Reversible thermosensitive recording material

Abstract

A reversible thermosensitive recording material is disclosed, which comprises (i) a reversible thermosensitive recording layer which comprises as the main components a matrix resin and an organic low-molecular-weight material dispersed in the matrix resin, and (ii) a light reflection layer made of a metal thin film, which is preferably surface-treated to have a specular gloss of 70 to 250% in accordance with JIS Z8741 or a surface roughness of 0.5 to 10 μm in terms of the ten-point average roughness defined in JIS B0601. This reversible thermosensitive recording material may further comprises a crystal-growth controlling agent in the reversible thermosensitive recording layer.

What is claimed is: 
     
       1. A reversible thermosensitive recording material comprising (i) a reversible thermosensitive recording layer which comprises a matrix resin and an organic low-molecular-weight material which is dispersed in said resin, (ii) a light reflection layer made of a metal thin film, and (iii) a transparent support interposed between said thermosensitive recording layer and said light reflection layer. 
     
     
       2. The reversible thermosensitive recording material as claimed in claim 1, further comprising an adhesive layer which is interposed between said transparent support and said light reflection layer, and a second transparent support formed on said light reflection layer on a side opposite to said adhesive layer. 
     
     
       3. The reversible thermosensitive recording material as claimed in claim 1, further comprising a second transparent support on said light reflection layer on a side opposite to said reversible thermosensitive recording layer. 
     
     
       4. The reversible thermosensitive recording material as claimed in claim 1, further comprising a light absorption layer which is interposed between said reversible thermosensitive recording layer and said light reflection layer. 
     
     
       5. The reversible thermosensitive recording material as claimed in claim 1, further comprising a transparent support for supporting said reversible thermosensitive recording layer thereon, and a light reflection layer support member for protecting said light reflection layer, with said reversible thermosensitive recording layer being disposed so as to be superimposed on said light reflection layer through said support. 
     
     
       6. The reversible thermosensitive recording material as claimed in claim 1, wherein said metal thin film has a specular gloss of 70 to 250% in accordance with JIS Z8741 or a surface roughness of 0.5 to 10 μm in terms of a ten-point average roughness as defined in JIS B0601. 
     
     
       7. The reversible thermosensitive recording material as claimed in claim 1, wherein said organic low-molecular-weight material has a melting point ranging from 30° C. to 200° C. 
     
     
       8. The reversible thermosensitive recording material as claimed in claim 1 wherein said organic low-molecular-weight material is a compound containing at least one group or a moiety selected from the group consisting of --OH, --COOH, --COOR (wherein R is NH 4  or an alkyl group having 1 to 20 carbon atoms), --CONH 2 , --NH--, --NH 2 , --S--, --S--S--, --O--, and a halogen. 
     
     
       9. The reversible thermosensitive recording material as claimed in claim 1, wherein said organic low-molecular-weight material is a higher fatty acid selected from the group consisting of lauric acid, dodecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, stearic acid, behenic acid, nonadecanoic acid, arachic acid and oleic acid. 
     
     
       10. The reversible thermosensitive recording material as claimed in claim 1, wherein said organic low-molecular-weight material is an ester of a higher fatty acid selected from the group consisting of methyl stearate, tetradecyl stearate, octadecyl stearate, octadecyl laurate, tetradecyl palmitate, and dodecyl behenate. 
     
     
       11. The reversible thermosensitive recording material as claimed in claim 1, wherein said organic low-molecular-weight material is an ether selected from the group consisting of: ##STR5## 
     
     
       12. The reversible thermosensitive recording material as claimed in claim 1, wherein said organic low-molecular-weight material is a thioether selected from the group consisting of ##STR6## 
     
     
       13. The reversible thermosensitive recording material as claimed in claim 1, wherein said organic low-molecular-weight material is a compound selected from the group consisting of: ##STR7## 
     
     
       14. The reversible thermosensitive recording material as claimed in claim 1, wherein said organic low-molecular-weight material is a compound selected from the group consisting of an alkanol; an alkane diol; a halogenated alkanol; a halogenated alkane diol; an alkylamine; an alkane; an alkene; an alkyne; a halogenated alkane; a halogenated alkene; a halogenated alkyne; a cycloalkane; a cycloalkene; a cycloalkyne; a saturated or unsaturated monocarboxylic acid, a saturated or unsaturated dicarboxylic acid, esters, amides and ammonium salts thereof; a saturated or unsaturated halogenated fatty acid, esters, amides and ammonium salts thereof; an arylcarboxylic acid, esters, amides and ammonium salts thereof; a halogenated arylcarboxylic acid, esters, amides and ammonium salts thereof; a thioalcohol; a thiocarboxylic acid, esters, amides and ammonium salts thereof; and a carboxylic acid ester of thioalcohol, each said compounds having 10 to 60 carbon atoms. 
     
