WO2011108411A1 - 感熱記録材料及びその製造方法 - Google Patents
感熱記録材料及びその製造方法 Download PDFInfo
- Publication number
- WO2011108411A1 WO2011108411A1 PCT/JP2011/053930 JP2011053930W WO2011108411A1 WO 2011108411 A1 WO2011108411 A1 WO 2011108411A1 JP 2011053930 W JP2011053930 W JP 2011053930W WO 2011108411 A1 WO2011108411 A1 WO 2011108411A1
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- WIPO (PCT)
- Prior art keywords
- heat
- sensitive recording
- recording material
- layer
- protective layer
- Prior art date
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Classifications
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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
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/44—Intermediate, backcoat, or covering layers characterised by the 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
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/04—Direct thermal recording [DTR]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/40—Cover layers; Layers separated from substrate by imaging layer; Protective layers; Layers applied before imaging
Definitions
- the present invention relates to a heat-sensitive recording material having a heat-sensitive recording layer and a protective layer that are colored by heat on a support in this order, and more particularly relates to a heat-sensitive recording material having excellent sticking resistance and good offset printing suitability, and a method for producing the same. .
- a heat-sensitive recording material generally comprises an electron-donating normally colorless or light-colored dye precursor and a heat-sensitive recording layer mainly composed of an electron-accepting compound on a support, and includes a thermal head, a thermal pen, and a laser. By heating with light or the like, an electron donating compound as a dye precursor and an electron accepting compound as a developer react instantaneously to obtain a recorded image.
- Such a heat-sensitive recording material has advantages such as that recording can be obtained with a relatively simple device, easy maintenance, no noise generation, etc., measurement recorder, facsimile, printer, computer terminal, It is used in a wide range of fields such as label printing machines, boarding tickets, and ticket issuing machines.
- heat-sensitive recording materials are also used for receipts of gas, water, electricity charges, etc., ATM usage statements of financial institutions, various receipts, lotteries, heat-sensitive recording labels or tags for POS systems. It has become.
- heat-sensitive recording materials used for tickets, chart paper for various devices, cash register receipts, CD / ATM specifications, receipts of gas issued by handy terminals, water charges, etc. develop color images by heat. May be pre-printed on the surface where appears.
- offset printing is usually performed because the printed image is clear and suitable for mass printing.
- Patent Document 1 discloses a heat-sensitive recording material having a protective layer in which a specific surface tension P defined by the surface tension and contact angle of water and linseed oil is 40 dyne / cm or less.
- a heat-sensitive recording material having a protective layer with a water contact angle of 45 ° or more is disclosed.
- Patent Document 3 discloses a heat-sensitive recording material having a protective layer containing an alkylbenzene sulfonate
- Patent Document 4 discloses an alkyl phosphate
- a heat-sensitive recording material having a protective layer containing a compound selected from waxes and higher fatty acids and a fluorosurfactant is disclosed.
- Patent Document 5 discloses a combination with a vinyl sulfone compound
- Patent Document 9 discloses a combination with a hydrazide compound
- Patent Document 10 discloses Sebacin.
- Patent Document 11 discloses a combination with an amino group-containing silane coupling agent
- Patent Document 12 discloses a combination with a specific aldehyde compound
- Patent Document 13 discloses a combination with dicarboxylic acid dihydrazide, but satisfactory offset printing suitability was not obtained.
- Patent Document 14 discloses a heat-sensitive recording material having a protective layer crosslinked with glyoxylate and a specific glyoxylate derivative as a heat-sensitive recording material having excellent water resistance and discoloration resistance.
- a heat-sensitive recording material excellent in printability, head residue, water resistance, sticking resistance, etc. discloses a heat-sensitive recording material having a protective layer obtained by crosslinking carboxy-modified polyvinyl alcohol with polyamidoamine epichlorohydrin.
- Reference 16 and the like disclose a heat-sensitive recording material having a protective layer in which silanol-modified polyvinyl alcohol is crosslinked with polyamidoamine epichlorohydrin as an example of a heat-sensitive recording material having excellent barrier properties against solvents and adhesion to printing inks. However, it was not satisfactory enough.
- An object of the present invention is to provide a heat-sensitive recording material that can solve these problems and achieve both sticking resistance and offset printing suitability, and a method for producing the same.
- An object of the present invention is to provide an acetoacetyl-modified polyvinyl alcohol in which a protective layer is crosslinked with a glyoxylate and an epichlorohydrin resin in a heat-sensitive recording material having a heat-sensitive recording layer and a protective layer that are colored by heat on the support in this order.
- This is basically achieved by a heat-sensitive recording material characterized by containing at least.
- the glyoxylate is preferably a metal salt of an alkaline earth metal and glyoxylic acid.
- the metal salt of alkaline earth metal and glyoxylic acid is preferably glyoxylic acid calcium salt or glyoxylic acid sodium salt, more preferably glyoxylic acid calcium salt.
- the epichlorohydrin resin is preferably a polyamide epichlorohydrin resin or a polyamine epichlorohydrin resin, and more preferably a polyamide epichlorohydrin resin.
