining solvent and the like in the film, providing a cause of reduction in recording abilities. Further, even if a light-heat-conversion layer is stored in the form of a coating solution, an infrared light absorbing colorant may sometimes be decomposed, a desired optical density is not obtained and reduction in image quality occurs.
For preventing such reduction in recording abilities of a heat transfer sheet, it is advantageous that a light-heat-conversion layer contains an additive having a quenching effect on oxidizer, and nucleophilic species and the like which cause decomposition of an infrared light absorbing colorant. In the present invention, by inclusion of the above-mentioned compound, reduction in recording abilities (optical density) of a heat transfer sheet can be prevented, and resolution can be improved.
The compounds having at least one functional group selected from a phosphate group, a phosphite group, an acid anhydride group, an acid halide group, a sulfonic halide group and an isocyanate group, used in the present invention, have a hydrogen atom, alkyl group or aryl group. The alkyl group and aryl group may also contain other functional group or groups. Further, compounds having an acid anhydride as a functional group may have closed ring structure.
Examples of the compounds having at least one functional group selected from a phosphate group, a phosphite group, an acid anhydride group, an acid halide group, a sulfonic halide group and an isocyanate group, used in the present invention, include compounds represented by the following general formulae (1) to (6). xe2x80x83R7xe2x80x94C(xe2x95x90O)xe2x80x94Oxe2x80x94C(xe2x95x90O)xe2x80x94R8xe2x80x83xe2x80x83General formula (3)
R9COXxe2x80x83xe2x80x83General formula (4)
R10SO2Xxe2x80x83xe2x80x83General formula (5)
R11NCOxe2x80x83xe2x80x83General formula (6)
In the formula, R1, R2, R3 R4, R5, R6, R7, R8, R9, R10, and R11 represent a hydrogen atom, an alkyl group or aryl group and said alkyl group and aryl group may include other functional group; R7 and R8 may be connected to have a closed ring structure; and X represents a halogen atom.
Preferable examples of the compounds having at least one functional group selected from a phosphate group, a phosphite group, an acid anhydride group, an acid halide group, a sulfonic halide group and an isocyanate group are the following compounds.
Trimethyl phosphate, triethyl phosphate, tributyl phosphate, triamyl phosphate, tri-2-ethylhexyl phosphate, tricycloethyl phosphate, triphenyl phosphate (these are phosphates), trimethyl phosphite, triethyl phosphite, tributyl phosphite, tridecyl phosphite, trilauryl phosphite, triocadecyl phosphite, triphenyl phosphite, dimethyl phosphite, diethyl phosphite, dibutyl phosphite, dipheyl phosphite (these are phosphates), maleic anhydride, succinic anhydride, glutaric anhydride, phthalic anhydride, acetic anhydride, isatoic anhydride, pyromellitic anhydride (these are acid anhydrides), acetic chloride, acetic bromide, propionic chloride, butanoic chloride, hexanoic chloride, octanoic chloride, lauric chloride, myristic chloride, palmitic chloride, stearic chloride, oleic chloride, acrylic chloride, methacrylic chloride, benzoic chloride, cinnamic chloride, phenylacetic chloride, oxalic dichloride, succinic dichloride, maleic dichloride, fumaric dichloride, phthalic dichloride, isophthalic dichloride, terephthalic dichloride, malonic dichloride, adipic dichloride, sebacic dichloride (these are acid halides), methanesulfonic dichloride, methanesulfonic chloride, p-toluenesulfonic chloride, benzenesulfonic chloride (these are sulfonic halides), n-butyl isocyanate, tert-butyl isocyanate, adamantyl isocyanate, octyl isocyanate, octadecyl isocyanate, phenyl isocyanate, cyclohexyl isocyanate, xylylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate (these are isocyanates) and the like.
The above-mentioned compound may contain two or more these functional groups in the sama molecule. Trimellitic anhydride mono-acid chloride and the like are examples.
Further, polymer compounds having at least one functional group selected from a phosphate group, a phosphite group, an acid anhydride group, an acid halide group, a sulfonic halide group and an isocyanate group may also be used as a compound to be contained in a light-heat-conversion layer. Use of a polymer compound as an additive is preferable since then, interlayer movement does not occur easily even under high humidity. For example, polymers of one or more polymerizable monomers (a) having at least one functional group selected from a phosphate group, a phosphite group, an acid anhydride group, an acid halide group, a sulfonic halide group and an isocyanate group, or copolymers of these polymerizable monomers (a) with polymerizable monomers other than the polymerizable monomers (a) may also be permissible. Further, polymer compounds may also be permissible which are obtained by exchanging functional groups of copolymers of polymerizable monomers (b) having a functional group other than a phosphate group, a phosphite group, an acid anhydride group, an acid halide group, a sulfonic halide group and an isocyanate group and polymerizable monomers other than the polymerizable monomers (b), for functional groups selected from a phosphate group, a phosphate group, an acid anhydride group, an acid halide group, a sulfonic halide group and an isocyanate group.
Examples of the polymerizable monomers having at least one functional group selected from a phosphate group, a phosphite group, an acid anhydride group, an acid halide group, a sulfonic halide group and an isocyanate group, include maleic anhydride, (meth)acrylic chloride, styrenesulfonic chloride, (meth)acryloyloxyethyl isocyanate, (meth)acryloyl isocyanate, and compounds represented by the following general formula (7) and the like.
[wherein, R14 represents a hydrogen atom or a methyl group, R15 represents an alkylene having 2 to 6 carbon atoms, R16 represents an alkyl group or aryl group. This alkyl group and aryl group may be substituted with a substituent. m is an integer from 1 to 3, and n is an integer from 0 to 2, providing n+m=3].
Examples of the polymer compound using these polymerizable monomers include, a styrene/maleic anhydride copolymer, methyl vinyl ether/maleic anhydride copolymer, (partial) reaction products of styrene/maleic anhydride copolymer with water, alcohol, and amines, (meth)acryloyloxyethyl isocyanate/(meth)acrylate copolymer, and the like.
The above-mentioned polymer compound may also be a polymer obtained by a polyaddition or polycondensation reaction. Examples of such a compound include polyamic acid obtained from di-acid anhydride and diamine, and the like.
The amount to be used of compounds represented by the general formulae (1) to (6) for suppressing decomposition of an infrared light absorbing colorant is preferably from 0.05 to 50 times the number of moles of the infrared light absorbing colorant. More preferably, it is in the range from 0.5 to 5 times the number of moles of the ingrared light absorbing colorant.
The compound having an acidic group used in the present invention is preferably a weak protonic acid having a carboxyl group, sulfonic group or the like. The pK of a compound having an acidic group is preferably in the range from 1 to 10. When the pK is greater than 10, the suppressing of decomposition of an infrared light absorbing colorant decreases, and when the pK is less than 1, a compound having an acidic group decomposes an infrared light absorbing colorant.
The compound having an acidic group used in the present invention may have an alkyl group or an aryl group. Further, this alkyl group or aryl group may also contain other functional group or groups.
Preferable examples of the compound having an acidic group are the following compounds:
acetic acid, propionic acid, butanoic acid, hexanoic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, acrylic acid, methacrylic acid, itaconic acid, benzoic acid, cinnamic acid, phenylacetic acid, oxalic acid, succinic acid, maleic acid, glutaric acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, malonic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid, tartaric acid, methanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid and the like.
The compound to be contained in a light-heat-conversion layer, may also be a polymer compound having an acidic group. Use of a polymer compound as an additive is preferable since then, interlayer movement does not occur easily even under conditions of high humidity. For example, polymers of at least one polymerizable monomer (a) having an acidic group, or copolymers of one of these polymerizable monomers (a) with a polymerizable monomer other than the polymerizable monomer (a) may also be used. Further, polymer compounds which are obtained by exchanging functional groups of copolymers of polymerizable monomers having no acidic group (b) and polymerizable monomers other than the polymerizable monomers (b),for acidic groups.
Examples of the polymerizable monomer having an acidic group include, (meth)acrylic acid, cinnamic acid, styrenesulfonic acid, styrenecarboxylic acid, maleic acid and the like. Examples of the polymer compound using these monomers include poly(meth)acrylic acid, (meth)acrylic acid/(meth)acrylate copolymer, and the like.
