WO2005000596A1 - 感熱記録体用増感剤分散体の製造方法及び感熱記録体 - Google Patents
感熱記録体用増感剤分散体の製造方法及び感熱記録体 Download PDFInfo
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- WO2005000596A1 WO2005000596A1 PCT/JP2004/005074 JP2004005074W WO2005000596A1 WO 2005000596 A1 WO2005000596 A1 WO 2005000596A1 JP 2004005074 W JP2004005074 W JP 2004005074W WO 2005000596 A1 WO2005000596 A1 WO 2005000596A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/337—Additives; Binders
- B41M5/3375—Non-macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/337—Additives; Binders
Definitions
- the present invention relates to a method for producing a dispersion in which a sensitizer is finely divided as a material for increasing the sensitivity of a thermosensitive recording medium, and a thermosensitive recording medium using the sensitizer dispersion.
- Thermal recording media utilizing thermal coloring reaction with dyes, developers and sensitizers are widely used in facsimile machines, printers, labels, tickets, etc. due to their inexpensive systems.
- sensitizers 1,2-bis (3-methylphenoxy) ethane and a dye are mixed together with a dye in a sand grinder (wet pulverizer) to have an average particle diameter of 0.40 ⁇ m, 0.25 m, and 0.15 ⁇ m. It is disclosed that when the powder is pulverized to 0 / m, the coloring property is excellent (see, for example, Japanese Patent Application Laid-Open No. 5-168695). However, as can be seen in Table 1, the average particle size of the sensitizer is currently 1 to 3 m.
- the sensitizer dispersion obtained by the grinding technique using a sand grinder is allowed to stand for a long time and stored or stored for a long period of time, the dispersion sediments to the lower layer, but the sediment remains in a firm and tight state.
- the sensitizer dispersion obtained by the grinding technique using a sand grinder is allowed to stand for a long time and stored or stored for a long period of time, the dispersion sediments to the lower layer, but the sediment remains in a firm and tight state.
- An object of the present invention is to solve the above-mentioned drawbacks of the prior art. That is, by producing a sensitizer dispersion which has a good volumetric efficiency and is micronized in a short time, the dispersion has excellent storage / storage stability, and further, by using the ⁇ sensitizer dispersion, An object of the present invention is to provide a thermosensitive recording medium which has high sensitivity, has almost no stain on the background, and has good storage stability of a recorded image.
- the present inventors have conducted intensive studies to solve the above-mentioned problems.As a result, the present inventors changed the idea of a method for forming fine particles of a sensitizer from a conventional pulverization method using a sand grinder, Was heated and melted and emulsified into fine particles in an oil-water system. As a result, it was found that an emulsion dispersion of a sensitizer having a good volumetric efficiency and an average particle diameter of 3 m or less was obtained in a short time.
- the present invention includes the following inventions.
- Emulsifying and dispersing agent A sensitizing agent dispersion, characterized in that a sensitizer for a thermal recording medium in water is emulsified into fine particles under heat and melt, and then the finely divided emulsified dispersion is crystallized under rapid cooling. Manufacturing method.
- the sensitizers include 1,2-bis (phenoxy) ethane, 1,2-bis (3-methylphenoxy) ethane, 1,2-bis (4-methylphenoxy) ethane, and 1-benzodibenzobiphenol , Oxalate: refers to at least one member selected from the group consisting of methinolevenezinole and ⁇ -naphthylbenzyl ether.
- a method for producing a mixed dispersion for a heat-sensitive recording material comprising wet-milling the dispersion of the heat-sensitive agent according to the above (4) and a dye for a heat-sensitive recording material or a developer for a heat-sensitive recording material.
- thermosensitive recording material obtained by the production method according to (5).
- a heat-sensitive recording material characterized by containing the sensitizer dispersion described in (4) or the mixed dispersion for heat-sensitive recording material described in (6) above on a support surface.
- the dye is 3-N, N-dibutylamine 6-methyl-7-anilinofluorane, 3-N, N-getylamino-6-methyl-7-anilinofluoran, 3-N, N-diamylamino 6-methyl-7- Anilinofluoran, 3 — N, N—Jetylamine 7— (m—Trifluoromethylanilino) Fluoro Orchid, 3- (N-isoamylyl N-ethyl) amino-6-methyl-7-arinofluoran, 3- (N-p-tolyl N-ethyl) amino-6-methyl-7-anilinofluoran, 3-1 (N— (Isopentyl-1N-ethyl) amino-6-methyl-7-anili-nofluoran, 3- (N-cyclohexyl N-methyl) amino-6-methyl-7-anili-nofluoran, 3-N, N-Jethylamino-16-clo (7) at least one
- the developing agents are 4,4'-dihydroxydiphenylsulfone, 2,4'-dihydroxydiphenylenolesnorefone, 4-hydroxy-4'-isopropoxydiphenylenolesnorefone, bis (3 —Aryl 1—4-Hydroxyphenyl) Snorrephon, 2,2-bis (4-Hydroxypheninole) Propane, Bis (4-Hydroxypheninoleretoxy) Methane, Bis (4-Hydroxypheninolecet) (Tinole) Ethenole, 4, 4'-cyclohexylidenediphenol, 4-benzinoleoxy-4, hydroxydiphenylsulfone, 4-arinoleoxy-4, hydroxydiphenylsulfone, p-hydroxybenzoate Benzyl acid, 3,5-di ( ⁇ -methylbenzyl) salicylic acid and its zinc salt, 2,4-bis (phenylsulfoninole)
- toluenesulfonyl ⁇ amino carbonitrile a two Li de,, a '- bis ⁇ 4-(P- arsenate de Loki Schiff Eni Roh less Honoré Hong) phenoxy ⁇ -1 p-xylene, 2,2-bis (hydroxymethyl) _1,3-propanediol polycondensate and 4-hydroxybenzoic acid dehydration condensate, 4,4,1 ⁇ Oxybis (ethyleneoxy-P-phenylenesulfonyl) ⁇ at least one member selected from the group consisting of diphenols, characterized in that it is at least one member selected from the group consisting of (7) and (8).