- thermosensitive recording layer It is preferable to have an intermediate layer containing calcined kaolin and / or organic hollow pigment between the support and the thermosensitive recording layer.
- the above-mentioned problem is a method for producing a heat-sensitive recording material having a heat-sensitive recording layer and a protective layer that are colored by heat on a support in this order, and a coating solution for a heat-sensitive recording layer is applied on the support, A heat-sensitive recording layer is formed by drying, and a coating liquid containing acetoacetyl-modified polyvinyl alcohol, glyoxylate and epichlorohydrin resin is coated on the heat-sensitive recording layer, and then dried to be a protective layer
- This is basically achieved by a method for producing a heat-sensitive recording material characterized by forming the film.
- an intermediate layer coating solution is applied on a support and then dried to form an intermediate layer, and a heat-sensitive recording layer and a protective layer are formed in this order on the intermediate layer. It is also possible to adopt a method to do this.
- the protective layer of the heat-sensitive recording material of the present invention contains at least acetoacetyl-modified polyvinyl alcohol crosslinked with glyoxylate and epichlorohydrin resin.
- the glyoxylate in the present invention refers to a compound having an aldehyde group in the molecule, and the aldehyde group cross-links with acetoacetyl-modified polyvinyl alcohol.
- the glyoxylate include various salts such as alkali metal and glyoxylic acid metal salts, alkaline earth metal and glyoxylic acid metal salts, amines and glyoxylic acid salts, and preferably alkali It is at least one glyoxylic acid metal salt selected from metal and glyoxylic acid metal salts, alkaline earth metal and glyoxylic acid metal salts, more preferably alkaline earth metal and glyoxylic acid metal salts, most preferably Is a calcium glyoxylate.
- the glyoxylate is acetalized with an aldehyde group such as alcohol having 3 or less carbon atoms such as methanol or ethanol, diol having 3 or less carbon atoms such as ethylene glycol or propylene glycol, and hemiacetal. Including the compound.
- an aldehyde group such as alcohol having 3 or less carbon atoms such as methanol or ethanol, diol having 3 or less carbon atoms such as ethylene glycol or propylene glycol, and hemiacetal.
- an aldehyde group such as alcohol having 3 or less carbon atoms such as methanol or ethanol, diol having 3 or less carbon atoms such as ethylene glycol or propylene glycol, and hemiacetal.
- Such an acetal group and a hemiacetal group readily react with the aldehyde group and function as a cross-linking agent because the alcohol is easily eliminated in water or at a high temperature and takes an equilibrium state with the al
- Examples of the epichlorohydrin resin in the present invention include polyamide epichlorohydrin resin and polyamine epichlorohydrin resin. Specific examples include trade names WS4010, WS4011, WS4020, WS4024, WS4030, CP8970 (WS4010 and WS4011 are polyamine epichlorohydrin resins and others are polyamide epichlorohydrin resins) manufactured by Seiko PMC, Taoka Chemical. Examples include trade name Sumire's Resin 650 (30), Sumire Resin 675A (both are polyamide epichlorohydrin resins) manufactured by Kogyo Co., Ltd. Among these, it is more preferable to use a polyamide epichlorohydrin resin.
- the content of the epichlorohydrin resin is preferably 0.5 to 30% by mass, particularly preferably 3 to 20% by mass with respect to acetoacetyl-modified polyvinyl alcohol.
- the acetoacetyl-modified polyvinyl alcohol in the present invention refers to a product obtained by introducing an acetoacetyl group into the side chain of polyvinyl alcohol.
- the degree of polymerization, the degree of saponification, and the degree of modification of acetoacetyl-modified polyvinyl alcohol are not particularly limited, but the average degree of polymerization is 500 or more and less than 4000 from the viewpoint of solubility, coating properties, water resistance of the film, layer strength, etc.
- a saponification degree of 90% or more and a modification rate of about 1 to 10 mol% are preferred.
- the content of acetoacetyl-modified polyvinyl alcohol in the protective layer is preferably 20 to 80% by mass, particularly preferably 30 to 60% by mass, based on the total solid content of the protective layer.
- the crosslinking reaction between acetoacetyl-modified polyvinyl alcohol and glyoxylate and epichlorohydrin resin is excellent in the balance between the maintenance of the coating liquid pot life and the crosslinking speed.
- a coating solution containing an acid salt and an epichlorohydrin resin is coated on the heat-sensitive recording layer formed on the support by a conventionally known technique described later, and then dried. A good cross-linked state between acetoacetyl-modified polyvinyl alcohol and glyoxylate and epichlorohydrin resin can be realized.
- the heat-sensitive recording layer according to the present invention can be obtained by mixing each aqueous dispersion obtained by finely pulverizing each coloring component and a resin, and coating and drying on a support.
- the electron-donating compounds that are usually colorless to light-colored dye precursors contained in the heat-sensitive recording layer are typically represented by pressure-sensitive recording materials and those used in heat-sensitive recording materials, but are particularly limited. is not.
