WO2020189183A1 - 感熱記録体 - Google Patents
感熱記録体 Download PDFInfo
- Publication number
- WO2020189183A1 WO2020189183A1 PCT/JP2020/007308 JP2020007308W WO2020189183A1 WO 2020189183 A1 WO2020189183 A1 WO 2020189183A1 JP 2020007308 W JP2020007308 W JP 2020007308W WO 2020189183 A1 WO2020189183 A1 WO 2020189183A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- heat
- sensitive recording
- resin
- recording layer
- acrylic resin
- Prior art date
Links
Images
Classifications
-
- 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
- B41M5/3372—Macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/323—Organic colour formers, e.g. leuco dyes
-
- 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
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/337—Additives; Binders
-
- 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]
Definitions
- the present invention relates to a thermal recorder having a high degree of water resistance and excellent surface properties.
- leuco dye colorless or light-colored electron-donating leuco dye
- color developer electron-accepting color developer
- thermal recording materials is also required to have a higher surface quality (also called surface feeling) as basic performance, and further, labels, tickets, handy terminal paper, delivery slips, etc.
- surface quality also called surface feeling
- a high degree of water resistance is required that can withstand rough handling during rainfall.
- a protective layer is provided on the heat-sensitive recording layer, and various acrylic resins are contained in the protective layer (Patent Documents 1 to 3, etc.), but protection is performed. Having a layer reduces the color development performance of the thermal recorder.
- the heat-sensitive recording layer does not have such a protective layer, and the heat-sensitive recording layer contains a carboxyl group-containing resin, an epichlorohydrin-based resin, and a polyamine / amide. It is known to contain a based resin (Patent Documents 4 and 5).
- an object of the present invention is to provide a thermal recording body having a high degree of water resistance and excellent surface properties without providing a protective layer.
- the heat-sensitive recording layer contains a carboxyl group-containing resin, an epichlorohydrin-based resin, and a polyamine / amide-based resin (Patent Documents 4 and 5), and variously used in combination with the carboxyl group-containing resin.
- Acrylic resin was examined.
- the glass transition point (Tg) is 50 ° C. or lower and the minimum film forming temperature (MFT) is 40.
- Tg glass transition point
- MFT minimum film forming temperature
- the present invention has a heat-sensitive recording layer containing a colorless or light-colored electron-donating leuco dye and an electron-accepting color developer as main components on the support, and the heat-sensitive recording layer is on the heat-sensitive recording layer.
- the heat-sensitive recording layer contains a carboxy-modified polyvinyl alcohol as a binder, and an epichlorohydrin-based resin and a polyamine / polyamide-based resin (in the epichlorohydrin-based resin) as a cross-linking agent.
- It is a thermal recording body containing an acrylic resin having a glass transition point (Tg) of 50 ° C. or lower and a minimum film forming temperature (MFT) of 40 ° C. or higher.
- the surface photograph of the solid printed matter of the thermal recording body is shown.
- A shows the printed matter of Example 1 and B shows the printed matter of Comparative Example 3.
- the thermal recording body of the present invention indispensably has a thermal recording layer on the support, and does not have a protective layer on the thermal recording layer.
- the heat-sensitive recording body may optionally have an undercoat layer between the support and the heat-sensitive recording layer, and may have a backcoat layer on the opposite surface of the support from the heat-sensitive recording layer.
- a coating layer appropriately configured according to the purpose of use may be provided between these layers.
- This support can be appropriately selected from conventionally known supports such as paper, recycled paper, synthetic paper, film, plastic film, foamed plastic film, and non-woven fabric according to the desired quality of the heat-sensitive recording material, and is particularly limited. It is not something that is done. Moreover, you may use the composite sheet which combined these as a support.
- the heat-sensitive recording layer of the present invention contains a carboxy-modified polyvinyl alcohol as a binder, and further contains an epichlorohydrin-based resin and a polyamine / polyamide-based resin (excluding those contained in the epichlorohydrin-based resin) as a cross-linking agent. It contains, and further contains a specific acrylic resin.
- the glass transition point (Tg) of this acrylic resin is 50 ° C. or lower, preferably 40 to 50 ° C.