Further, polymers obtained by a polyaddition or polycondensation reaction are also permissible. Examples of such compounds include polyurethane and plyurea polymers and the like, obtained by polyaddition of a diamine or diol having an acidic group with a isocyanate.
Compounds represented by the general formula (8) or (9) can be used as a compound having an acidic group.
R1COOHxe2x80x83xe2x80x83General formula (8)
R2SO3Hxe2x80x83xe2x80x83General formula (9)
In the formulae, R1 and R2 represent an alkyl group or aryl group; and said alkyl group and aryl group may include other functional group or groups.
The addition amount of compounds represented by the general formula (8) or (9) for suppressing decomposition of an infrared light absorbing colorant is preferably from 0.05 to 50 times the number of moles of the infrared light absorbing colorant. More preferably, it is in the range from 0.5 to 5 times the number of moles of the infrared light absorbing colorant.
In the compound represented by the above-mentioned general formula (10) used in the present invention, A in the formula represents an aromatic ring or heterocyclic ring optionally having a substituent. Examples of the aromatic ring include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, azulene ring and the like, and of these, a benzene ring is preferable. As the above-mentioned heterocyclic ring, those containing a S atom or N atom are preferable. Further examples of the above-mentioned substituent are an alkyl group, aryl group, halogen group, hydroxyl group, amino group, ether group, thioether group, ester group, thioester group, thiol group, amide group, thioamid group, alkyl groups having a substituent and the like. Of these, an alkyl group, aryl group, hydroxyl group, thiol group, ether group, thioether group are preferable.
Specific examples of the above-mentioned A include, but are not limited to, the following (I-1) to (I-17).
In the compound represented by the above-mentioned general formula (10) used in the present invention, B in the formula represents a hydrogen atom, xe2x80x94Sxe2x80x94Axe2x80x2, or xe2x80x94C(xe2x95x90O)R1. Axe2x80x2 represents an aromatic ring or heterocyclic ring optionally having a substituent. The aromatic ring or heterocyclic ring may be the same rings as those listed as examles for A. Axe2x80x2 and A may be the same.
R1 represents an alkyl group which may be branched having 1 to 18 carbon atoms. Of these, alkyl groups having 1 to 4 carbon atoms are preferable. When the carbon number is over 18, the effect of suppressing decomposition of an infrared light absorbing colorant decreases. Further, R1 may have a functional group, which may be, a hydroxyl group, ether group, ester group, carbonate group and the like.
In the general formula (10), B is preferably a hydrogen atom, or xe2x80x94Sxe2x80x94Axe2x80x2 in which Axe2x80x2 is the same as A shown in the general formula (10).
In the general formula (10), xe2x80x94Sxe2x80x94B is selected from a thiol, a thioester having a protective group introduced by an ester, or a dimer structure comprised of thiols linked by a disulfide bond.
Specific examples of the thioester include acetates, trifluoroacetates, pivalates, propionates, 2-ethylhexanoates, decanoates, laurates, stearates and the like. The present invention is not limited to these.
The compound represented by the general formula (10) is preferably a compound represented by the following general formula (11) or the general formula (12).
In the above-mentioned general formulae (11) and (12), X each independently represents an atomic group forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring, and in the general formula (12), atomic groups represented by X may be the same or different. In the nitrogen-containing heterocyclic ring, an aromatic ring and a heterocyclic ring may also be condensed. The aromatic ring and heterocyclic ring may be the same rings as those listed as examples for A. Further, the aromatic ring and heterocyclic ring may have a substituent, and as the substituent, the same groups as described above are listed.
In the general formula (11), Bxe2x80x2 represents a hydrogen atom or xe2x80x94C(xe2x95x90O)R2. R2 represents an alkyl group which may be branched having 1 to 18 carbon atoms. Of these, alkyl groups having 1 to 4 carbon atoms are preferable. When the number of carbon atoms is over 18, the effect of suppressing decomposition of an infrared light absorbing colorant is decreased. Further, the above-mentioned R2 may have a functional group, and as this functional group, a hydroxyl group, ether group, ester group, carbonate group and the like are listed.
Specific examples (II-1) to (II-26) of compounds represented by the general formulae (10) to (12) are listed below, but the present invention is not limited to these.
[Tautomer]
In addition to compounds represented by the general formula (10), the compounds to be contained in a light-heat-conversion layer of the present invention may also include tautomers having a relationship described below with a compound represented by the general formula (10).
Specific examples (III-1) to (III-7) of compounds having a tautomeric relationship with a compound represented by the above-mentioned general formulae (10) to (12) are listed below, but the present invention is not limited to these compounds.
In the compound represented by the above-mentioned general formula (13) used in the present invention, D in the formula represents a 5-membered or 6-membered nitrogen-containing heterocyclic ring or aromatic ring. The aromatic ring and heterocyclic ring may have a substituent, and as the substituent, the same groups as described above are listed. Further, as the above-mentioned heterocyclic ring, those containing an S atom or N atom are preferable. Further, as the above-mentioned substituent, the same substituents as described above are listed.
In the above-mentioned aromatic ring and heterocyclic ring, the aromatic ring or heterocyclic ring may also be condensed, further.
As the compound represented by the general formula (13), compounds having a tautomeric relationship with a compound represented by the general formulae (10) are also included. Specific examples of the compound represented by the general formula (13) are listed below, but the present invention is not limited to these.
The amount of a compound represented by the general formula (10) or (13) to be added to a light-heat-conversion layer is preferably from 0.1 to 10 mol for each mol of an infrared light absorbing colorant contained in a light-heat-conversion layer. It is more preferably from 0.5 to 5 mol, and an amount from 1 to 2 mol for each mol of an infrared light absorbing colorant is particularly preferable. When the amount of an additive represented by the general formula (10) or (13) is over 10 mol for each mol of an infrared light absorbing colorant contained in a light-heat-conversion layer, there is a possibility that side actions such as bleeding of the additive onto the surface layer, and the like may occur, decreasing abilities of a heat transfer sheet. On the other hand, when the above-mentioned addition amount is less than 0.1 mol, the effect of the present invention can not be sufficiently achieved.
(Binder)
As the binder used in a light-heat-conversion layer, resins having a high glass transition temperature and high heat conductivity, for example, general heat-resistant resins such as polymethyl methacrylate, polycarbonate, polystyrene, ethylcellulose, nitrocellulose, polyvinyl alcohol, polyvinyl chloride, amide-based resins, polyimide, poyetherimide, polysulfone, polyether sulfone, aramide and the like, can be used. Among them, polyvinyl alcohol is particularly preferable since it does not easily cause scattering of a light-heat-conversion layer. Further, a polyimide resin is particularly preferable from the standpoint of heat-resistance.
The film thickness of a light-heat-conversion layer is preferably from 0.1 to 3 xcexcm. The optical density of a light-heat-conversion layer at wavelengths from 800 to 830 nm is required to be from 0.3 to 2.0. When the optical density is less than 0.3, irradiated light cannot be converted into heat, and when over 2.0, a light-heat-conversion layer is decomposed at the time of recording, thereby causing fogging.
 less than Image Formation Layer greater than
In a heat transfer sheet of the present invention, an image formation layer is provided on a light-heat-conversion layer or a peel layer described below. In the present invention, the image formation layer means a layer which is transferred to an image receiving material by ablation or heat melting at the time of heating. The image formation layer contains a pigment, and an amorphous organic polymer compound. It is not necessary for this image formation layer to be transferred in a completely melted state.
(Coloring Material)
The coloring material to be contained in an image formation layer include pigments and dyes. Pigments are generally classified roughly into an organic pigments and an inorganic pigments, and the former is excellent particularly in transparency of a coated film, and the latter is generally excellent in masking property. Examples of the inorganic pigment include titanium dioxide, carbon black, zinc oxide, Prussian blue, cadmium sulfide, iron oxide, and chromates of lead, zinc, barium and calcium, and the like. Examples of the organic pigment include azo-based pigments, thioindigo-based pigments, anthraquinone-based pigments, anthanthrone-based pigments, triphenedioxazine-based pigment, bat dye pigments, isoindolinone-based pigments, nitro-based pigments, phthalocyanine-based pigments, for example, copper phthalocyanine and derivatives thereof, and quinacridone-based pigments and the like.