- Triarylmethane compounds 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone), 3,3-bis (p-dimethylaminophenyl) phthalide, 3- (P-dimethylaminophenyl) -3- (1,2-dimethylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3- (P-dimethylaminophenyl) -3- (2-phenylindol-3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3 -Bis (1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol
- Diphenylmethane compounds 4,4'-bis (dimethylaminophenyl) benzhydrylbenzyl ether, N-chlorophenylleucooramine, N-2,4,5-trichlorophenylleucooramine, etc.
- Spiro compounds 3-methylspirodinaphthopyrans, 3-ethylspirodinaphthopyrans, 3,3′-dichlorospirodinaphthopyrans, 3-benzylspirodinaphthopyrans, 3-methylnaphthyl (3-methoxy) Benzo) spiropyran, 3-propyl spirobenzopyran and the like.
- These dye precursors can be used alone or in admixture of two or more as required.
- pressure-sensitive recording materials or acidic substances used in heat-sensitive recording materials can be generally used, but are not particularly limited.
- phenol derivatives, aromatic carboxylic acid derivatives, N, N′-diarylthiourea derivatives, arylsulfonylurea derivatives, polyvalent metal salts such as zinc salts of organic compounds, benzenesulfonamide derivatives, urea urethane compounds, etc. Can do.
- Salicylanilide 5-chlorosalicylanilide, salicylic acid, 3,5-di-tert-butylsalicylic acid, 3,5-bis ( ⁇ -methylbenzyl) salicylic acid, 4- [2 '-(4-methoxyphenoxy) ethyloxy] salicylic acid , 3- (octyloxycarbonylamino) salicylic acid or metal salts of these salicylic acid derivatives (for example, zinc salts),
- the heat-sensitive recording layer can contain a heat-fusible substance as a sensitizer in order to improve its thermal response.
- a heat-fusible substance as a sensitizer in order to improve its thermal response.
- those having a melting point of 60 to 180 ° C. are preferred, and those having a melting point of 80 to 140 ° C. are more preferably used.
- stearic acid amide N-hydroxymethyl stearic acid amide, N-stearyl stearic acid amide, ethylene bis stearic acid amide, methylene bis stearic acid amide, methylol stearic acid amide, N-stearyl urea, benzyl-2- Naphthyl ether, m-terphenyl, 4-benzylbiphenyl, 2,2'-bis (4-methoxyphenoxy) diethyl ether, ⁇ , ⁇ '-diphenoxy-o-xylene, bis (4-methoxyphenyl) ether, adipic acid Diphenyl, dibenzyl oxalate, bis (4-methylbenzyl) oxalate, bis (4-chlorobenzyl) oxalate, dimethyl terephthalate, dibenzyl terephthalate, phenyl benzenesulfonate, bis (4-allyloxyphene) Ny
- the sensitizer accounts for 5 to 50% by mass in the total solid content of the thermosensitive recording layer.
- one or more intermediate layers can be provided between the support and the heat-sensitive recording layer as necessary, for example, to increase the color development sensitivity.
- one or more back coat layers such as a magnetic recording layer, an antistatic layer, and an adhesive layer can be provided on the opposite surface (back surface) of the thermosensitive recording layer with the support interposed therebetween.
- Inorganic pigments such as aluminum oxide, aluminum hydroxide, magnesium hydroxide, titanium dioxide, barium sulfate, zinc sulfate, amorphous silica, amorphous calcium silicate, colloidal silica, melamine resin, urea-formalin resin, polyethylene Organic pigments such as nylon, styrene plastic pigments, acrylic plastic pigments, and hydrocarbon plastic pigments can be used together with an adhesive.
- the calcined kaolin and / or organic hollow pigment is preferable as the intermediate layer pigment, and a heat-sensitive recording material having excellent heat response due to high heat insulation can be obtained.
- organic hollow pigment by including air in the hollow part, higher heat insulation is obtained, and since the pigment shape is nearly spherical, it can be arranged in nectar without impairing the flexibility of the layer, Since an intermediate layer having both high strength and flexibility can be obtained, excellent thermal response and surface strength are exhibited.
- the organic hollow pigment in the present invention refers to a resin pigment having a closed space inside the pigment, vinyl chloride, vinylidene chloride, vinyl acetate, styrene, methyl acrylate, ethyl acrylate, butyl acrylate, acrylonitrile, methyl methacrylate.
- the organic hollow pigment used in the present invention is not particularly limited within the scope of the effect of the present invention, but preferably has an average particle diameter of 0.1 to 5.0 ⁇ m as measured by a particle size distribution measurement method using a laser diffraction method. Further, those having a thickness of 0.5 to 2.0 ⁇ m are more preferable.
- the content of these organic hollow pigments is preferably 3 to 80% by mass with respect to the total solid content of the intermediate layer.
- an arbitrary resin is used as an adhesive for the support and an arbitrary layer (intermediate layer or back coat layer).