- the glass transition temperature (Tg) is such that each element of the composition (monomer) constituting the resin is in accordance with JIS K-7122, and a scanning differential calorimeter (10 mg sample is raised at 25 ° C./min under a nitrogen atmosphere).
- the glass transition temperature (Tg) of the resin Tg1 ⁇ ⁇ 1 + Tg2 ⁇ ⁇ 2 + ... + Tgn ⁇ ⁇ n (Tg1, Tg2 ... Tgn: measured), where the change in specific heat accompanying the secondary transition measured in temperature) is taken as the glass transition temperature. It is calculated from the calculation formula of the glass transition temperature of each composition unit, ⁇ 1, ⁇ 2 ... ⁇ n: weight fraction (%) of each composition unit with respect to the total weight of the resin.
- the minimum film formation temperature (MFT) of this acrylic resin is 40 ° C. or higher, preferably 50 ° C. or higher, and more preferably 60 to 80 ° C.
- This minimum film thickening temperature (MFT) is based on JIS K-6828, and the resin adjusted to 20% by weight is spread over the entire surface of the slide glass and dried at a predetermined temperature, and the dried resin is a uniform continuous film. The temperature is set to the minimum temperature at which the film is not clouded.
- acrylic resin examples include A537 (manufactured by Johnson Polymer Co., Ltd., Tg 49 ° C., MFT 42 ° C.) and A25 (manufactured by Aica Kogyo Co., Ltd., Tg 47 ° C., MFT 70 ° C.).
- the acrylic resin used in the present invention includes unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid, which contain a methyl methacrylate (MMA) monomer, and monoesters thereof and acetic acid. It is synthesized by polymerization of unsaturated group-containing polymerizable monomers such as vinyl esters such as vinyl and vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether.
- the content of methyl methacrylate (MMA) is preferably 50% or more, more preferably 60% or more.
- Examples of such an acrylic resin include A25 (manufactured by Aica Kogyo Co., Ltd., containing 60% or more of MMA).
- the acrylic resin used in the present invention preferably does not contain styrene as a monomer component, and is preferably a non-core shell type acrylic resin.
- examples of such an acrylic resin include A25 (manufactured by Aica Kogyo Co., Ltd.).
- the carboxy-modified polyvinyl alcohol used in the present invention is a reaction product of a polyvinyl alcohol and a polyvalent carboxylic acid such as fumaric acid, phthalic acid anhydride, meritonic acid anhydride, itaconic acid anhydride, an esterified product of these reactants, and acetic acid. It is obtained as a saponified product of a copolymer of vinyl with an ethylenically unsaturated dicarboxylic acid such as maleic acid, fumaric acid, itaconic acid, crotonic acid, acrylic acid and methacrylic acid. Specifically, for example, the production method exemplified in Example 1 or 4 of JP-A-53-91995 can be mentioned.
- the saponification degree of the carboxy-modified polyvinyl alcohol is preferably 72 to 100 mol%, and the degree of polymerization is 500 to 2400, more preferably 1000 to 2000.
- a binder other than carboxy-modified polyvinyl alcohol may be used in combination as long as the desired performance is not impaired.
- binders fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, Olefin-modified polyvinyl alcohol, nitrile-modified polyvinyl alcohol, pyrrolidone-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, cationic-modified polyvinyl alcohol, terminal alkyl-modified polyvinyl alcohol and other polyvinyl alcohols, hydroxye
- Cellulose ether and its derivatives starch, enzyme-modified starch, thermochemical-modified starch, oxidized starch, esterified starch, etherified starch (eg, hydroxyethylated starch, etc.), starches such as cationized starch, polyacrylamide, cationic Polyacrylamides such as polyacrylamide, anionic polyacrylamide, and amphoteric polyacrylamide, polyurethane resins such as polyester polyurethane resins, polyether polyurethane resins, urethane resins such as polyurethane ionomer resins, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile Copolymers, styrene-butadiene resins such as styrene-butadiene-acrylic copolymers, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, polyolefin resins such as ethylene
- the binder of the heat-sensitive recording layer of the present invention is preferably a total amount of carboxy-modified polyvinyl alcohol, but when a binder other than carboxy-modified polyvinyl alcohol is used in combination, the amount thereof is preferably 40 with respect to the total amount of the binder. By weight or less, more preferably 30% by weight or less.