     
       15. The reversible thermosensitive recording material as claimed in claim 1, wherein said matrix resin is a vinyl chloride copolymer. 
     
     
       16. The reversible thermosensitive recording material as claimed in claim 15, wherein said vinyl chloride copolymer is selected from the group consisting of polyvinyl chloride, vinyl chloride - vinyl acetate copolymer, vinyl chloride - vinyl acetate - vinyl alcohol copolymer, vinyl chloride - vinyl acetate - maleic acid copolymer and vinyl chloride - acrylate copolymer. 
     
     
       17. The reversible thermosensitive recording material as claimed in claim 1, wherein said matrix resin is a vinylidene chloride copolymer. 
     
     
       18. The reversible thermosensitive recording material as claimed in claim 17, wherein said vinylidene chloride copolymer is selected from the group consisting of polyvinylidene chloride, vinylidene chloride - vinyl chloride copolymer and vinylidene chloride - acrylonitrile copolymer. 
     
     
       19. The reversible thermosensitive recording material as claimed in claim 1, wherein said matrix resin is selected from the group consisting of polyester, polyamide, polyacrylate, polymethacrylate, acrylate - methacrylate copolymer, and silicone resin. 
     
     
       20. The reversible thermosensitive recording material as claimed in claim 1, wherein the ratio by weight of the amount of said organic low-molecular-weight material to the amount of the matrix resin is in the range of about 1:0.5 to 1:16. 
     
     
       21. The reversible thermosensitive recording material as claimed in claim 1 wherein said reversible thermosensitive recording layer has a thickness of 1 to 30 μm. 
     
     
       22. The reversible thermosensitive recording material as claimed in claim 1, wherein said reversible thermosensitive recording layer further comprises a crystal-growth controlling agent which can control the crystal growth of said organic low-molecular-weight material. 
     
     
       23. The reversible thermosensitive recording material as claimed in claim 22, wherein said crystal-growth controlling agent is selected from the group consisting of polyhydric alcohol higher fatty acid esters; polyhydric alcohol higher alkyl ethers; sub-olefin oxide addition products of polyhydric alcohol higher fatty acid ester, higher alcohol, higher alkylphenol, higher alkylamine of higher fatty acid, amides of higher fatty acid, fat and oil of higher fatty acid and polypropylene glycol; acetylene glycol; sodium, calcium, barium and magnesium salts of higher alkyl benzenesulfonic acid; sodium, calcium, barium and magnesium salts of higher fatty acid, aromatic carboxylic acid, higher aliphatic sulfonic acid, aromatic sulfonic acid, sulfuric monoester, phosphoric monoester and phosphoric diester lower sulfated oil; long-chain polyalkyl acrylate; acrylic oligomer; long-chain polyalkyl methacrylate; long-chain alkyl methacrylate - amine-containing monomer copolymer; styrene - maleic anhydride copolymer; and olefin - maleic anhydride copolymer. 
     
     
       24. The reversible thermosensitive recording material as claimed in claim 22, wherein said crystal-growth controlling agent is selected from the group consisting of tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, butyl oleate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, dioctyldecyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, dibutyl adipate, di-n-hexyl adipate, di-2-ethylhexyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate, diethylene glycol dibenzoate, triethylene glycol, di-2-ethylbutyrate, methyl acetylricinoleate, butyl acetylricinoleate, butylphthalyl butyl glycolate and tributyl acetylcitrate. 
     
     
       25. The reversible thermosensitive recording material as claimed in claim 22, wherein the ratio by weight of the amount of said organic low-molecular-weight material to the amount of said crystal-growth controlling agent is in the range of 1:0.01 to 1:0.8. 
     
     
       26. The reversible thermosensitive recording material as claimed in claim 1, wherein said metal thin film is made of a metal selected from the group consisting of Al, Ge, Au, Ag, Cu and Ti, and alloys thereof. 
     