The content of pigments in an image formation layer is preferably from 20 to 80% by weight.
Further, a dye may also be used as the coloring material. The organic dyes include acidic dyes, direct dyes, dispersed dyes, oil-soluble dyes, metal-containing oil-soluble dyes and heat sublimation colorants. Examples of this heat sublimation colorant include cyan colorants, magenta colorants and yellow colorants.
Examples of the above-mentioned cyan colorant are naphthquinone-based colorants, anthraquinone-based colorants, azomethine-based colorants and the like described in JP-A Nos. 59-78896, 59-227948, 60-24966, 60-53563, 60-130735, 60-131292, 60-239289, 61-19396, 61-22993, 61-31292, 61-31467, 61-35994, 61-49893, 61-148269, 62-191191, 63-91288, 63-91287, 63-290793, and the like.
Examples of the magenta colorant are anthraquinone-based colorants, azo-based colorants, azomethine-based colorants and the like described in JP-A Nos. 59-78896, 60-30392, 60-30394, 60-253595, 61-262190, 63-5992, 63-205288, 64-159, 64-63194, and the like.
Examples of the yellow colorant are methine-based colorants, azo-based colorants, quinophthalone-based colorants, anthraisothiazole-based colorants and the like described in JP-A Nos. 59-78896, 60-27594, 60-31560, 60-53565, 61-12394, 63-122594, and the like.
The heat sublimation colorants are preferably azomethine colorants obtained by a coupling reaction of compounds having a open chain type or closed chain type active methylene group with an oxidized p-phenylenediamine derivative or an oxidized a p-aminophenol derivative, and indoaniline colorants obtained by a coupling reaction with phenol or naphthol derivative, an oxidezed p-phenylenediamine derivative or an oxidized a p-aminophenol derivative.
The heat sublimation colorant to be contained in an image formation layer may be any of yellow colorants, magenta colorants and cyan colorants, providing an image formed has a single color.
The content of a coloring material in an image formation layer is usually in the range from 5 to 70% by weight, and preferably in the range from 30 to 70% by weight.
(Binding Agent)
As the binding agents which can be used in an image formation layer of the present invention, substances which melt when heated, substances which soften when heated and thermoplastic resins are listed. The substance which melts when heated is usually a solid or semi-solid substance having melting temperatures in the range from 40 to 150xc2x0 C. measured by using Yanagimoto MJP-2 type apparatus.
Specific examples of the substance which melts when heated include waxes like vegetable wax such as carnauba wax, haze wax, auricury wax, espar wax and the like; animal wax such as beeswax, insect wax, shellac wax, spermaceti and the like; petroleum wax such as paraffin wax, microcrystalline wax, polyethylene wax, ester wax and acid wax and the like; and mineral wax such as montan wax, ozokerite, ceresin and the like, and in addition to these waxes; higher fatty acids such as palmitic acid, stearic acid, margaric acid, behenic acid and the like; higher alcohols such as palmityl alcohol, stearyl alcohol, behenyl alcohol, marganyl alcohol, myricyl alcohol, eicosanol and the like; higher fatty esters such as cetyl palmitate, myricyl palmitate, cetyl stearate, myricyl stearate and the like; amides such as acetamide, propionic amide, palmitic amide, stearic amide, amid wax and the like; and higher amines such as stearylamine, behenylamine, palmitylamine and the like, and these may be used alone or in combination.
Specific examples of the substance which soften when heated include, waxes such as vegetable wax, animal wax, petroleum wax, mineral wax and the like. Further, in addition to these waxes, higher fatty acids, higher alcohols, higher fatty esters, amides and higher amines and the like are listed.
(Amorphous Organic Polymer)
Further, amorphous organic polymers having softening temperatures from 40 to 150xc2x0 C. are also preferable. As such amorphous organic polymers, for example, a polyviylbutyral resin, butyral resin, polyamide resin, polyethyleneimine resin, sulfonamide resin, polyester polyol resin, petroleum resin, homopolymers and copolymers of styrene, derivatives thereof and substituted materials thereof such as styrene, vinyltoluene, xcex1-methylstyrene, 2-methylstyrene, chlorostyrene, vinylbenzoic acid, sodium vinylbenzensulfonate, aminostyrene and the like, homopolymers or copolymers with other monomers of vinyl-based monomers such as methacrylates such as methyl methacryalte, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacryalte and the like and methacrylic acid, acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, xcex1-ethylhexyl acrylate and the like and acrylic acid, dienes such as butadiene, isoprene and the like, acrylonitrile, vinyl ethers, maleic acid and maleates, maleic anhydride, cinnamic acid, vinyl chloride, vinyl acetate and the like, can be used. These resins can be used in admixture of two or more.
The thermoplastic resin includes polymer compounds having softening temperatures from 50 to 150xc2x0 C. and the like. These include resins such as an ethylene copolymer, polyamide resins, polyester resin, polyurethane resin, polyolefin resin, acrylic resin, vinyl chloride resin, cellulose resin, rosin resin, ionomer resin and petroleum resin and the like; elastomers such as natural rubber, styrene-butadiene rubber, isoprene rubber, chloroprene rubber and the like; rosin derivatives such as ester gum, rosin-maleic acid resin, rosin-phenol resin, hydrogenated rosin and the like; phenol resins, terpene resins, cyclopentadiene resins, aromatic hydrocarbon resins and the like.
Among these binding agents, amorphous organic polymers having softening temperatures from 40 to 150xc2x0 C. are preferably used. The content of the amorphous organic polymer in an image formation layer is from 20 to 80% by weight, preferably from 30 to 70% by weight, particularly preferably from 40 to 60% by weight.
The image formation layer may further contain surfactants, inorganic or organic fine particles (metal powder, silica gel and the like), oils (linseed oil, mineral oil and the like) and the like, in addition to the above-mentioned components. Excepting the case of obtaining black images, energy required for transfer can be reduced by inclusion of a substance which absorbs the wavelength of a light source used in image recording. As the substance which absorbs the wavelength of a light source, any of pigments and dyes may be used, however, in the case of obtaining color images, it is preferable from the standpoint of color reproduction that a dye manifesting little absorption in visible portions and large absorption of the wavelength of a light source is used in image recording by using a light source of infrared ray such as semi-conductor laser and the like. Examples of a near infrared dye include compounds described in JP-A No. 3-103476.
(Matting Agent)
A matting agent can be added to an image formation layer. When a support has cushioning property, or when a cushion layer which has not been roughened is provided on a support, it is preferable to add a matting agent to the image formation layer, for roughening of the surface. Examples of the matting agent are inorganic fine particles and organic fine particles. Examples of this inorganic fine particle include particles of metal salts such as silica, titanium oxide, aluminum oxide, zinc oxide, magnesium oxide, barium sulfate, magnesium sulfate, aluminum hydroxide, magnesium hydroxide, boron nitride and the like, kaolin, clay, talc, zinc white, white lead, sieglite, quartz, diatomaceous earth, pearlite, bentonite, mica, synthetic mica, and the like. Examples of the organic fine particle include resin particles such as a fluoroplastic particle, guanamine resin particle, acrylic resin particle, styrene-acrylic copolymer resin particle, silicone resin particle, melamine resin particle, epoxy resin particle and the like.
If a matting agent which is broken by pressure when a heat transfer sheet and an image receiving material are laminated and pressed or heat-pressed in transferring images is contained in a heat transfer sheet, a cushioning effect can be obtained even if a cushion layer is not provided on, or cushioning property is not imparted to a support.
Examples of the matting agent which is broken when pressure is applied include fine particles made of materials having rubber elasticity. Specific examples inlude elastomers such as acrylate rubber, butyl rubber, nitrile rubber, butadiene rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, urethane rubber, silicone rubber, acrylic rubber, fluororubber, neoprene rubber, chlorosulfonated polyethylene, epichlorohydrine, EPDM, and the like. Examples of the matting agent which is broken by pressing with heat, fine particles composed of wax having low hardness such as paraffin wax, beeswax, wax having significant oil content, wax containing lower molecular components in considerable amount, and the like, can be used. A heat transfer sheet roughened by this wax fine particles can be produced at a temperature lower than the melt initiation temperature of wax which forms fine particles, by 10xc2x0 C. or more.