- Specific examples include starches, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, polyacrylic acid ester, polymethacrylic acid ester, polyacrylic acid.
- the protective layer and / or heat-sensitive recording layer preferably contains a lubricant such as a higher fatty acid metal salt, a higher fatty acid amide, paraffin, polyolefin, polyethylene oxide, or caster wax for the purpose of improving the sticking resistance.
- the content of the lubricant is preferably 5 to 50% by mass with respect to the total solid content of the protective layer or the heat-sensitive recording layer.
- the present invention works particularly effectively in a system containing such a lubricant.
- the protective layer and / or the thermosensitive recording layer is an interface containing an anionic or nonionic high molecular weight as a UV absorber such as benzophenone or benzotriazole, or a dispersing / wetting agent.
- An activator, further a fluorescent dye, an antifoaming agent, and the like are added as necessary.
- paper various woven fabrics, non-woven fabrics, synthetic resin films, synthetic resin laminated papers, synthetic papers, metal foils, vapor-deposited sheets, or composite sheets in which these are bonded together are used depending on the purpose. Can be used arbitrarily. Among them, paper such as neutral paper and acid paper is particularly preferably used because the water content can be easily controlled.
- the method for forming the heat-sensitive recording layer, the protective layer, the intermediate layer, and the backcoat layer is not particularly limited, and can be formed according to a conventionally known technique. Specific examples include applying film coating by film press coating, air knife coating, rod blade coating, bar coating, blade coating, gravure coating, curtain coating, E-bar coating, etc. Each layer can then be formed by drying. In addition, each layer may be formed by various printing machines or the like using a system such as a lithographic plate, a relief plate, a flexo, a gravure, a screen, and a hot melt. Furthermore, each layer may be applied and dried sequentially, or each layer may be applied and dried (wet-on-wet), and each layer may be applied and dried simultaneously.
- the coating amount of the heat-sensitive recording layer is usually preferably 0.05 to 2.0 g / m 2 in terms of the absolute dry coating amount of the dye precursor in order to obtain sufficient thermal response. 0 g / m 2 is more preferable.
- Ze'inuinurikoryou protective layer is preferably 0.2 ⁇ 10g / m 2, and more preferably 1 ⁇ 5g / m 2.
- Ze'inuinurikoryou of the intermediate layer is preferably 1 ⁇ 30g / m 2, and more preferably 3 ⁇ 20g / m 2.
- the absolute dry coating amount of the backcoat layer is appropriately selected depending on the required function and the like.
- the print image quality can be improved by supercalendering after intermediate layer coating, after heat-sensitive recording layer coating, after protective layer coating, or after backcoat layer coating.
- the present invention will be described in more detail with reference to examples. However, it is not limited to these.
- the parts and% shown below are based on mass, and the coating amount is the absolute dry coating amount.
- Example 1 Preparation of coating liquid for intermediate layer Firing kaolin (manufactured by BASF: trade name Ancilex) 50 parts, organic hollow pigment particle dispersion having a solid concentration of 27.5% [manufactured by ROHM & Haas: trade name HP91] A composition comprising 100 parts, 40 parts of 50% styrene / butadiene latex, 50 parts of 10% aqueous starch starch solution and 100 parts of water was mixed and stirred to prepare a coating solution for an intermediate layer.
- Firing kaolin manufactured by BASF: trade name Ancilex
- ROHM & Haas trade name HP91
- a protective layer coating liquid was prepared by mixing in the following composition. 10% acetoacetyl-modified polyvinyl alcohol [manufactured by Nippon Synthetic Chemical Industry Co., Ltd .: trade name Z-200 (average polymerization degree: about 1100, saponification degree: 99.0% or more)] aqueous solution 50 parts 20% kaolin [manufactured by BASF: trade name UW90 ] Water dispersion 20 parts 30% zinc stearate aqueous dispersion [manufactured by Chukyo Yushi Co., Ltd .: trade name Hydrin Z-7-30] 6 parts Glyoxylic acid calcium salt 0.25 part 25% polyamide epichlorohydrin resin aqueous solution 1 part 30 parts of water
- a neutral high-quality paper roll having a basis weight of 66 g / m 2 has a solid coating amount of 5 g / m 2 for the intermediate layer coating solution and a solid coating of the heat-sensitive recording layer coating solution.
- Air knife coater and air floating dryer so that the coating amount of the dye precursor is 0.5 g / m 2 and the solid coating amount of the coating liquid for the protective layer is 3 g / m 2.
- Example 2 In the preparation of the coating liquid for protective layer (4) of Example 1, heat sensitive as in Example 1 except that 0.25 part of sodium glyoxylate was used instead of 0.25 part of calcium glyoxylate. A recording material was prepared.
- Example 3 In preparation of the coating solution for protective layer (4) of Example 1, 10% acetoacetyl-modified polyvinyl alcohol instead of 50 parts of 10% acetoacetyl-modified polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd .: trade name Z-200) Thermosensitive in the same manner as in Example 1 except that 50 parts of an alcohol aqueous solution (manufactured by Nippon Synthetic Chemical Industry Co., Ltd .: trade name Z-410 (average polymerization degree of about 2300, saponification degree of 97.5 to 98.5%)) was used. A recording material was prepared.