- Thermal recording body a two Li de,, a '- bis ⁇ 4-(P- arsenate de Loki Schiff Eni Roh less Honoré Hong) phenoxy ⁇ -1 p-xylene, 2,2-bis (hydroxymethyl) _1,3-propanediol polycondensate and 4-hydroxybenzoic acid
- the sensitizer for a heat-sensitive recording medium can be converted into emulsion microparticles in a short time, and the obtained sensitizer dispersion is stored for a long time. Later, even when used as a coating material for a thermal recording medium, the power or time required for re-dispersion can be greatly reduced compared to the conventional method, and a coating liquid can be prepared in a short time at any time. Above is very advantageous.
- a heat-sensitive recording material using the obtained sensitizer dispersion is excellent in coloring property and preservability of a recorded image, and can obtain a heat-sensitive recording material having less background fog under heat and humidity.
- thermosensitive recording medium that requires high sensitivity color development contains a finely divided photosensitive agent in a thermosensitive recording layer. If this sensitizer has an extremely high melting point, the function as a sensitizer will not be exhibited, and the color developability (recording sensitivity) of the thermosensitive recording medium will not be improved. On the other hand, if the melting point is too low, there is a problem that when the thermal recording medium is exposed to a high temperature, the color develops spontaneously and stains (ground fog) occur. For these reasons, a sensitizer having a melting point of 80 to 130 ° C. is preferable.
- the sensitizer used in the present invention has a melting point of 80 to 130 ° C., 1,2-bis (phenoxy) ethane (mp 96 ° C.), 1,2-bis (3 —Methylphenoxy) ethane (mp 98 ° C), 1,2-bis (4-methylphenoxy) ethane (mp125 ° C), benzylbiphenyl (mp 86 ° C), oxalate — Characterized by using at least one selected from the group consisting of methinolebenzinole (mp 103 ° C) and ⁇ -naphthinolebenzineoleatenole (mp101 ° C).
- these sensitizers are particularly excellent in color development sensitivity, storage stability of recorded images, background stains, and the like in combination with a dye and a color developer described below.
- the embodiment of the present invention will be described by dividing it into a method for producing a sensitizer dispersion and a thermosensitive recording medium using the same.
- the present invention is to provide a method for micronizing a sensitizer in a short time, with good volumetric efficiency, and at a low cost, in place of the conventional grinding method using a sand grinder.
- the sensitizer is emulsified into fine particles under the heating temperature at which the sensitizer melts with the emulsifying dispersant water.
- Polysulfonate, sodium polyacrylate, polybutyl alcohol comprising various degrees of modification, PH, modification method and degree of polymerization
- carboxymethylcellulose hydroxyxetinoresenorelose, hydroxypropinoresenole Loose, Methynoresululose, Hydroxyshetinole Methynoresenorelose, Hydroxypropinolemethinoresulorose, Polyacrylamide, Starch, Styrene Maleic anhydride copolymer salt, Ethylene acrylic acid copolymer salt, Styrene Butadiene copolymer, urine resin, melamine resin, amide resin, methyl methacrylate butadiene copolymer, methyl methacrylate 'styrene' butadiene copolymer, Atari mouth-tolyl butadiene copolymer, styrene Polymer, isoprene polymer, but
- Combinations are exemplified, but those with high emulsifiability but too easy to foam are poor in operability and are not preferred as emulsifying dispersants.On the other hand, the used emulsifying dispersants make the heat-sensitive recording material easily stain. Or poor water resistance Those that cause desensitization are not preferred. Therefore, among these, polybutyl alcohol, various celluloses, alkyl sulfates, dialkyl sulfosuccinates, polyoxyethylene alkyl sulfates, phenyl ethers and the like are preferable.
- the amount of the emulsifying dispersant used is preferably from 0.01 to 10% by mass based on the sensitizer. More preferably, it is 0.05 to 6% by mass. By the way, when the content is less than 0.01% by mass, it is difficult to sufficiently emulsify and disperse. When the ratio exceeds / 0 , the foaming of the emulsified dispersion increases, and further, the heat-sensitive recording medium using the same has disadvantages such as reduced water resistance.
- the equipment includes: (1) a homomixer type, a comb-type or intermittent jet flow generating type high-speed rotary emulsifier, (2) a colloid mill type emulsifier, (3) a high-pressure emulsifier, and (4) a roll mill type.
- a homomixer type a comb-type or intermittent jet flow generating type high-speed rotary emulsifier
- a colloid mill type emulsifier (3) a high-pressure emulsifier
- (4) a roll mill type examples thereof include an emulsifying apparatus, (5) an ultrasonic emulsifying apparatus, (6) a membrane emulsifying apparatus, and a combination thereof.