The particle size of the matting agent is usually from 0.3 to 30 xcexcm, preferably from 0.5 to 20 xcexcm, and the addition amount thereof is from 0.1 to 100 mg/m2.
The thickness of an image formation layer is usually in the range from 0.1 to 3 xcexcm, and preferably in the range from 0.2 to 1.0 xcexcm.
(Scatter Prevention Layer)
If high intensity energy such as laser beam and the like is used as light source, a scatter prevention layer may be provided to prevent scattering of a light-heat-conversion substance or a binder due to heat generated when the above-mentioned light-heat-conversion layer rapidly absorbs light energy. The scatter prevention layer is preferably composed of a material having sufficient strength to suppress scattering of a light-heat-conversion layer, with a thin film, and having high heat conductivity to enable heat generated in a light-heat-conversion layer to be transferred quickly to an image formation layer. The scatter prevention layer is formed of general heat-resistant resins etc. such as those used as the binder in a light-heat-conversion layer. However, of these polyvinyl alcohol is preferable since it has large scatter preventing effect, it can be dissolved in water and then applied, and mixing with an image formation layer or light-heat-conversion layer is small.
When irradiation with light is effected from the support side of a heat transfer sheet, a scatter prevention layer may also be opaque, and a metal deposited film such as aluminum and the like also have a scatter preventing effect. When the film thickness of a scatter prevention layer is smaller, sensitivity is higher, and when the thickness is large, a scatter preventing effect is higher, and generally, the thickness is from 0.05 to 1.0 xcexcm.
(Peel Layer)
A peel layer can be provided between a light-heat-conversion layer and an image formation layer. Owing to the presence of a peel layer, peeling of an image formation layer at the time of heat-sensitive transfer recording becomes easy, and image of high quality can be obtained. Though the peel layer can be composed of a compound which melts when heated, it is usually preferable that the peel layer is composed of a binder resin and the like such as a compound which melts when heated and/or thermoplastic resin and the like.
The compound which melts when heated used as the main component of the peel layer may be appropriately selected from known compounds. Specific examples thereof include those in JP-A No. 63-193886, p. 4, upper left column, line 8 to upper right column, line 12. Specific examples of the thermoplastic resin include ethylene copolymers such as an ethylene-vinyl acetate resin and the like, polyamide resins, polyester resins, polyurethane resins, polyolefine resins, acrylic resins and cellulose resins and the like. In addition, for example, resins such as vinyl chloride resins, rosin resins, petroleum resins, ionomer resins and the like, elastomers such as natural rubber, styrene-butadiene rubber, isoprene rubber, chloroprene rubber and the like, ester gum, rosin-derivatives such as rosin-maleic acid resins, rosin-phenol resins and hydrogenated rosins and the like, and phenol resins, terpene resins, cyclopentadiene resins and aromatic resins and the like can also be used depending on the case.
In the present invention, of the thermoplastic resin which can be used as a component of a peel layer, those having melting temperatures or softening temperatures usually in the range from 50 to 150xc2x0 C., particularly in the range from 60 to 120xc2x0 C., or those which obtain such a range by two or more of them being mixed, are suitably used.
 less than Production of Heat Transfer Sheet greater than
For production of a heat transfer sheet of the present invention, the above-mentioned components forming respective layers are first mixed while being heated, or dispersed or dissolved the components in a solvent, to prepare coating solutions for forming respective layers. These coating solutions are applied sequentially on the surface of a support, and if necessary, a solvent is removed, to obtain the desired heat transfer sheet.
The solvent for preparing a coating solution include water, alcohols (e.g., ethanol, or methanol), cellosolves (e.g., methylcellosolve, or ethylcellosolve), aromatics (e.g., toluene, xylene, or chlorobenzene), ketones (e.g., acetone, or methyl ethyl ketone), ester solvents (e.g., ethyl acetate, or butyl acetate), ethers (e.g., tetrahydrofuran, or dioxane), chlorine-containing solvents (e.g., chloroform, or trichloroethylene) and the like.
The coating method may be a conventionally known gravure roll coating method, extrusion coating method, wire bar coating method, roll coating method and the like.
The image formation layer may be formed as a layer containing coloring materials of a single color in the whole surface or parts of the surface of a support. Alternatively, yellow image formation layers containing a binder and a yellow colorant, magenta image formation layers containing a binder and a magenta colorant, and cyan image formation layers containing a binder and a cyan colorant may be repeatedly formed on the whole surface or parts of the surface of a support along the plane direction. Further, these image formation layers having the respective colors may also be laminated.
Use of a heat transfer sheet, can be facilitated by forming perforations or providing detection marks for detecting positions of regions of different hues.
Light-Heat-Conversion Type Image Formation Material
A light-heat-conversion material of the present invention is composed of the above-mentioned heat transfer sheet of the present invention and image receiving materials (including an image receiving material used as an intermediate transfer body).
 less than Image Receiving Material greater than
The image receiving material indicates an image recording medium which receives an image formation layer which has been peeled image-wise from a heat transfer sheet, to thereby form images. This image receiving material usually has a support and an image receiving layer, however, it may be formed only of a support in some cases.
The image receiving material is not particularly restricted providing it can be applied to a heat transfer sheet of the present invention, however, it is desirable that it has appropriate heat-resistance since an image formation layer melted by heat is transferred to the image receiving material and that it has excellent dimensional stability so that images are formed appropriately.
 less than Support greater than
Examples support of an image receiving material include resin films or resin sheets and the like made of polyethylene, polypropylene, polyethylene terephthalate, polystyrene, polyvinyl chloride, polyimide and the like when images are seen through the support from the surface opposite that having the transferred images. Further, when images are not seen through the support from the surface opposite that having the transferred images, but are seen from the surface on which transferred images (reflection image) are formed, white films formed by adding a white pigment such as barium sulfate, calcium carbonate, titanium oxide and the like to a resin film or a resin sheet, and papers such as coated paper, art paper, RC paper and the like, etc., can be used as the support. The thickness of the support of an image receiving material is usually from 10 to 400 xcexcm, preferably from 25 to 200 xcexcm. Further, the support is preferable a white material containing air spaces such as air bubbles and the like from the standpoint of cushioning property, visibility of images and the like. Particularly, a foamed polyester support such as white polyethylene terephthalate and the like is most preferable from the standpoint of mechanical properties. The surface of a support may also be subjected to surface treatments such as a corona discharge treatment, glow discharge treatment and the like in order to increase adhesion with the image receiving layer.
In order to impart cushioning properties to the support, the support may be formed of the above mentioned materials which impart cushioning properties. It may also be formed of a composite film or composite sheet formed by combining the resin film or the resin sheet with a film or sheet formed from the material which imparts cushioning properties.
The support is formed of a binder and various additives as necessary. When the support does not have cushioning property, the above-mentioned material for imparting cushioning property may also be added to an image receiving layer.
 less than Image Receiving Layer greater than