- Example 4 In the preparation of the coating liquid for protective layer (4) of Example 1, instead of using 1 part of 25% polyamide epichlorohydrin resin aqueous solution, 1.25 parts of 20% polyamine epichlorohydrin resin aqueous solution was used. A thermosensitive recording material was produced in the same manner as in Example 1.
- Example 5 In the preparation of the coating liquid for protective layer (4) in Example 1, 0.25 part of calcium glyoxylate was changed to 0.05 part, and 1 part of 25% polyamide epichlorohydrin resin aqueous solution was changed to 1.8 parts. A heat-sensitive recording material was produced in the same manner as in Example 1 except for the change.
- Example 6 In the preparation of the coating liquid for protective layer (4) of Example 1, 0.25 part of calcium glyoxylate was changed to 0.3 part, and 1 part of 25% polyamide epichlorohydrin resin aqueous solution was changed to 0.8 part. A heat-sensitive recording material was produced in the same manner as in Example 1 except for the change.
- Comparative Example 1 Instead of 50 parts of 10% acetoacetyl-modified polyvinyl alcohol [manufactured by Nippon Synthetic Chemical Industry: trade name Z-200], 50% aqueous solution of 10% fully saponified polyvinyl alcohol [manufactured by Nippon Synthetic Chemical Industry: trade name NM-11] A heat-sensitive recording material was produced in the same manner as in Example 1 except that the part was used.
- Comparative Example 2 Instead of 50 parts of an aqueous solution of 10% acetoacetyl-modified polyvinyl alcohol [manufactured by Nippon Synthetic Chemical Industry: trade name Z-200], 50 parts of an aqueous solution of 10% carboxy-modified polyvinyl alcohol [trade name: KL-318] is used. A thermosensitive recording material was produced in the same manner as in Example 1 except that.
- Comparative Example 3 Instead of 50 parts of an aqueous solution of 10% acetoacetyl-modified polyvinyl alcohol [manufactured by Nippon Synthetic Chemical Industry: trade name Z-200], 50 parts of an aqueous solution of 10% silanol-modified polyvinyl alcohol [product of Kuraray: trade name R-1130] was used. A thermosensitive recording material was produced in the same manner as in Example 1 except that.
- Example 1 (4) In the preparation of the protective layer coating solution, Example 1 was used except that 0.25 part of glyoxylic acid calcium salt was not used and the 25% polyamide epichlorohydrin resin aqueous solution was changed to 2 parts. A thermosensitive recording material was produced in the same manner.
- Comparative Example 5 Thermosensitive recording was performed in the same manner as in Example 1 except that 0.25 part of adipic acid dihydrazide was used instead of 0.25 part of glyoxylic acid calcium salt in the preparation of the coating liquid for protective layer (4) of Example 1. The material was made.
- Example 1 (4) In the preparation of the protective layer coating solution, Example 1 was used except that 1 part of 25% polyamide epichlorohydrin resin aqueous solution was not used and the calcium glyoxylate salt was changed to 0.5 part. A thermosensitive recording material was produced in the same manner.
- Comparative Example 7 In the preparation of the coating solution for protective layer (4) of Example 1, the same procedure as in Example 1 was conducted except that 0.25 part of adipic acid dihydrazide was used instead of 1 part of 25% polyamide epichlorohydrin resin aqueous solution. Thus, a heat-sensitive recording material was produced.
- Example 4 In the production of the protective layer coating solution, the same procedure as in Example 1 was used except that 0.63 part of 40% aqueous glyoxal aqueous solution was used instead of 1 part of 25% polyamide epichlorohydrin resin aqueous solution. Thus, a heat-sensitive recording material was produced.
- Example 1 (4) In preparing the protective layer coating solution, Example 1 was used except that 0.56 parts of 45% zirconium ammonium carbonate aqueous solution was used instead of 1 part of 25% polyamide epichlorohydrin resin aqueous solution. A thermosensitive recording material was produced in the same manner as described above.
- Example 1 (4) In preparation of the protective layer coating solution, Example 1 and Example 1 were used except that 1 part of 25% aqueous solution of methylolated melamine resin was used instead of 1 part of 25% polyamide epichlorohydrin resin aqueous solution. A thermosensitive recording material was produced in the same manner.
- Offset printing aptitude Offset printing was performed using an RI printer. After adding 0.5 ml of water to 0.25 g of UV ink (trade name Best Cure UV NVR Red, manufactured by T & K), and printing with an ink kneading roller for 1 minute to knead the ink and water, UV irradiation was performed, and the uniformity of the printed portion was visually evaluated in four stages. The evaluation criteria followed the following indicators. ⁇ : Very good ⁇ : Good ⁇ : Inferior ⁇ : Very inferior
- the heat-sensitive recording materials of Examples 1 to 6 have high printing density, good sticking resistance and offset printability, and the present invention can achieve both sticking resistance and offset printability. It can be seen that a possible thermal recording material is obtained.