- the solid content concentration of the mixed dispersion of the sensitizer and the emulsifying dispersant water when emulsifying into fine particles using such an apparatus is preferably adjusted to 10 to 65% by mass. By the way, 65 mass. If the ratio exceeds / 0 , phase inversion occurs in the emulsified system. On the other hand, if it is less than 10% by mass, the processing efficiency is poor, and it is economically useless.
- the average particle size when the sensitizer is emulsified into fine particles by using the above apparatus is 3.0 ⁇ or less, preferably 1.5 / xm or less. It is preferable that the thickness be 5 ⁇ m or less. Incidentally, when the average particle size exceeds 3.0 ⁇ m, there is a problem that it is difficult to obtain the expected color sensitivity.
- the sensitizer dispersion emulsified into fine particles under heating and melting is crystallized under rapid cooling.
- the means for crystallizing under quenching together with the means for forming the sensitizer at the preceding stage into fine particles under heating and melting forms an important configuration in the present invention.
- a dispersion having good fluidity without emulsification can be obtained, and furthermore, a sensitizer dispersion having excellent storage stability can be obtained. it can.
- the emulsified and dispersed fine particle dispersion under heating and melting is slowly cooled, the fine particles become large crystals (several tens of m / m).
- the function of the sensitizer as a color developing agent cannot be exhibited.
- the crystallization conditions under quenching will be described in more detail. It is important to cool quickly.
- the cooling method is as follows.
- the cooling rate is preferably 3 ° CZ minutes or more, more preferably 10 ° CZ minutes or more.
- Table 2 shows a comparison between the conventional sand grinder method and the method of the present invention in order to explain how efficient the present invention is as a method for producing a sensitizer dispersion.
- the conventional sand grinder method requires a desired average particle size for producing a sensitizer dispersion.
- the time required for milling to achieve a mean particle size of 2.0 zm is 90 minutes, for 1.0 ⁇ m it is 180 minutes, and 0.3 ⁇ m.
- the time required for emulsification to obtain the corresponding average particle diameter is 2.48 minutes for O / zm, whereas 480 minutes for m. It can be seen that the method of the present invention is advantageous in that the time required for the treatment is markedly 1.5 minutes in the case of 01, and 3.0 to 21.5 minutes in the case of 0.3 m, with a marked difference.
- the dispersion of the photosensitive agent finely divided by the conventional sand grinder method is particularly flat. If the average particle size is up to about 1 IX m, the dispersion will precipitate in the lower layer after storage for a long time, and the precipitate will be firm and tight. Therefore, there is a problem with storage and storage stability that requires a great deal of power or time when re-dispersing by resolving this during use, and sufficient attention must be paid to the storage method.
- the sensitizer dispersion finely divided by the method of the present invention has a mean particle size of about 1.0 to 2.0 ⁇ even if it is stored and stored for a long period of time. It is a surprising feature that re-dispersion of sediment is extremely easy and requires little power or time to re-disperse. Such characteristics of the sensitizer dispersion are derived for the first time by the method of the present invention, and are considered to be attributable to the spherical morphology of the particles.
- an antifoaming agent consisting of higher alcohols, aliphatic esters, oils, silicones, modified hydrocarbon oils, balffins, etc. is used in the production of the present sensitizer dispersion. May be.
- the method for producing the sensitizer emulsified dispersion of the present invention may be carried out in a batch system, but may also be carried out in a continuous system using the method described below. In other words, as a continuous process flow,
- a second invention according to the present invention relates to a thermosensitive recording medium using a sensitizer dispersion produced by the above method.
- the emulsion dispersion of the sensitizer is used as it is.
- An emulsified dispersion of the sensitizer and a dye for a heat-sensitive recording medium are pulverized with a sand grinder or the like to form a mixed dispersion of a sensitizer and a dye.
- An emulsified dispersion of the sensitizer and a developer for a heat-sensitive recording medium are pulverized with a sand grinder or the like to form a mixed dispersion of a sensitizer and a developer. And combinations thereof.
- the sensitizer constituting another sensitizer dispersion already micronized includes diphenylsulfone, dibenzyl oxalate, p-chlorobenzyl oxalate, and stearic acid amine.
- stearic acid amide and ethylenebisstearic acid amide are preferred as color developing agents.
- thermosensitive recording medium can be made using ⁇ , ⁇ , surfactant, defoamer, dispersant and the like.
- the dye conventionally known compounds, for example, a fluoran compound, an indolyl phthalide compound, a dibutyl phthalide compound, a pyridine compound, a spiro compound, a fluorene compound, a triarylmethane compound, a diarylmethane compound and the like can be preferably used. As specific examples, the following are preferably used.
- Diaryl methane compounds such as 4,4-bis-dimethinoleaminobenzhydrin benzylbenzene sulfate, N-halopheninoleuroikouramin, and N-2,4,5-trichloromethylpheninoleurocholamine, etc. .
- the quality of the dye as a dye is excellent even if the heat-sensitive recording material is excellent in color development, but if the heat-sensitive recording material is easily stained by heat, light, humidity, etc., it is not preferable as a dye. At least, dyes that easily lose the recorded image are not preferable dyes.
- These dyes may be used alone or as a mixture of two or more of them for the purpose of adjusting the color tone of a color image or obtaining a multicolor heat-sensitive recording material.
- the amount of the dye to be used is preferably 100 to 500 parts by mass, more preferably 20 to 400 parts by mass, and most preferably 30 to 200 parts by mass with respect to 100 parts by mass of the sensitizer. 0 0 Mass part.
- examples of the developer include conventionally known ones, for example, phenolic compounds, sulfone compounds, zeolite compounds, nitrogen compounds and salicylic acid compounds.