The image receiving layer is a layer formed mainly of an organic polymer binder. The binder is preferably a thermoplastic resin, example of which include: homopolymers and copolymers of acrylic monomers such as acrylic acid, methacrylic acid, acrylate, methacrylate and the like; cellulose polymers such as methylcellulose, ethylcellulose, cellulose acetate and the like; homopolymers and copolymers of vinyl-based monomers such as polystyrene, polyvinylpyrrolidone, polyvinylbutyral, polyvinyl alcohol, polyvinyl chloride and the like; condensed type polymers such as polyester, polyamide and the like; rubber polymers such as a butadiene-styrene copolymer. The binder in an image receiving layer is preferably a polymer having a glass transition temperature (Tg) lower than 90xc2x0 C., in order to obtain appropriate adhesive force between the image receiving layer and an image formation layer. It is also possible to add a plasticizer to the image receiving layer in order obtain an appropriate adhesive force. Further, the binder polymer in the image receiving layer preferably has a Tg of 30xc2x0 C. or more, in order to prevent blocking between sheets. It is particularly preferable that the binder polymer in the image receiving layer is the same polymer as the binder polymer in an image formation layer or one similar to it in order to improve adhesion with the image formation layer in laser recording, and to improve sensitivity and image strength.
The thickness of the image receiving layer is from 0.3 to 7 xcexcm, preferably from 0.7 to 4 xcexcm. When it is 0.3 xcexcm or less, film strength at the time of re-transfer to printing paper is deficient, easily leading to breakage. When it is too thick, gloss of images after re-transfer to paper increases, and likeness of transferred image to the printed product lowers.
 less than Cushioning Layer greater than
In an image receiving material of the present invention, it is preferable to provide a cushioning layer between a support and an image receiving layer instead of imparting cushioning property to the support or image receiving layer. In this case, detailed descriptions of the cushioning layer will be omitted since this is the same as the above-mentioned cushioning layer in a heat transfer sheet. The thickness of a support in an image receiving material containing a support, cushioning layer and image receiving layer, or the thickness of a support in an image receiving material formed only of a support, is not particularly restricted. The thickness of the cushioning layer is the same as the thickness of the cushioning layer in a heat transfer sheet. The thickness of an image receiving layer is usually from 0.1 to 20 xcexcm, however, this is not the case when a cushioning layer is used as an image receiving layer.
The surface of an image receiving material which will be in contact with a heat transfer sheet in forming images may have excellent smoothness, or may have been roughened appropriately. Further, when the surface of an image formation layer of a heat transfer sheet is roughened by addition of the above-mentioned matting agent or by roughening of a cushioning layer, it is preferable that this surface of an image receiving material which will contact a heat transfer sheet has excellent smoothness. On the other hand, when an image formation layer is not roughened, it is preferable that the surface of the image receiving material which will contact an image formation layer is roughened by addition of the above-mentioned matting agent or by roughening of a cushioning layer. Further, both of an image formation layer, and the surface of an image receiving material which contact the image formation layer may also be roughened. In the case where the both the heat transfer sheet and the image receiving material have not been roughened, it is preferable that the image receiving material having a cushioning layer is subjected to a roughening process immediately before the heat transfer sheet and the image receiving material are closely adhered to each other, and then when they are in a state of being closely adhered due to a vacuum, the roughened parts are made smooth once again.
 less than Matting Agent greater than
The matting agent used for the image receiving layer are the same as for the heat transfer sheet. Therefore, the detailed descriptions are omitted. By using a matting agent which breaks due to pressure or due to a combination of heat and pressure, it is not necessary to use a material or an image receiving layer having cushioning properties for the image receiving material, nor is it necessary to provide a cushioning layer. This is the same as the case for the matting agent of the heat transfer sheet.
By using a matting agent in a heat transfer sheet or an image receiving material, and suitably roughening a contact surface between a heat transfer sheet and an image receiving material, the disadvantage of excessively close adhesion of the surfaces to each other can be eliminated. On the other hand, disadvantages caused by use of a matting agent, namely, generation of unevenness at the time of close adhesion, reduction in resolution, color turbidity and the like can be eliminated by imparting cushioning property to the image receiving material.
The above-described image receiving material can be utilized as a final image recording material when images are transferred and formed by a heat transfer sheet.
When a plurality of heat transfer sheets having colorants with different colors from each other, and one image receiving material are used, and an image formation layer having single color is transferred image-wise by respective heat transfer sheet to the image receiving material to form multi-color of full color transferred images, then, it is necessary that the image receiving material has cushioning property. Particularly, it is preferable to form a support having cushioning property or a cushioning layer with a recoverable shape memory resin.
 less than Image Receiving Material Used as an Intermediate Transfer Body greater than
In general, when an image formation layer is heat-transferred image-wise by a heat transfer sheet to an image receiving material, it is preferable that the surface of an image receiving material is smooth in order to obtain transferred images having high image quality. In other words, with an image receiving material having low surface smoothness, images having high quality cannot be recorded.
For forming images of high quality on an image receiving material having low surface smoothness, it is preferable to first transfer images to an image receiving material used as an intermediate transfer body having high surface smoothness by a heat transfer sheet, then, to re-transfer images to an image receiving material having low surface smoothness.
This image receiving material used as an intermediate transfer body can have the same composition as that of the final image receiving material. However, it is necessary that an image receiving material used as an intermediate transfer body has cushioning property. Further, an image receiving material used as an intermediate transfer body is not required to be roughened. When an image receiving material used as an intermediate transfer body has a cushioning layer, the thickness thereof is preferably at least 20 xcexcm or more since when high quality paper, for example, is used, it usually has a swell of 10 to 20 xcexcm.
It is desired that an image receiving material which is used as an intermediate transfer body has excellent ability to receive an image formation layer and has excellent re-transfer property to the final image receiving material. Examples of the image receiving material used as an intermediate transfer body and has the desired propertie include polyethylene, polypropylene, ethylene-vinyl acetate copolymer of low VA type, ethylene-ethyl acrylate copolymer (EEA), ethylene-methacrylate copolymer (EMA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-vinyl acetate copolymer, ionomer resin, chlorinated ethylene, chlorinated polypropylene, chlorinated polyolefin, butadiene rubber, isoprene rubber, SBR, SBS, SIP, polyvinylbutyral, polyvinyl acetal, polyvinyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, olefin polymers such as various acrylic resins and the like, polyester resin, polyurethane resin, polyamide resin, celluloses such as nitrocellulose, cellulose acetate, ethylcellulose and the like, fluoroplastic, silicone resin and the like.
An image receiving material used as an intermediate transfer body is laminated with the final image receiving material, and pressurized or heat-pressurized to re-transfer images of the image receiving material used as an intermediate transfer body to the surface of the final image receiving material. When monochrome images are re-transferred, one image receiving material which is an intermediate transfer body and one final image receiving material are used. When multi-color re-transfer images or full-color re-transfer images are transferred to the final image receiving material, a plurality of image receiving materials which are intermediate transfer bodies may be used for one final image receiving material, or, multi-color or full-color transfer images may be transferred and formed on one image receiving material used as an intermediate transfer body, which is then re-transferred to the final image receiving material.
Both when monochrome images are re-transferred and when multi-color images or full-color images are re-transferred, any of a method to re-transfer the whole image receiving layer of an image receiving material used as an intermediate transfer body to the final image receiving material, and a method to re-transfer transferred images on an image receiving material used as an intermediate transfer body without transferring the image receiving layer, can be used.
When images only are re-transferred without re-transferring an image receiving layer, it is preferable that the image receiving layer of an image receiving material used as an intermediate transfer body does not adhere to the final image receiving material.