- the heat-sensitive recording materials of Comparative Examples 1 to 6 lack any one component of glyoxylate, epichlorohydrin resin and acetoacetyl-modified polyvinyl alcohol as a constituent component of the protective layer. At least one of the sticking property and the offset printability is inferior.
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Abstract
Description
(1)トリアリールメタン系化合物:3,3-ビス(p-ジメチルアミノフェニル)-6-ジメチルアミノフタリド(クリスタルバイオレットラクトン)、3,3-ビス(p-ジメチルアミノフェニル)フタリド、3-(p-ジメチルアミノフェニル)-3-(1,2-ジメチルインドール-3-イル)フタリド、3-(p-ジメチルアミノフェニル)-3-(2-メチルインドール-3-イル)フタリド、3-(p-ジメチルアミノフェニル)-3-(2-フェニルインドール-3-イル)フタリド、3,3-ビス(1,2-ジメチルインドール-3-イル)-5-ジメチルアミノフタリド、3,3-ビス(1,2-ジメチルインドール-3-イル)-6-ジメチルアミノフタリド、3,3-ビス(9-エチルカルバゾール-3-イル)-5-ジメチルアミノフタリド、3,3-ビス(2-フェニルインドール-3-イル)-5-ジメチルアミノフタリド、3-p-ジメチルアミノフェニル-3-(1-メチルピロール-2-イル)-6-ジメチルアミノフタリド等、
(1)中間層用塗液の作製
焼成カオリン〔BASF社製:商品名アンシレックス〕50部、固形分濃度27.5%の有機中空顔料粒子分散液〔ローム&ハース社製:商品名HP91〕100部、50%のスチレン/ブタジエン系ラテックス40部、10%の酸化澱粉水溶液50部及び水100部からなる組成物を混合攪拌し、中間層用塗液を調製した。
下記の(A)(B)(C)の混合液を、それぞれダイノミル(WAB社製サンドミル)で体積平均粒子径1μm以下となるように粉砕し、各分散液を得た。
(A)染料前駆体分散液
3-ジブチルアミノ-6-メチル-7-アニリノフルオラン 30部
2.5%スルホン変性ポリビニルアルコール水溶液 69部
1%アセチレングリコール系界面活性剤水溶液 1部
(B)電子受容性化合物分散液
4-ヒドロキシ-4′-イソプロポキシジフェニルスルホン 30部
2.5%スルホン変性ポリビニルアルコール水溶液 69部
1%アセチレングリコール系界面活性剤水溶液 1部
(C)顔料・増感剤分散液
水酸化アルミニウム(昭和電工社製:商品名ハイジライトH42)50部
1,2-ビス(3-メチルフェノキシ)エタン 30部
2.5%スルホン変性ポリビニルアルコール水溶液 199部
1%アセチレングリコール系界面活性剤水溶液 1部
次に、(A)、(B)、(C)の各分散液の他に下記のものを混合、攪拌して感熱記録層用塗液を調製した。
(A)染料前駆体分散液 100部
(B)電子受容性化合物分散液 100部
(C)顔料・増感剤分散液 280部
30%ステアリン酸亜鉛水分散液〔中京油脂社製:商品名ハイドリンZ-7-30〕 25部
40%メチロールステアリン酸アミド水分散液 25部
20%パラフィンワックス水分散液 25部
10%完全鹸化ポリビニルアルコール〔クラレ社製:商品名PVA117〕水溶液 200部
水 100部
下記に示す配合にて混合して保護層用塗液を調製した。
10%アセトアセチル変性ポリビニルアルコール
〔日本合成化学工業社製:商品名Z-200(平均重合度約1100、鹸化度99.0%以上)〕水溶液 50部
20%カオリン〔BASF社製:商品名UW90〕水分散液 20部
30%ステアリン酸亜鉛水分散液〔中京油脂社製:商品名ハイドリンZ-7-30〕 6部
グリオキシル酸カルシウム塩 0.25部
25%ポリアミドエピクロロヒドリン樹脂水溶液 1部
水 30部
坪量66g/m2の中性の上質紙ロールに、中間層用塗液の固形分塗工量が5g/m2、感熱記録層用塗液の固形分塗工量が染料前駆体の塗工量で0.5g/m2、保護層用塗液の固形分塗工量が3g/m2となるようにそれぞれの層をエアナイフコーター及びエアフローティング式乾燥機にて塗工および乾燥し、カレンダー処理を行い感熱記録材料を作製した。
実施例1の(4)保護層用塗液の作製において、グリオキシル酸カルシウム塩0.25部の代わりに、グリオキシル酸ナトリウム塩0.25部を用いた以外は、実施例1と同様にして感熱記録材料を作製した。
実施例1の(4)保護層用塗液の作製において、10%アセトアセチル変性ポリビニルアルコール〔日本合成化学工業社製:商品名Z-200〕水溶液50部の代わりに、10%アセトアセチル変性ポリビニルアルコール〔日本合成化学工業社製:商品名Z-410(平均重合度約2300、鹸化度97.5~98.5%)〕水溶液50部を用いた以外は、実施例1と同様にして感熱記録材料を作製した。
実施例1の(4)保護層用塗液の作製において、25%ポリアミドエピクロロヒドリン樹脂水溶液1部の代わりに、20%ポリアミンエピクロロヒドリン樹脂水溶液1.25部を用いた以外は、実施例1と同様にして感熱記録材料を作製した。