- thermosensitive recording medium Considering the coloring properties of the thermosensitive recording medium, the storage stability of the recorded image, and the soiling of the background, among these, 4,4'-dihydroxydiphenylsulfone, 2,4, -dihydroxydiphene Ninores norephone, 4-hydroxy 4 -'- isopropoxy diphenenores-no-rehon, bis (3-aryl-1 4-hydroxy-pheno-nore) sunorehon, 2,2-bis (4-hydroxy-droxy-fu-inole) propane, bis (4-Hydroxypheninolethioethoxy) Methane, bis (4-Hydroxypheninolethioethane) ether, 4,4, -cyclohexylidenedipheno //, 4-benzyloxy-4, -hydroxyloxy Pheninolenolephon, 4-arinoleoxy-1,4-hydroxydiphenenoresnolephone, p-hydroxybenzoic acid benzinole, 3,5-di ( ⁇ -
- the amount of the developer used is preferably from 100 to 500 parts by mass, more preferably from 30 to 400 parts by mass, and still more preferably from 50 to 100 parts by mass, per 100 parts by mass of the sensitizer. 300 parts by mass.
- the amount is less than 10 parts by mass, the original coloring properties to be provided as a heat-sensitive recording material cannot be satisfied, while if the amount is more than 500 parts by mass, the background of the recording material becomes conspicuous, and conversely, No improvement in coloring is obtained, and it is economically useless.
- pigments are used for the purpose of improving the adhesion of scum to the recording head and making the recording layer whiter.
- the pigments include kaolin, silica, amorphous silica, calcined kaolin, and oxidized oxide.
- Inorganic fine powders such as zinc, calcium carbonate, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, magnesium sulfate, magnesium oxide, titanium oxide, barium sulfate, and synthetic aluminum silicate can be used.
- An organic resin fine powder such as a methacrylic acid copolymer, a polystyrene resin, and a urea-formalin resin can be used in combination with the pigment.
- the amount of these pigments to be used is preferably from 100 to 2000 parts by mass, more preferably from 20 to 100 parts by mass, based on 100 parts by mass of the dye. By the way, if it is less than 10 parts by mass, the intended use cannot be achieved. On the other hand, if the amount exceeds 2000 parts by mass, the color developability is reduced.
- any of a water-soluble resin and a water-dispersible resin can be used as the adhesive.
- a water-soluble resin and a water-dispersible resin can be used as the adhesive.
- saponified polyvinyl alcohol completely (partially) saponified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, silicon-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, sulfonate-modified polyvinyl alcohol, polyvinylpyrrolidone, Starch and its induction
- Water-soluble resin vinyl acetate latex, acrylate copolymer latex, methacrylate copolymer latex, vinyl acetate- (meth) acrylate copolymer latex, polyurethane latex, polyvinyl chloride Latex, polyvinylidene chloride And water-dispersible resins such as styrene-butadiene latex.
- two or more of these adhesives can be used in combination.
- the amount of the adhesive used is 2 to 40 mass of the total solid content of the heat-sensitive recording layer. / 0 , preferably about 5 to 30% by mass. By the way, if it is less than 2% by mass, the intended purpose cannot be achieved. On the other hand, if the amount exceeds 2000 parts by mass, the coloring property is reduced.
- Metal lithography and waxes are used to prevent thermal recording media from sticking due to contact with recording equipment and recording heads.
- examples of such materials include stearous acid, calcium stearate, and aluminum stearate.
- Higher fatty acid metal salts candelilla wax, rice wax, wood wax, beeswax, lanolin, montan wax, carnapa wax, ceresin wax, paraffin butter, microcrystalline wax, natural wax such as tallow and coconut oil, and polyethylene Derivatives such as wax, stearic acid and the like, and wax with a wax mouth. These may be used alone or as a mixture.
- the surfactant and the dispersant As the surfactant and the dispersant, the above-mentioned emulsifying dispersants described when producing the present sensitizer dispersion are used.
- antifoaming agent examples include higher alcohols, fatty acid esters, oils, silicones, polyethers, modified hydrocarbon oils, and paraffins. Further, if necessary, 1, 1, 3-tris (2-methyl- 5074
- Benzotriazole-based ultraviolet absorbers such as 2- (2-hydroxy-15-methylphenyl) benzotriazonole and 2- (2-hydroxy-3-tex butylinole-5-methinorefue are used as lightfastness improvers.
- 1-5-chloro benzotriazole 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -16- (2H-benzotriazole-1-yl) phenol
- microencapsulated 2- (2-hydroxy-3-dodecyl-5-methylphenyl) benzotriazole is benzotriazole-based ultraviolet absorbers such as 2- (2-hydroxy-15-methylphenyl) benzotriazonole and 2- (2-hydroxy-3-tex butylinole-5-methinorefue are used as lightfastness improvers.
- 1-5-chloro benzotriazole 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -16- (2H-benz
- each coating liquid of the components of the thermosensitive recording medium can be prepared by a conventionally known preparation method. That is, for dyes, developers, pigments, water resistance improvers, plasticizer resistance improvers, metal stones, waxes, etc., a ball mill is used in an aqueous medium containing a surfactant, an antifoaming agent and a dispersant. , Attritors, sand grinders, etc., and each dispersion is separated and crushed and dispersed so that the average particle size is usually 5 ⁇ or less, preferably 1.5 or less. Can be adjusted.
- the coating solution of the heat-sensitive recording layer can be adjusted.