Further, when re-transferring is effected while heating, it is desired that the image receiving layer of an image receiving material used as an intermediate transfer body does not have heat sealing properties at the time of re-transferring. When the method is such that re-transfer is carried out while the image receiving material is being heated, it is necessary to provide a means for preventing the image receiving layer and the cushioning layer which are on the image receiving material used as an intermediate transfer body from being stripped off due to heat. An examples of such a means is providing an adhesive layer between the image receiving layer and the cushioning layer.
When image are re-transferred together with the image receiving layer of an image receiving material used as an intermediate transfer body, it is preferable that unlike the above-described case a peelable layer is intercalated between the image receiving layer and cushioning layer.
An image receiving material comprising a cushioning layer and an image receiving layer on a support and an image receiving material used as an intermediate transfer body can be obtained by mixing the above-mentioned components for forming the respective layers while heating, or else by dispersing or dissolving the components in a solvent to prepare coating solutions for forming the layers, then, applying the coating solutions on a support, if necessary removing the solvent and then repeating the process for applying and drying the solution.
Examples of the solvent used for application of coating solutions for forming the layers include water, alcohols (e.g., ethanol, or propanol, etc.), cellosolves (e.g., methylcellosolve, or ethylcellosolve, etc.), aromatics (e.g., toluene, xylene, or chlorobenzene, etc.), ketones (e.g., acetone, or methyl ethyl ketone, etc.), ester solvents (e.g., ethyl acetate, or butyl acetate, etc.), ethers (e.g., tetrahydrofuran, or dioxane, etc.), chlorine-containing solvents (e.g., methylene chloride, chloroform, or trichloroethylene, etc.) and the like.
For application of coating solutions for forming various layers, conventionally known gravure roll coating method, extrusion coating method, wire bar coating method, roll coating method and the like can be adopted. In addition to the above-mentioned coating methods, an image receiving layer can be formed by a hot melt extrusion-lamination method and the like in which a mixture containing components for forming an image receiving layer is melt-extruded and laminated.
Lamination by a hot melt extrusion-laminate method can be effected by usual methods described in JP-A Nos. 1-263081, 1-271289, 2-106397, 2-111586, 2-305688, 3-49991 and the like.
Image Formation
 less than Monochrome Image greater than
A heat transfer recording method to form a monochrome image using a heat transfer sheet of the present invention is conducted as follows. First, a heat transfer sheet and an image receiving material are superposed on a substrate. In this case, either of the heat transfer sheet or an image receiving material may be placed first on a substrate.
As the substrate, any of a cylindrical drum and a flat substrate can be used. Preferable is a cylindrical drum. When a cylindrical drum is used as a substrate, transferred images can be formed at higher speed by high-speed rotation. Further, by decreasing the space for a light irradiation system and by simplifing the optical system, energy efficiency when laser light and the like is used can be enhanced. Thus the apparatus can also be made more compact.
At the time of this operation, a heat transfer sheet and/or an image receiving material are brought into close contact with to a substrate. The means for bringing a heat transfer sheet or image receiving material in close contact with a substrate are not particularly restricted, and an example is providing a plurality of penetration holes in a substrate, and effecting exhaustion through the penetration holes using an exhaustion means, to thereby fix a heat transfer sheet or an image receiving material on the substrate by a suction force caused by the exhaustion.
In order to improve an adhesion property between the image receiving material and a substrate, if necessary, a cover sheet can be covered over a light-heat-conversion type image formation material which is a laminate of a heat transfer sheet and an image receiving material, or the size of an outer sheet can be made larger slightly than the size of an inner sheet.
A method for closely adhering and for separating two sheets, is disclosed in Japanese Utility Model Application Laid-Open No. 63-87031.
For decreasing the time it takes to closely adhere the sheets to the substrate, it is preferable to apply pressure reduction while squeezing a heat transfer sheet and an image receiving material. Further, if at least one of a heat transfer sheet and an image receiving material has a cushioning layer, when the heat transfer sheet or the image receiving material is closely adhered by first forcefully applying reduced pressure, the degree of vacuum necessary for maintaining the close-adhesion thereafter may be reduced. Therefore, if vacuum degree is once raised to a high enough level at the time of close adhesion, a high degree of vacuum is not required at the time of recording and this is advantageous in terms of the design of the apparatus.
The degree of vacuum necessary for close-adhesion by vacuum suction is from 13.3 to 4.67xc3x97104 Pa though it varies depending on the extent to which the surfaces of a heat transfer sheet and image receiving material has been roughened, and after completion of close-adhesion, it may be lower. The pressurizing force when a light-heat-conversion type image formation material into which a matting agent is compounded is pressurized, is usually from 0.1 to 5 kg/cm2. When a matting agent having small particle size is used, the pressurizing force may be small, while when a matting agent having larger particle size is used, it is necessary to increase pressurizing force.
After closely adhering a light-heat-conversion type image formation material to a substrate, irradiation with light, for example, laser beam is effected image-wise from the rear side of a support if the support is transparent or from the cover sheet side. A laser beam is converted into heat by an infrared light absorbing colorant in a heat transfer sheet then an image formation layer is melted image-wise and adhered to an image receiving material. If, thereafter, the heat transfer sheet is stripped from the image receiving material, an image receiving material on which monochrome images are adhered image-wise can be obtained.
 less than Multi-Color, Full-Color Image greater than
For obtaining multi-color images or full-color images, first, a heat transfer sheet is prepared which comprises a cyan image formation layer, a magenta image formation layer and a yellow image formation layer formed sequentially on a support. Alternatively, a monochrome heat transfer sheet having a cyan image formation layer on a support, a monochrome heat transfer sheet having a magenta image formation layer on a support, and a monochrome heat transfer sheet having a yellow image formation layer on a support, are prepared.
Then, an image receiving material is fixed on a substrate by suction action, and a heat transfer sheet is laminated thereon. In the case of formation of multi-color images or full-color images, it is necessary to repeatedly change the heat transfer sheet under a condition in which an image receiving material is closely adhered to a substrate by suction. Therefore, for forming images in a short period of time, it is preferable not to use a cover sheet.
As described above, irradiation with light is effected image-wise to form, for example, cyan images on the surface of an image receiving material, and a heat transfer sheet is peeled from the surface of an image receiving material. Then, a heat transfer sheet having a different color is laminated, and irradiation with light is effected image-wise in the same manner as described above, to form, for example, magenta images. After formation of the images, this heat transfer sheet is peeled from an image receiving material, and a heat transfer sheet having another color is laminated to the image receiving material. Then, irradiation with light is effected image-wise, to form, for example, yellow images.
It is necessary to fix an image receiving material on a substrate so as not to cause color displacement during the changing of the plurality of heat transfer sheets. Therefore, it is desirable that the surface of a substrate is formed, for example, with sticky material, and an image receiving material is fixed on a substrate by suction force generated due to exhaustion even at the time when the heat transfer sheets are changed.
Further, when an image receiving material has a cushioning layer formed of a shape memory resin, the cushioning layer is heated in order to recover the shape thereof after each color transfer.
Also in the case of transferring images to an image receiving material used as an intermediate transfer body, the above-mentioned method can be used. By using the image receiving material used as an intermediate transfer body obtained in this manner which has images on the surface, precise image can be formed even on the final image receiving material whose surface is not smooth.