     
       27. The reversible thermosensitive recording material as claimed in claim 1, further comprising a second transparent support for supporting said light reflection layer and an adhesive layer, wherein said adhesive layer is interposed between said light reflection layer and said second transparent support. 
     
     
       28. The reversible thermosensitive recording material as claimed in claim 27, wherein said adhesive layer comprises a resin selected from the group consisting of saturated polyester resin, vinyl chloride - vinyl acetate - maleic acid copolymer, and vinyl chloride - vinyl acetate - vinyl alcohol copolymer. 
     
     
       29. The reversible thermosensitive recording material as claimed in claim 2, 3 or 27, wherein said second transparent support is a polyester film. 
     
     
       30. The reversible thermosensitive recording material as claimed in claim 1, wherein said metal thin film has a specular gloss of 70 to 250% in accordance with the following formula: ##EQU2## or a surface roughness of 0.5 to 10 μm in terms of a ten-point average roughness. .Iadd. 
     
     
       31.  A reversible thermosensitive recording material comprising (i) a reversible thermosensitive recording layer which comprises a matrix resin and a low-molecular weight organic material dispersed therein, (ii) a support, and (iii) a light reflection layer made of a thin metal film, interposed between the thermosensitive recording layer and the support. .Iaddend..Iadd.32. The reversible thermosensitive recording material as claimed in claim 31 further comprising an adhesive layer interposed between said support and said light reflection layer. .Iaddend..Iadd.33. The reversible thermosensitive recording material as claimed in claim 32, wherein said adhesive layer comprises a resin selected from the group consisting of saturated polyester resins, vinyl chloride - vinyl acetate - maleic acid copolymers, and vinyl chloride - vinyl acetate - vinyl alcohol copolymers. .Iaddend..Iadd.34. The reversible thermosensitive recording material as claimed in claim 31, further comprising an adhesive layer interposed between said reversible thermosensitive recording layer and said light reflection layer. .Iaddend..Iadd.35. The reversible thermosensitive recording material as claimed in claim 34, wherein said adhesive layer comprises a resin selected from the group consisting of saturated polyester resins, vinyl chloride - vinyl acetate - maleic acid copolymers, and vinyl chloride - vinyl acetate - vinyl alcohol copolymers. .Iaddend..Iadd.36. The reversible thermosensitive recording material as claimed in claim 31, further comprising a light absorption layer interposed between said reversible thermosensitive recording layer and said light reflection layer. .Iaddend..Iadd.37. The reversible thermosensitive recording material of claim 31, further comprising a transparent support for supporting said reversible thermosensitive recording layer thereon, wherein said reversible thermosensitive recording layer is disposed so as to be superimposed on said light reflection layer through said transparent support. .Iaddend..Iadd.38. The reversible thermosensitive recording material as claimed in claim 31, wherein said metal thin film has a specular gloss of 70-250% in accordance with JIS Z8741 or a surface roughness of 0.5-10 μm in terms of a 10-point average roughness as defined in JIS B0601. .Iaddend..Iadd.39. The reversible thermosensitive recording material as claimed in claim 31, wherein said organic low-molecular weight material has a melting point 
     
     
        ranging from 30° C. to 200° C. .Iaddend..Iadd.40.  The reversible thermosensitive recording material as claimed in claim 31, wherein said organic low-molecular-weight material is: a higher fatty acid selected from the group consisting of lauric acid, dodecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, stearic acid, behenic acid, nonadecanoic acid, arachic acid, and oleic acid;   an ester of a higher fatty acid selected from the group consisting of methyl stearate, tetradecyl stearate, octadecyl stearate, octadecyl laurate, tetradecyl palmitate, and dodecyl behenate;   an ester selected from the group consisting of ##STR8## a thioether selected from the group consisting of ##STR9## an amine selected from the group consisting of ##STR10## a compound selected from the group consisting of an alkanol; an alkane diol; a halogenated alkanol; a halogenated alkane diol; an alkylamine; an alkane; an alkene; an alkyne; a halogenated alkane; a halogenated alkene; a halogenated alkyne; a cycloalkane; a cycloalkene; a cycloalkyne; a saturated or unsaturated monocarboxylic acid, a saturated or unsaturated dicarboxylic acid, esters, amides and ammonium salts of said saturated or unsaturated monocarboxylic and dicarboxylic acids; a saturated or unsaturated halogenated fatty acid, esters, amides, and ammonium salts of said saturated or unsaturated halogenated fatty acid; an arylcarboxylic acid, esters, amides and ammonium salts of said arylcarboxylic acid; a halogenated arylcarboxylic acid, esters, amides and ammonium salts of said halogenated arylcarboxylic acid; a thioalcohol; a thiocarboxylic acid, esters, amides and ammonium salts of said thiocarboxylic acid; and a carboxylic acid ester of a thioalcohol, each of said compounds having 10   
     