- the thus obtained coating solution for the present heat-sensitive recording layer is coated on the support surface with a coating device such as an air knife coater blade, a coater-no-coater rod, a coater gravure coater, a force coater or a wire parser. Apply and dry to form a heat-sensitive recording layer.
- a coating device such as an air knife coater blade, a coater-no-coater rod, a coater gravure coater, a force coater or a wire parser.
- the coating amount of the coating liquid is not particularly limited, generally dry weight 0. 5 ⁇ 5 0. 0 g Zm 2, is adjusted preferably 1 ⁇ 0-2 0.0 range g Zm 2
- paper neutral paper, acid paper
- plastic sheet synthetic paper, non-woven fabric, etc. are used.
- an undercoat layer (intermediate layer) is provided between the heat-sensitive recording layer and the support.
- the material of the undercoat layer mainly comprises a pigment or organic hollow particles and an adhesive.
- pigment those having a large oil absorption are preferable, and calcined kaolin, magnesium carbonate, amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, calcium carbonate, urea-formalin resin filler, and other porous materials Cosmetics and the like.
- organic hollow particles examples include, but are not particularly limited to, a single monomer such as biel chloride, vinylidene chloride, butyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, acrylonitrile, and styrene. Homopolymer or copolymer resins.
- adhesives gelatin, casein, starch and derivatives thereof, methinoresenorelose, ethi / rese / reloose, pi-xicetyl cellulose, canolepoxmethylcellulose, methoxycellulose, complete (partial) saponification
- High water-solubility such as polyvinyl alcohol, carboxy-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, silicon-modified polyvinyl alcohol, acrylamido acrylate copolymer, styrene-maleic anhydride copolymer, etc.
- the method for forming the undercoat layer is not particularly limited.
- the undercoat layer can be formed in the same manner as the above-described method for forming the thermosensitive recording layer.
- a protective layer may be provided on the heat-sensitive recording layer for the purpose of preventing unnecessary color formation due to rubbing or scratching, and loss of the recorded image due to the plasticizer.
- a protective layer is mainly composed of a film-forming adhesive, a pigment, or the like, and, if necessary, a microcapsule containing an ultraviolet absorbent or a finely divided ultraviolet absorbent. In contrast, yellowing of the background and fading of the recorded image are remarkably improved.
- a fluorescent dye, a lubricant, a colorant, and the like can be contained.
- thermosensitive recording medium having excellent printability, vermilion suitability, writing suitability, and the like can be obtained.
- the protective layer water-soluble, water-dispersible, It is also possible to provide a layer containing an electron beam curable or ultraviolet curable resin.
- Examples of the adhesive having a film forming property include carboxy-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, silicon-modified polyvinyl alcohol, and diacetone-modified polyvinyl alcohol.
- a crosslinking agent When a protective layer is formed using such an adhesive, it is desirable to use a crosslinking agent in order to further increase the water resistance of the protective layer.
- a cross-linking agent include dialdehyde compounds such as dalioxal and dialhde starch, polyamine compounds such as polyethyleneimine, epoxy compounds, polyamide resins, melamine resins, boric acid, borax, and magnesium chloride. .
- pigment and the ultraviolet absorber those used for forming the heat-sensitive recording layer described above can be used.
- the method for forming such a protective layer is not particularly limited. For example, it can be formed in the same manner as the above-described method for forming a thermosensitive recording layer.
- the coating amount of the protective layer is 0.5 to 15 g / m 2 , preferably 1 to 8 g / m 2 in terms of dry weight. By the way, if it is less than 0.5 g Zm 2 , the function as a protective layer is not exhibited, while if it is more than 15 g / m 2 , the coloring sensitivity is lowered.
- the thermosensitive recording medium may be provided with a protective layer on the back side of the support, if necessary, or a natural rubber-based adhesive, an acrylic resin-based adhesive, a styrene isoprene block copolymer, or a two-component crosslinker. It is also possible to provide an adhesive paper by providing an adhesive layer mainly composed of a type acryl resin-based adhesive. In this case, if necessary, a barrier layer may be provided between the support and the adhesive layer to enhance the storability.
- thermosensitive recording medium can be formed into a thermosensitive / magnetic recording body by providing a magnetic recording layer on the back side of the support, if necessary.
- a smoothing treatment such as super-rendering may be performed after the application of each layer.
- the discharge cock was opened, the inner diameter was 6 mm, the pipe length was 300 cm, the coil was formed, and the outside was quenched through a heat exchanger cooled with ice water.
- the outlet temperature was 15 ° C.
- the discharged liquid was poured into a 500 ml flask equipped with a stirrer cooled with cold water at 15 ° C while adjusting the discharge cock of a plasticizer so that the temperature became 20 ° C or less while stirring. It took 20 minutes to discharge all the emulsified liquid in the Taliamitas emulsification kettle.
- the thus-obtained emulsified dispersion had good flowability and had an average particle diameter of 2.0 ⁇ m as measured by a particle size measuring device of SALD-2000J manufactured by Shimadzu Corporation.
- the removal amount was 290 parts, and the solid concentration was 52.3%.
- the emulsified dispersion thus obtained had good fluidity and an average particle size of 1.5 / m.
- the removal amount was 390 parts, and the solid content concentration was 31.3%.
- the outlet cock was opened, the inner diameter was 6 mm, the pipe length was 300 cin, the coil was cooled, and the outside was quenched through a heat exchanger cooled with ice water.
- the outlet temperature was 15.