Heat transfer sheet and light-heat-conversion type image-forming material

Abstract: A heat transfer sheet comprising a light-heat-conversion layer which includes an infrared light absorbing colorant and an image formation layer, the layers being disposed in that order, on a support, wherein the above-mentioned light-heat-conversion layer further comprises at least one compound from any group selected from a) compounds having at least one functional group selected from a phosphate group, a phosphite group, an acid halide group, an acid anhydride group and an isocyanate group, b) compounds having an acidic group, c) compounds represented by the following general formula (10), and tautomers thereof, and compounds represented by the following general formula (13).


A method of checking for restrictions in a string of tubing formed of a plurality of tubing sections. The method involves providing a profile in the tubing string, providing a drift member adapted to engage with the profile, passing the drift member through the tubing string, and determining whether the drift member has engaged with the profile prior to separating the tubing sections.

In the oil and gas exploration and production industry long strings of jointed tubing or pipe are utilised to carry fluids between the surface and downhole locations within drilled bores, which strings and bores may be several kilometres long. In all downhole operations there is a small possibility of the pipe bore becoming restricted by, for example, cement residue or foreign objects such as a piece of wood or a metal bolt. In most cases this does not have any detrimental effect on operations. However, there are numerous tools and procedures that require a ball, dart or plug to travel through the pipe to perform a specific function downhole. Accordingly, prior to such operations it is necessary to inspect the pipe for the presence of any restrictions which would hold up the ball, dart or plug. Such inspections are normally achieved by checking the pipe string in stages as the string is pulled out of the bore and the pipe sections are separated at surface, before being reassembled in preparation for the operation involving the passage of the ball, dart or plug. Pipe strings are normally formed of large numbers of pipe sections that are typically around 10 metres long and have threaded ends. The pipe sections are often made up and stored as "stands", each formed of three pipe sections, and thus around 30 metres long. Accordingly, when a pipe string is being pulled out of a bore, the string is lifted in 30 metre stages, to allow the uppermost stand to be removed.
One other commonly used method of checking the pipe bore for restrictions is to drop a hollow sleeve, of a slightly larger diameter than the ball, sleeve or plug, on a 40 m length of wire into the upper end of the pipe string. The pipe string is then pulled out of the bore to allow removal of the top pipe stand. If the wire is visible when the stand is separated from the string the operator knows that the sleeve is in the next stand and that the stand that has been separated from the string is unobstructed. This operation may be carried out relatively rapidly, but on many occasions the sleeve will not drop through the pipe, and the wire may become tangled or drop down such that it is not visible when the stand is separated. Thus, the drift and the obstruction point may go unnoticed.
In another method, an operator working at an elevated level simply drops an object, or drift, of a slightly larger diameter than the ball, sleeve or plug, through each pipe stand as it is being racked. The drift is retrieved at the bottom of the stand and then returned to the operator by means of the elevators used to lift the pipe out of the bore. This process is relatively slow, and it is not unknown for the drift to be dropped or otherwise fall, at significant risk to operators working below.
Bjørnstad U.S. Pat. No. 6,581,453 teaches a method of drifting pipe where the drift includes a radio transmitter or radioactive source. The drift is used in conjunction with a detection device positioned at surface to locate the position of the drift inside the drillpipe as the pipe is pulled from the hole. Such electronic detection of a drift has the drawback of being somewhat complicated, and the equipment would require to be physically robust. The equipment would also have to be intrinsically safe so as not to provide an ignition source If the drift incorporated a radioactive source, regulations would require the drift to be handled and stored with great care. Bjørnstad also teaches a 30 m long drift in the form of a pipe that will be detected by default as the pipe is pulled from the hole. However, it is believed that the considerable weight of the drift and other issues would pose significant practical difficulties for an operator.
Polley U.S. Pat. No. 4,452,306 describes apparatus for detecting ruptures in drill pipe above and below the drill collar. The apparatus is deployed in response to surface loss in drilling pressure, indicative of washout in the drill pipe. The apparatus comprises a tool that may be pumped down through a drill pipe string to seat in a sub in the drill string above the drill collars. The drill pipe string is then pressurised above the tool to a predetermined pressure and the pressure held for a predetermined time. The pressure is monitored and, if the pressure holds, any rupture in the drill pipe is below the tool. If the pressure holds, the pressure in the string above the tool is increased to shear pins in the tool, allowing an actuator within the tool body to move and expose by-pass apertures. This allows fluid to drain from string as the string is retrieved to permit drill pipe repair below the drill collars. If, on the other hand, the drill pipe does not hold pressure above the tool, the drill pipe is pulled one section at a time. The stands are checked until the drill pipe washout is located. The damaged pipe is replaced and the drill string is tested again. If the pressure holds, the pressure is increased until the pins shear, to allow circulation through the tool. The tool may then be retrieved on wireline.
Morrill U.S. Pat. No. 5,343,946 describes a drop-in check valve used to re-establish control of a well in circumstances where there may be a gas build-up downhole. The valve is pumped from surface to lock into a landing sub provided in the string close to the bottom of the hole. The valve includes a ball that is pushed against a seat when the downhole pressure exceeds the pressure above the valve.
It is among the objectives of embodiments of the present invention to provide an efficient, technically simple and safe method for drifting tubing.


Methods, systems, computer readable media, and apparatuses for electronically clipping coupons are presented. In one aspect, a user request to electronically clip a vendor coupon may be received at a user device, where the vendor may be different from a supplier of the content. Account information associated with the user may be identified. Thereafter, information identifying the electronically clipped coupon and the account information may be transmitted to the vendor. The vendor subsequently may allow the user to redeem the clipped coupon the next time that the user visits the vendor and presents matching account information to the vendor.

Commonly, many consumers search for and collect coupons in hopes of saving money on a variety of goods and services, and many businesses create such coupons in hopes of increasing business and revenues. In the past, the coupons created by businesses and collected by consumers were often pieces of paper circulated by mail and other physical distribution methods. This disclosure provides more convenient, functional, and usable ways of creating, distributing, clipping, and/or redeeming coupons.


Electric switch mechanism for relays and contactors comprises a slider movable within a fixed housing and provided with cams which convert the movement of the slider into contact movement of contact pairs of the switch. The action of the slider with the cams to induce movement to the contacts is opposite to that of springs which apply closing forces to contact pairs.

The present invention relates to an electric switch of the type in which at least two fixed contact arms are connected by at least a conducting bridge, having at least one movable contact pair opposed to at least one fixed contact pair on the fixed arms. Such a switch can be specifically employed in auxiliary switch blocks assembled on electromechanical devices, such as contactors or relays, in which the smallest possible force from actuating members is required in order to actuate contact closure and/or opening while the force applied to the closing contacts must be well higher than the force required from the actuating members.
In the contemporary electromechanical devices, such as contactors, many accessory devices such as latching devices, time delaying devices, and, specifically, many contacts having auxiliary tasks, are provided, which require high forces from the actuating members.

CGE Compagnia Generale Electtromeccanica S.p.A.


A system for use in monitoring an operation of a classification model in generating estimated labels for item records is described herein. The system receives a current labeling budget value including a number of trusted labels available for use in a labeling operation, determines a current selection probability for each item record included in an item list as a function of the current labeling budget value, selects a plurality of item records from the item list as a function of each corresponding current selection probability, and generates a sampling list including the selected item records. The system determines a risk measurement value associated with the classification model indicating an accuracy of the estimated labels as compared to trusted labels associated with the item records.