- the epichlorohydrin-based resin used in the present invention is a resin characterized by containing an epoxy group in the molecule, and examples thereof include polyamide epichlorohydrin resin and polyamine epichlorohydrin resin. These can be used alone or in combination. Further, as the amine present in the main chain of the epichlorohydrin-based resin, primary to quaternary amines can be used, and there is no particular limitation. Further, since the water resistance is good, the degree of cationization and the molecular weight are preferably 5 meq / g ⁇ Solid or less (measured value at pH 7) and a molecular weight of 500,000 or more.
- epichlorohydrin-based resin examples include violet resin 650 (30), violet resin 675A, violet resin 6615 (manufactured by Sumitomo Chemical Corporation), WS4002, WS4020, WS4024, WS4030, WS4046, WS4010, CP8970. (The above is manufactured by Seiko PMC) and the like.
- the polyamine / polyamide resin used in the present invention means a polyamine resin and / or a polyamide resin, and does not include those contained in the above epichlorohydrin resin.
- Examples of such polyamine / polyamide-based resins include polyamide urea resin, polyalkylene polyamine resin, polyalkylene polyamide resin, polyamine polyurea resin, modified polyamine resin, modified polyamide resin, and poly, which do not have an epoxy group in the molecule.
- Examples thereof include an alkylene polyamine urea formalin resin and a polyalkylene polyamine polyamide polyurea resin, and these can be used alone or in combination.
- Such a polyamine / polyamide resin examples include violet resin 302 (manufactured by Sumitomo Chemical Co., Ltd .: polyamine polyurea resin), violet resin 712 (manufactured by Sumitomo Chemical Co., Ltd .: polyamine polyurea resin), and violet resin 703.
- polyamine-based resin polyalkylene polyamine resin, polyamine polyurea resin, modified polyamine resin, polyalkylene polyamine urea formalin resin, polyalkylene polyamine polyamide polyurea tree
- polyamine-based resin polyalkylene polyamine resin, polyamine polyurea resin, modified polyamine resin, polyalkylene polyamine urea formalin resin, polyalkylene polyamine polyamide polyurea tree
- the heat-sensitive recording layer of the present invention essentially contains a leuco dye and a color developer in addition to the above binder and cross-linking agent and the above acrylic resin, and optionally cross-links other than the sensitizer, pigment and the above-mentioned cross-linking agent. It may contain an agent, an image stabilizer, and other components.
- leuco dye used in the present invention all conventional leuco dyes known in the field of pressure-sensitive or thermal recording paper can be used, and are not particularly limited, but are triphenylmethane-based compounds, fluorene-based compounds, and fluorene. System, divinyl compound and the like are preferable. Specific examples of typical colorless or light-colored leuco dyes (dye precursors) are shown below. Moreover, these leuco dyes may be used alone or in mixture of 2 or more types.
- Triphenylmethane leuco dye 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide [also known as crystal violet lactone]; 3,3-bis (p-dimethylaminophenyl) phthalide [also known as malachite green lactone]
- color developer used in the present invention those known in the field of conventional pressure-sensitive or heat-sensitive recording paper can be used, and are not particularly limited, but for example, active white clay, attapulsite, colloidal silica, and the like.
- Inorganic acidic substances such as aluminum silicate, 4,4'-isopropyridene diphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 4, , 4'-dihydroxydiphenylsulfide, hydroquinone monobenzyl ether, benzyl 4-hydroxybenzoate, 4,4'-dihydroxydiphenylsulfone, 2,4′-dihydroxydiphenylsulfone, 4-hydroxy-4′-isopropoxydiphenylsulfone, 4-Hydroxy-4'-n-propoxydiphenyl sulfone, bis (3-allyl-4-hydroxyphenyl) sulfone,
- Examples thereof include a salt with a polyvalent metal salt, an antipyrine complex of zinc thiocyanate, and a composite zinc salt of terephthalaldehyde acid and another aromatic carboxylic acid. These color developeres can be used alone or in combination of two or more.
- 1- [4- (4-Hydroxyphenylsulfonyl) phenoxy] -4- [4- (4-isopropoxyphenylsulfonyl) phenoxy] butane is available, for example, under the trade name TOMILAC214 manufactured by Mitsubishi Chemical Co., Ltd.