- the discharged liquid was injected into a 50-mL flask with a stirrer cooled with cold water at 15 ° C while adjusting the discharge cock of the gasifier so that the temperature became 20 ° C or less while stirring. It took 20 minutes to discharge all the emulsion in the Clearmitas emulsification kettle.
- the emulsified dispersion thus obtained had good fluidity and an average particle size of 1.
- the removal amount was 291 parts, and the solid content concentration was 52.2%.
- Example 3 200 parts of the emulsified dispersion obtained in Example 3 was passed through a heat exchanger immersed in hot water at 95 ° C for 1,00 Om. Then, the outside was cooled with ice water and cooled to 5 ° C, and then poured while stirring so that the temperature of the kettle would be 30 ° C or less. After the discharge, stirring was continued at 30 ° C or less for 2 hours to complete the crystallization of the emulsified dispersion, which was then sieved with a test sieve (mesh size: 20 zm). No solids remained.
- the seasoned dispersion thus obtained had good flowability and an average particle size of 1.0 m.
- the removal amount was 485 parts, and the solid content concentration was 52.3%.
- thermometer a thermometer, a stirrer, and a condenser were attached to the 1,000 ml receiving receiver of Nanomizer Inc. PE L-20 type container, and 205 parts of water was put into the receiving container. Then, the temperature was raised to 105 ° C at the contact part on the main body side with a lipo heater from the receiver to the discharge part through the generation part.
- a heat exchanger immersed in hot water at 95 ° C was attached to the discharge part of the nanomizer main body in a coil shape with an inner diameter of 6 mm and a pipe length of 50 cm.
- the operation of the nanomizer was started under the conditions of 40 kg / cm 2 and one pass.
- the nanomizer was operated while adjusting the internal temperature of the emulsified dispersion storage flask to 30 ° C. or less, and it took 20 minutes to complete.
- the internal temperature of the emulsified dispersion storage tank flask was stirred at 30 ° C or lower for 2 hours to complete the crystallization of the emulsified dispersion. Next, it was sieved with a test sieve (mesh size: 20 / m), but hardly any solid matter remained on the mesh.
- the thus obtained emulsified dispersion had good fluidity and an average particle diameter of 0.3 ⁇ .
- the removal amount was 480 parts and the solid content concentration was 31.0%.
- the discharge cock was opened, and it was injected into the cooling tank through a pipe with an inner diameter of 6 mni and a length of 20 cm, while adjusting the discharge cock of the emulsifier so that the temperature of the cooling tank *) was 20 ° C or less. It took 10 minutes to discharge all the emulsion in the Clearmitas emulsification kettle. After charging the whole amount, stirring was continued at 20 ° C or less for 2 hours to complete the crystallization of the emulsified dispersion, which was then sieved with a test sieve (opening 20 / zm). Almost no solid remained. The emulsified dispersion thus obtained had good fluidity and an average particle size of 0.3 ⁇ . In addition, the removal amount was 686 parts, and the solid content concentration was 31.5%.
- cooling tank * means that 280 parts of ice is put in a 1 000 ml kettle, and a stirrer and temperature This is a tank equipped with a gauge and cooled with ice water.
- Example 3 The procedure of Example 3 was repeated, except that the sensitizer, the dispersant, the temperature and the total pressure were changed as follows. The results are shown in Table 3.
- the dispersion was sieved using a test sieve manufactured by Iida (mesh size: 20 / zm), and 83 parts of a dispersion of 1,2-bis (3-methylphenoxy) ethane having an average particle size of 2.0 ⁇ m was obtained. Got. The solid content of the dispersion was 41.8%.
- This dispersion was sieved using a test sieve (aperture: 20 ⁇ ) manufactured by Iida Co., Ltd., and 80 parts of a dispersion of 1,2-bis (3-methylphenoxy) ethane having an average particle diameter of 1.0 ⁇ m was added. Obtained. The solid content of the dispersion was 41.8%.
- This dispersion is sieved using a test sieve (manufactured by Iida Co., Ltd.) with an aperture of 20 ⁇ . 40 parts of a dispersion of 1,2-bis (3-methylphenoxy) ethane having a particle diameter of 0.3 ⁇ m were obtained. The solid content of the dispersion was 31.4%.
- Taliamitas C LM manufactured by AM Technology Co., Ltd. 150 parts of 1,2-bis (3-methylphenoxy) ethane in a 0.8-ml 350 ml pot, 60 parts of a 10% aqueous solution of Kuraray PVA205, 60 parts manufactured by Kao Corporation ⁇ 1.5 parts of Rex TR and 88.5 parts of water were charged, and the powder was thoroughly infiltrated into the dispersed water with a spatula. Next, the pot and the mixer body were set, and the temperature was quickly raised to 105 ° C. The pressure in the kettle was total pressure 1. 4 k gZ cm 2. Stirring was started, and it was made 18,00 Orpm over 30 seconds, and subsequently, it stirred at the same rotation speed for 60 seconds.
- Table 4 shows a method for producing a sensitizer dispersion according to the present invention and a conventional sand grinder method.
- the method according to the present invention is a very efficient method of forming a sensitizer into fine particles.
- composition according to the present invention has good storage stability regardless of the average particle size of the dispersion.
- Example 2 10 parts of the emulsified dispersion of 1,2-bis (3-methylphenoxy) ethane obtained in Example 1 was diluted with 6.7 parts of water to adjust the concentration of the sensitizer to 30%.