実施例1の(4)保護層用塗液の作製において、グリオキシル酸カルシウム塩0.25部を0.05部に変更し、25%ポリアミドエピクロロヒドリン樹脂水溶液1部を1.8部に変更した以外は実施例1と同様にして感熱記録材料を作製した。
実施例1の(4)保護層用塗液の作製において、グリオキシル酸カルシウム塩0.25部を0.3部に変更し、25%ポリアミドエピクロロヒドリン樹脂水溶液1部を0.8部に変更した以外は実施例1と同様にして感熱記録材料を作製した。
10%アセトアセチル変性ポリビニルアルコール〔日本合成化学工業社製:商品名Z-200〕水溶液50部の代わりに、10%完全鹸化ポリビニルアルコール〔日本合成化学工業社製:商品名NM-11〕水溶液50部を用いた以外は、実施例1と同様にして感熱記録材料を作製した。
10%アセトアセチル変性ポリビニルアルコール〔日本合成化学工業社製:商品名Z-200〕水溶液50部の代わりに、10%カルボキシ変性ポリビニルアルコール〔クラレ社製:商品名KL-318〕水溶液50部を用いた以外は、実施例1と同様にして感熱記録材料を作製した。
10%アセトアセチル変性ポリビニルアルコール〔日本合成化学工業社製:商品名Z-200〕水溶液50部の代わりに、10%シラノール変性ポリビニルアルコール〔クラレ社製:商品名R-1130〕水溶液50部を用いた以外は、実施例1と同様にして感熱記録材料を作製した。
実施例1の(4)保護層用塗液の作製において、グリオキシル酸カルシウム塩0.25部を用いず、25%ポリアミドエピクロロヒドリン樹脂水溶液を2部に変更した以外は、実施例1と同様にして感熱記録材料を作製した。
実施例1の(4)保護層用塗液の作製において、グリオキシル酸カルシウム塩0.25部の代わりに、アジピン酸ジヒドラジド0.25部を用いた以外は、実施例1と同様にして感熱記録材料を作製した。
実施例1の(4)保護層用塗液の作製において、25%ポリアミドエピクロロヒドリン樹脂水溶液1部を用いず、グリオキシル酸カルシウム塩を0.5部に変更した以外は、実施例1と同様にして感熱記録材料を作製した。
実施例1の(4)保護層用塗液の作製において、25%ポリアミドエピクロロヒドリン樹脂水溶液1部の代わりに、アジピン酸ジヒドラジド0.25部を用いた以外は、実施例1と同様にして感熱記録材料を作製した。
実施例1の(4)保護層用塗液の作製において、25%ポリアミドエピクロロヒドリン樹脂水溶液1部の代わりに、40%グリオキザール水溶液0.63部を用いた以外は、実施例1と同様にして感熱記録材料を作製した。
実施例1の(4)保護層用塗液の作製において、25%ポリアミドエピクロロヒドリン樹脂水溶液1部の代わりに、45%炭酸ジルコニウムアンモニウム水溶液0.56部を用いた以外は、実施例1と同様にして感熱記録材料を作製した。
実施例1の(4)保護層用塗液の作製において、25%ポリアミドエピクロロヒドリン樹脂水溶液1部の代わりに、25%メチロール化メラミン樹脂水溶液1部を用いた以外は、実施例1と同様にして感熱記録材料を作製した。
作製した各感熱記録材料それぞれについて、大倉電機社製のファクシミリ試験機で型番TH-PMDを用いて印字した。ドット密度8ドット/mm、ヘッド抵抗1685Ωのサーマルヘッドを使用し、印加電圧20ボルトで、印加パルス幅1.0msecで黒ベタ及び文字を印字した。印字濃度をマクベスRD-918型反射濃度計(ビジュアルフィルター)(マクベス社製)にて測定した。印字濃度の実用下限値は1.0で、好ましくは1.2以上である。
キヤノン(株)製のプリンターで商品名プレアCT-1を使用し、5℃の環境条件で印字して、印字面のスティッキングの程度を4段階で評価した。評価基準は以下の指標に従った。
◎:スティッキングが全く発生しない
○:スティッキングがごく僅かに発生する
△:スティッキングが発生する
×:スティッキングが全面に発生する
RI印刷機を用いてオフセット印刷を行った。UVインク〔T&K社製の商品名ベストキュアーUV NVR 紅)0.25gに水0.5mlを加え、インキ練りローラーで1分間インキと水を練りインキを乳化させたものを用いて印刷した後、UV照射して、印刷部の均一性を目視にて4段階で評価した。評価基準は以下の指標に従った。
◎:非常に良好
○:良好
△:劣る
×:非常に劣る
Claims (9)
- 支持体上に、熱により発色する感熱記録層及び保護層をこの順に有する感熱記録材料であって、該保護層がグリオキシル酸塩及びエピクロロヒドリン樹脂により架橋されたアセトアセチル変性ポリビニルアルコールを少なくとも含有することを特徴とする感熱記録材料。
- 該グリオキシル酸塩が、アルカリ土類金属とグリオキシル酸の金属塩である請求項1に記載の感熱記録材料。
- 該アルカリ土類金属とグリオキシル酸の金属塩が、グリオキシル酸カルシウム塩またはグリオキシル酸ナトリウム塩である請求項2に記載の感熱記録材料。
- 該アルカリ土類金属とグリオキシル酸の金属塩が、グリオキシル酸カルシウム塩である請求項3に記載の感熱記録材料。
- 該エピクロロヒドリン樹脂が、ポリアミドエピクロロヒドリン樹脂またはポリアミンエピクロロヒドリン樹脂である請求項1~4のいずれか1項に記載の感熱記録材料。
- 該エピクロロヒドリン樹脂が、ポリアミドエピクロロヒドリン樹脂である請求項5に記載の感熱記録材料。