Many consumers desire to order items or goods remotely, e.g., on-line, through the Internet, or using a specially designed application or app on a personal computer or mobile device, such as a tablet or cell phone. At least some known web hosting systems include search engines that allow consumers to enter search criteria and generate search results based on the consumer's search criteria. Known search engines may generate and display product lists to consumers via a website including products that are selected based on the search criteria.
At least some known system include classification servers that generate product listings that are stored in databases for use by search engines to generate and display product lists to consumers. However, in at least some known classification systems, the information associated with product records may include information that is not relevant to and/or does not accurately describe the associated product, resulting search results that are not relevant to the corresponding search query.
In supervised learning it is necessary to have labeled training and test data to learn and evaluate a given computer labeling model. Collecting labels is generally an expensive operation and is important to minimize the number of labels required to both train and test the classification computer. At least one common approach when a large set of unlabeled items is available, is to label a randomly selected subsets of the items. The labeled data is then divided between a train and a test set at random. Even though this approach is commonly used, for a given number of labeled data points it might not be optimal and it might also not work well in some practical situations that are often encountered in a production system.
For example, a common situation is for the set of items under evaluation to change over time. In such a case, the labeled test dataset might not be fully representative of the whole set and any evaluation of a corresponding computer model might be in error for the new set of items. A simple solution is to sample a new test data set every time an evaluation is required, however, this is clearly very expensive and wasteful because the previously acquired test data is not able to be reused. Another situation that very often arises includes multiple labeled data sets that have been obtained from subsets of the whole space of items. Simply using the union of such test datasets is incorrect in general because the test datasets might not be representative of the whole set of items. In this case as well, a simple solution is to sample a new test data set for evaluation. Again this approach would be expensive and wasteful.
Because the number of items that may be included in a product database may increase overtime, significant computing time and resources are required to determine the accuracy of classifications systems used to label each of the corresponding item records that are used in response to search queries requested by consumers. As the amount of product records being included in a database increases, the amount of computing time and resources that are required to determine the accuracy of classifications systems used to label item records for use in response to search queries requested by consumers increase, thus reducing the overall performance of known computer web hosting systems.
The present invention is aimed at one or more of the problems identified above.

Server computer and networked computer system for evaluating, storing, and managing labels for classification model evaluation and training


The present invention provides a method for producing a cyclodextrin-panobinostat adduct, comprising: a) providing a first aqueous solution comprising a buffering agent, the solution having a pH in the range 2.0 to 4.0; b) dissolving panobinostat in said first aqueous solution to provide a second aqueous solution; and c) mixing said second aqueous solution comprising panobinostat with a third aqueous solution comprising a cyclodextrin to form a fourth aqueous solution comprising a cyclodextrin-panobinostat adduct. Also provided is an artificial cerebrospinal fluid (CSF) solution comprising the cyclodextrin-panobinostat adduct and medical uses of the cyclodextrin-panobinostat adduct, including in the treatment of brain tumours.

The present invention is directed at pharmaceutical compositions and formulations, and methods of making and administering such compositions and products, for use in the treatment of brain tumours, including glioma such as diffuse intrinsic pontine glioma (DIPG).
Histone deacetylase (HDAC) inhibitors show significant potential for the treatment of various cancers. Panobinostat (Farydak®, LBH-589, 2-(E)-N-hydroxy-3-[4[[[2-(2-methyl-1H-indol-3-yl)ethyl]amino]methyl]phenyl]-2-propenamide) is a non-selective HDAC inhibitor used in the treatment of multiple myeloma. Combination therapy of panobinostat and radiation has been proposed for the treatment of solid tumours (WO2007/050655). However, hydroxamate compounds, including panobinostat, exhibit poor aqueous solubility and stability (WO2009/039226). Panobinostat formulations have been proposed that employ at least one alcohol to reduce oxidation and hydrolysis (WO2008/086330).
Wehrmann et al., PLOS ONE, 2012, Vol. 7, Issue 10, e48561, describe lowering of intracellular cholesterol levels in Niemann-Pick Type C Fibroblasts by vorinostat, panobinostat, beta-cyclodextrin and combinations thereof.
Grasso et al., Nature Medicine, 2015, Vol. 21, No. 6, pp. 555-559, report that the multi-histone deacetylase inhibitor, panobinostat, demonstrated therapeutic efficacy both in vitro and in DIPG orthotopic xenograft models. However, panobinostat was formulated in dimethyl sulphoxide (DMSO) for convection-enhanced delivery (CED) to the xenograft tumour-bearing mice. DMSO is a mild oxidising agent and has a number of shortcomings for clinical use in humans.
WO2015/191931 describes pharmaceutical compositions containing a hydrophobic drug (which may be an HDAC inhibitor), prodrug thereof, salt thereof, isoform thereof, or a combination thereof; cyclodextrin, prodrug thereof, salt thereof, of combination thereof; polyethylene glycol, propylene glycol, or combination thereof; and a pharmaceutically acceptable carrier, as well as medical uses thereof, including in the treatment of a brain disease.
WO2008/002862 describes pharmaceutical compositions containing inhibitors of histone deacetylase and B vitamins and medical uses thereof, including in the treatment of proliferative disorders.
Hockly et al., PNAS, 2003, Vol. 100(4), pp. 2041-2046, describes treatment of a mouse model of Huntington's disease using the HDAC inhibitor suberoylanilide hydroxamic acid (SAHA), administered orally.
US2013177499 proposes use of bacterially derived minicells as delivery vehicles for active agents against brain tumours.
WO2013/135727 describes a method for treatment of glioma by convection enhanced delivery (CED) using a composition of carboplatin in artificial cerebrospinal fluid (CSF).
There remains an unmet need for pharmaceutical formulations that are stable and amenable to central administration (e.g. via CED) for the treatment of brain tumours, including glioma. The present invention addresses these and other needs.


In a method of handling mail items in a postal sorting machine, in which method the mail items pass a first time and then a second time through the machine in compliance with a sorting plan, the following steps are performed: during the first sorting pass, and for each current mail item, measuring a physical magnitude specific to the mail item, and determining an expected sequence of mail items for the second sorting pass; and, during the second sorting pass, and for each current mail item, measuring the same physical magnitude once again, and, if it is determined that said current mail item is not the item expected in said sequence, comparing the physical magnitudes as measured for the same mail item respectively during the first pass and during the second pass so as to identify the presence of mail items in multiple takes.

Mail items are inserted into a postal sorting machine by means of an unstacker which separates the mail items one-by-one from the stack and injects them into a conveyor serving the sorting outlets of the machine. Unstacking is a very important and difficult step in handling mail items. One known type of malfunctioning of a sorting machine is related to the fact that mail items might not be unstacked correctly, and are thus injected as a "multiple take" into the conveyor, i.e. by being mutually superposed or overlapping. This type of malfunctioning can occur during successive sorting passes.
A method is already known from Patent Document DE 19 625 043 for identifying the presence of mail items in multiple takes by combining probabilities on measurements of mail item length, height, and thickness.
Another method is also known from Patent Document GB 2 279 634 for detecting multiple takes by means of a system of belts driven at various speeds combined with measuring mail item length at the inlets and at the outlets of the system of belts.
Other methods of identifying the presence of mail items in multiple takes are also described in Patent Documents U.S. Pat. Nos. 3,955,812, 4,121,716 and FR 2 841 487.

Method of identifying overlapping articles


A keyboard unit may comprise a keyboard body having a top face and a planar bottom face. The keyboard body may be adapted for installation in a laptop computer. The planar bottom face of the keyboard body may be disposed toward a bottom case of the laptop when installed therein. A plurality of key tops may be disposed on the top face of the keyboard body. A plurality of bosses may have end openings aligned at same plane as the planar bottom face.

The present invention relates generally to keyboards, and, more specifically, to flat bottom keyboards which can be used for different designs or models of notebook personal computers (hereinafter "notebook PCs").
Keyboards for desktop computers come in a package, along with the computer system units, when sold. Users can plug in the keyboard cord to a port of the computer system and then start to type on the keyboard when the desktop is working. In the case of notebook PCs, the keyboard is part of the computer system unit and cannot be separated from the system unit without dissembling the system unit.
Computer manufactures have developed different models and designs of notebook PCs to serve needs of the customers. Sometimes, keyboards have to be designed differently in order to fit different models of notebook PCs, which may increase the manufacturing cost of notebook PCs.
Therefore, it can be seen that there is a need for a common keyboard for notebook PCs of different models or designs.