- thermosensitive recording medium Of 64 gr / m 2 on one surface of woodfree neutral paper, undercoat layer coating liquid ⁇ Pi thermosensitive recording layer A thermosensitive recording medium was obtained by sequentially applying and drying the coating solution for use with a wire bar such that the coating amounts after drying were 10 gr / m 2 and 3 gr / m 2 , respectively. After forming each layer, a super calendar treatment was performed.
- Example 12 10 parts of 1,2-bis (3-methylphenoxy) ethane emulsified dispersion obtained in Example 4 was diluted with 6.7 parts of water, A heat-sensitive recording material was obtained in the same manner as in Example 12, except that a sensitizer dispersion having a concentration of 30% was used.
- Example 12 was repeated except that the sensitizer dispersion used in Example 12 was replaced with the emulsified dispersion of 1,2-bis (3-methylphenoxy) ethane obtained in Example 5 as it was. Thus, a thermosensitive recording medium was obtained.
- Example 12 was repeated except that the 1,2-bis (3-methylphenoxy) ethane emulsified dispersion obtained in Example 6 was directly used instead of the sensitizer dispersion used in Example 12. Thus, a thermosensitive recording medium was obtained.
- the developer dispersion liquid and the coating liquid for the heat-sensitive recording layer instead of the sensitizer dispersion liquid used in Example 12, the developer dispersion liquid and the coating liquid for the heat-sensitive recording layer, the following sensitizer-developer mixed dispersion and heat-sensitive recording layer were used.
- a heat-sensitive recording material was obtained in the same manner as in Example 12 except that the coating solution was used.
- the particle size was measured over time using S ALD—2000 J manufactured by Shimadzu Corporation. The average particle size became 1 to 0 m after 45 minutes.
- This dispersion is sieved using a test sieve (mesh opening 20 // m), and 1,2-bis (3-methylphenoxy) ethane having an average particle diameter of 1 • 0 ⁇ m: 4- There was obtained 140 parts of a dispersion having a solids concentration of 40.8% in which hydroxy-1,4-isopropoxydiphenyl sulfone (100: 100) was mixed.
- thermosensitive recording medium was obtained in the same manner as in Example 12 except that the liquid was used.
- This dispersion is sieved using a test sieve (mesh size: 20 m), and 1,2-bis (3-methinolephenoxy) ethane having an average particle diameter of 1.0 / 111: 3-N , N-Dibutylamino-6-methyl-7-anilinofluoran (100: 50) were mixed to obtain 125 parts of a dispersion having a solids concentration of 41.0%.
- Example 12 10 parts of the 1,2-bis (phenoxy) ethane emulsified dispersion obtained in Example 7 was diluted with 6.7 parts of water, and the concentration was reduced. A heat-sensitive recording material was obtained in the same manner as in Example 12, except that the sensitizer dispersion of 30% was used.
- thermosensitive recording medium was obtained in the same manner as in Example 12 except that the agent dispersion was used.
- thermosensitive recording medium was prepared in the same manner as in Example 12 except that the sensitizer dispersion liquid was used. Obtained.
- Example 12 10 parts of the emulsified dispersion of 1,2-bis (4-methylphenoxy) ethane obtained in Example 10 was replaced with 6.7 parts of water.
- a heat-sensitive recording material was obtained in the same manner as in Example 12, except that a sensitizer dispersion liquid diluted to a concentration of 30% was used.
- thermosensitive recording medium was obtained in the same manner as in Example 12 except that a sensitizer dispersion liquid containing 30% was used.
- thermosensitive recording material was obtained in the same manner as in Example 12, except that a sensitizer dispersion liquid containing 30% of the sensitizer was used.
- thermosensitive recording medium was obtained in the same manner as in Example 12, except that the sensitizer dispersion having a concentration of 30% was used after diluting the mixture with 30 parts.
- thermosensitive recording material was obtained in the same manner as in Example 12, except that a sensitizer dispersion liquid containing 30% of the sensitizer was used.
- the heat-sensitive recording medium obtained in Examples 12 to 21 and Comparative Examples 5 to 8 was subjected to a heat-sensitive head using a heat-sensitive recording medium color test apparatus (trade name: TH-PMD, manufactured by Okura Electric Co., Ltd.).
- a heat-sensitive recording medium color test apparatus (trade name: TH-PMD, manufactured by Okura Electric Co., Ltd.).
- KYOCER A TYPE KJT-256-8 MG FI-ASH
- the measurement was performed using a Macbeth densitometer (RD-918 type manufactured by Macbeth).
- the background and the print density after standing at a temperature of 45 ° C and a humidity of 85% for 24 hours were measured with a Macbeth densitometer.
- thermosensitive recording medium according to the present invention is not inferior to the conventional one based on the particle size of the sensitizer, but the smaller the particle size of the sensitizer, the better the heat sensitivity.
- a recording medium fine particles of about 0.3 ⁇ , which were difficult to obtain industrially with the conventional method, can be inexpensively produced by the present invention.
- a heat-sensitive recording medium having excellent preservability of the recorded image without soiling the background can be obtained more advantageously.
- the sensitizer for a heat-sensitive recording medium can be converted into emulsion microparticles in a short time, and the obtained sensitizer dispersion can be stored and stored for a long period of time. Even when used as a coating material for thermal recording media, the power or time required to redisperse This is extremely advantageous in the production of a thermosensitive recording medium because the time can be greatly reduced compared to the conventional method, and the coating liquid can be prepared in a short time at any time.