- 支持体と感熱記録層の間に、焼成カオリン及び/または有機中空顔料を含有する中間層を有する請求項1~6のいずれか1項に記載の感熱記録材料。
- 支持体上に、熱により発色する感熱記録層及び保護層をこの順に有する感熱記録材料の製造方法であって、支持体上に感熱記録層用塗液を塗工し、次いで乾燥することにより感熱記録層を形成し、該感熱記録層上にアセトアセチル変性ポリビニルアルコール、グリオキシル酸塩及びエピクロロヒドリン樹脂を含有する塗工液を塗工し、次いで乾燥することにより保護層を形成することを特徴とする感熱記録材料の製造方法。
- 支持体上に、熱により発色する感熱記録層及び保護層をこの順に有する感熱記録材料の製造方法であって、支持体上に中間層用塗液を塗工し、次いで乾燥することにより中間層を形成し、該中間層上に感熱記録層用塗液を塗工し、次いで乾燥することにより感熱記録層を形成し、該感熱記録層上にアセトアセチル変性ポリビニルアルコール、グリオキシル酸塩及びエピクロロヒドリン樹脂を含有する塗工液を塗工し、次いで乾燥することにより保護層を形成することを特徴とする感熱記録材料の製造方法。
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DE112011100779.5T DE112011100779B4 (de) | 2010-03-04 | 2011-02-23 | Thermisches Aufzeichungsmaterial und Verfahren zur Herstellung desselben |
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Cited By (2)
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JP2017193111A (ja) * | 2016-04-20 | 2017-10-26 | 王子ホールディングス株式会社 | 感熱記録体 |
JP2017209915A (ja) * | 2016-05-27 | 2017-11-30 | 王子ホールディングス株式会社 | 感熱記録体 |
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WO2014077145A1 (ja) * | 2012-11-19 | 2014-05-22 | 日本合成化学工業株式会社 | 感熱記録媒体および感熱発色層形成用塗工液 |
DE102014107567B3 (de) * | 2014-05-28 | 2015-11-05 | Papierfabrik August Koehler Se | Wärmeempfindliches Aufzeichnungsmaterial |
JP6436807B2 (ja) * | 2014-08-28 | 2018-12-12 | 日本合成化学工業株式会社 | 保護層用塗工液、保護層及び感熱記録媒体 |
JP2016124126A (ja) * | 2014-12-26 | 2016-07-11 | 日本合成化学工業株式会社 | 保護層用塗工液、および感熱記録媒体 |
JP2015083391A (ja) * | 2015-01-22 | 2015-04-30 | 三菱製紙株式会社 | 感熱記録材料の製造方法 |
DE102015104306B4 (de) * | 2015-03-23 | 2018-05-03 | Papierfabrik August Koehler Se | Wärmeempfindliches Aufzeichnungsmaterial |
DE102017111022A1 (de) | 2017-05-19 | 2018-11-22 | Mitsubishi Hitec Paper Europe Gmbh | Beschichtungszusammensetzung zur Herstellung eines Schichtverbundes |
WO2018211063A2 (de) | 2017-05-19 | 2018-11-22 | Mitsubishi Hitec Paper Europe Gmbh | Beschichtungszusammensetzung zur herstellung eines schichtverbundes |
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Also Published As
Publication number | Publication date |
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DE112011100779B4 (de) | 2022-10-06 |
JP5485749B2 (ja) | 2014-05-07 |
JP2011178139A (ja) | 2011-09-15 |
US20120329646A1 (en) | 2012-12-27 |
DE112011100779T5 (de) | 2012-12-20 |
CN102781678B (zh) | 2015-09-30 |
CN102781678A (zh) | 2012-11-14 |
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