     
        to 60 carbon atoms. .Iaddend..Iadd.41.  The reversible thermosensitive recording material as claimed in claim 31, wherein said matrix resin is selected from the group consisting of a vinyl chloride copolymer, a vinylidene chloride copolymer, a polyester, a polyamide, a polyacrylate, a polymethacrylate, an acrylate-methacrylate copolymer, and a silicone 
     
     
        resin. .Iaddend..Iadd.42.  The reversible thermosensitive recording material as claimed in claim 41, wherein said matrix resin is a vinyl chloride copolymer or a vinylidene chloride copolymer, said vinyl chloride copolymer being selected from the group consisting of polyvinyl chloride, a vinyl chloride - vinyl acetate copolymer, a vinyl chloride - vinyl acetate - vinyl alcohol copolymer, a vinyl chloride - vinyl acetate - maleic acid copolymer and a vinyl chloride - acrylate copolymer, and said vinylidene chloride copolymer being selected from the group consisting of polyvinylidene chloride, a vinylidene chloride - vinyl chloride copolymer and a vinylidene chloride - acrylonitrile copolymer. .Iaddend..Iadd.43. The reversible thermosensitive recording material as claimed in claim 31, wherein the ratio by weight of the amount of said organic low-molecular-weight material to the amount of the matrix resin is in the range of about 1:0.5 to 1:16. .Iaddend..Iadd.44. The reversible thermosensitive recording material as claimed in claim 31, wherein said reversible thermosensitive recording layer has a thickness of 1 to 30 μm. .Iaddend..Iadd.45. The reversible thermosensitive recording material as claimed in claim 31, wherein said reversible thermosensitive recording layer further comprises a crystal-growth controlling agent which can control the crystal growth of said organic low-molecular-weight material. .Iaddend..Iadd.46. The reversible thermosensitive recording material as claimed in claim 45, wherein said crystal-growth controlling agent is selected from the group consisting of polyhydric alcohol higher fatty acid esters; polyhydric alcohol higher alkyl ethers; sub-olefin oxide addition products of polyhydric alcohol higher fatty acid esters, higher alcohols, higher alkylphenols, higher alkylamines of higher fatty acids, amides of higher fatty acids, fats and oils of higher fatty acids and polypropylene glycol; acetylene glycol; sodium, calcium, barium and magnesium salts of higher alkyl benzenesulfonic acids; sodium, calcium, barium and magnesium salts of higher fatty acids, aromatic carboxylic acids, higher aliphatic sulfonic acids, aromatic sulfonic acids, sulfuric acid monoesters, phosphoric acid monoesters and phosphoric acid diesters; lower sulfated oils; long-chain polyalkyl acrylates; acrylic oligomers; long-chain polyalkyl methacrylates; long-chain alkyl methacrylate-amine-containing monomer copolymers; styrene-maleic anhydride copolymers; and olefin - maleic anhydride copolymers. .Iaddend..Iadd.47. The reversible thermosensitive recording material as claimed in claim 45, wherein said crystal-growth controlling agent is selected from the group consisting of tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, butyl oleate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, dioctyldecyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, dibutyl adipate, di-n-hexyl adipate, di-2-ethylhexyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate, diethylene glycol dibenzoate, triethylene glycol, di-2-ethylbutyrate, methyl acetylricinoleate, butyl acetylricinoleate, butylphthalyl butyl glycolate and tributyl acetylcitrate. .Iaddend..Iadd.48. The reversible thermosensitive recording material as claimed in claim 45, wherein the ratio by weight of the amount of said organic low-molecular-weight material to the amount of said crystal-growth controlling agent is in the range of 1:0.01 to 1:0.8. .Iaddend..Iadd.49. The reversible thermosensitive recording material as claimed in claim 31, wherein said thin metal film is selected from the group consisting of Al, Ge, Au, Ag, Cu, Ti, and alloys thereof. .Iaddend.