- a heat-sensitive recording material using the obtained sensitizer dispersion is excellent in coloring property and preservability of a recorded image, and a heat-sensitive recording material having less background fog under heat and humidity can be obtained.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/560,942 US7557065B2 (en) | 2003-06-25 | 2004-04-08 | Method for producing material containing sensitizer dispersed therein for thermal recording article and a thermal recording article |
EP04726661A EP1645430B1 (en) | 2003-06-25 | 2004-04-08 | Method for producing material containing sensitizer dispersed therein for heat-sensitive recording material |
ES04726661T ES2378151T3 (es) | 2003-06-25 | 2004-04-08 | Método para producir un material que contiene un sensibilizador dispersado en su interior para material de registro termosensible |
US12/473,012 US20090233246A1 (en) | 2003-06-25 | 2009-05-27 | Method for producing material containing sensitizer dispersed therein for thermal recording article and thermal recording article |
Applications Claiming Priority (2)
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JP2003180869A JP3945705B2 (ja) | 2003-06-25 | 2003-06-25 | 増感剤分散体の製造方法及び感熱記録体 |
JP2003-180869 | 2003-06-25 |
Related Child Applications (1)
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US12/473,012 Continuation US20090233246A1 (en) | 2003-06-25 | 2009-05-27 | Method for producing material containing sensitizer dispersed therein for thermal recording article and thermal recording article |
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WO2005000596A1 true WO2005000596A1 (ja) | 2005-01-06 |
Family
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PCT/JP2004/005074 WO2005000596A1 (ja) | 2003-06-25 | 2004-04-08 | 感熱記録体用増感剤分散体の製造方法及び感熱記録体 |
Country Status (7)
Country | Link |
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US (2) | US7557065B2 (ja) |
EP (1) | EP1645430B1 (ja) |
JP (1) | JP3945705B2 (ja) |
KR (1) | KR100746873B1 (ja) |
CN (1) | CN100423951C (ja) |
ES (1) | ES2378151T3 (ja) |
WO (1) | WO2005000596A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8300207B2 (en) | 2007-05-17 | 2012-10-30 | Nikon Corporation | Exposure apparatus, immersion system, exposing method, and device fabricating method |
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---|---|---|---|---|
JP2008073893A (ja) * | 2006-09-19 | 2008-04-03 | Ricoh Co Ltd | 組成物及び感熱記録材料 |
CA2680371A1 (en) | 2007-03-15 | 2008-09-18 | Basf Se | Heat-sensitive coating compositions based on resorcinyl triazine derivatives |
ES2377852T3 (es) | 2007-08-22 | 2012-04-02 | Datalase Ltd | Composición de revestimiento sensible al láser |
US8900414B2 (en) | 2007-11-07 | 2014-12-02 | Datalase, Ltd. | Fiber products |
JP5151681B2 (ja) * | 2008-05-20 | 2013-02-27 | 王子ホールディングス株式会社 | 親展用感熱記録体 |
US20120045624A1 (en) | 2008-10-27 | 2012-02-23 | Basf Se | Aqueous laser-sensitive composition for marking substrates |
JP5485749B2 (ja) * | 2010-03-04 | 2014-05-07 | 三菱製紙株式会社 | 感熱記録材料 |
JP6238006B2 (ja) * | 2013-12-27 | 2017-11-29 | 三光株式会社 | ステアリン酸アミドを主成分とする感熱記録体用増感剤微粒子分散体の製造方法 |
ES2623811T3 (es) | 2014-07-29 | 2017-07-12 | Mitsubishi Hitec Paper Europe Gmbh | Material de registro termosensible con un derivado del ácido salicílico como revelador (del color) capaz de reaccionar con un precursor de colorante |
US10208472B1 (en) * | 2017-12-26 | 2019-02-19 | Yueh-Ming Liu | Outer wall of a building |
CN110497709A (zh) * | 2019-08-28 | 2019-11-26 | 江苏傲伦达科技实业股份有限公司 | 一种新型热敏记录材料及其制备方法 |
CN115491924B (zh) * | 2021-06-18 | 2023-04-18 | 上海吉康生化技术有限公司 | 一种温度调节的热敏染色材料 |
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- 2003-06-25 JP JP2003180869A patent/JP3945705B2/ja not_active Expired - Lifetime
-
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- 2004-04-08 US US10/560,942 patent/US7557065B2/en active Active
- 2004-04-08 EP EP04726661A patent/EP1645430B1/en not_active Expired - Lifetime
- 2004-04-08 CN CNB2004800144619A patent/CN100423951C/zh not_active Expired - Lifetime
- 2004-04-08 KR KR1020057024700A patent/KR100746873B1/ko active IP Right Grant
- 2004-04-08 WO PCT/JP2004/005074 patent/WO2005000596A1/ja active Application Filing
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- 2009-05-27 US US12/473,012 patent/US20090233246A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
---|---|
US20090233246A1 (en) | 2009-09-17 |
KR20060022711A (ko) | 2006-03-10 |
CN1795108A (zh) | 2006-06-28 |
EP1645430B1 (en) | 2011-11-30 |
KR100746873B1 (ko) | 2007-08-07 |
JP3945705B2 (ja) | 2007-07-18 |
ES2378151T3 (es) | 2012-04-09 |
EP1645430A4 (en) | 2007-08-15 |
US20060252645A1 (en) | 2006-11-09 |
CN100423951C (zh) | 2008-10-08 |
US7557065B2 (en) | 2009-07-07 |
JP2005014337A (ja) | 2005-01-20 |
EP1645430A1 (en) | 2006-04-12 |
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