- the phenol condensation composition described in Kai 2003-154760 is available, for example, under the trade name TOMILAC224 manufactured by Mitsubishi Chemical Co., Ltd., and the diphenyl sulfone cross-linked compound described in International Publication WO 97/16420 is Nippon Soda Co., Ltd. It is available under the trade name D-90.
- the compounds described in WO02 / 081229 and the like are available under the trade names NKK-395 and D-100 manufactured by Nippon Soda Corporation.
- sensitizer that can be used in the present invention
- a conventionally known sensitizer can be used.
- sensitizers include fatty acid amides such as stearic acid amide and palmitate amide, ethylene bisamide, montanic acid wax, polyethylene wax, 1,2-di- (3-methylphenoxy) ethane, p-benzylbiphenyl and ⁇ -.
- pigments examples include inorganic or organic fillers such as silica, calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium oxide, and aluminum hydroxide. These may be used alone or in combination of two or more.
- cross-linking agent other than the above-mentioned cross-linking agent examples include glioxal, methylol melamine, melamine formaldehyde resin, melamine urea resin, potassium persulfate, ammonium persulfate, sodium persulfate, ferric chloride, magnesium chloride, and alum.
- glioxal methylol melamine, melamine formaldehyde resin, melamine urea resin
- potassium persulfate ammonium persulfate
- sodium persulfate ferric chloride
- magnesium chloride magnesium chloride
- alum Boric acid, alum, ammonium chloride and the like can be exemplified.
- 4,4'-butylidene (6-t-butyl-3-methylphenol) is used as an image stabilizer that exhibits an oil resistance effect of recorded images within a range that does not impair the desired effect on the above-mentioned problems.
- 2,2'-di-t-butyl-5,5'-dimethyl-4,4'-sulfonyldiphenol 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) Butane, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 4-benzyloxy-4'-(2,3-epoxy-2-methylpropoxy) diphenylsulfone, etc.
- benzophenone-based or triazole-based ultraviolet absorbers, dispersants, antifoaming agents, antioxidants, fluorescent dyes and the like can be used.
- the types and amounts of the electron-donating leuco dye, the electron-accepting color developer, and various other components used in the heat-sensitive recording material of the present invention are determined according to the required performance and recording suitability, and are not particularly limited. Usually, about 0.5 to 10 parts by weight of an electron-accepting color developer and 0 to 10 parts by weight of a sensitizer are used with respect to 1 part by weight of an electron-donating leuco dye.
- the types and amounts of other optional components such as binders, pigments, lubricants, cross-linking agents, image stabilizers, and other components are determined according to the required performance and recordability, and are not particularly limited, but are usually used.
- the binder is suitable for 100 parts by weight of the heat-sensitive recording layer (solid content) with a solid content of about 5 to 50 parts by weight
- the pigment is suitable for 100 parts by weight of the heat-sensitive recording layer (solid content) with a solid content of about 0 to 50 parts by weight.
- the content of the lubricant is preferably about 5 to 10 parts by weight in terms of solid content with respect to 100 parts by weight of the thermal recording layer (solid content).
- the total amount of the carboxy-modified polyvinyl alcohol and the acrylic resin used in the present invention is about 1 to 50 parts by weight, preferably 3 to 40 parts by weight, based on 100 parts by weight of the heat-sensitive recording layer (solid content). , More preferably 4 to 20 parts by weight. If it is too small, the strength and water resistance of the coating layer will be insufficient, and if it is too large, the sensitivity will easily decrease.
- the weight ratio of the carboxy-modified polyvinyl alcohol to the acrylic resin (carboxy-modified polyvinyl alcohol / acrylic resin) used in the present invention is preferably 80/20 to 20/80, more preferably 70/30 to 30/70, and even more preferably. Is 60/40 to 40/60.
- the contents of the epichlorohydrin-based resin and the polyamine / polyamide-based resin (excluding those contained in the epichlorohydrin-based resin) used in the present invention are preferably 100 parts by weight of carboxy-modified polyvinyl alcohol. It is 1 to 100 parts by weight, more preferably 5 to 50 parts by weight. If the content is too small, the cross-linking reaction will be insufficient and good water resistance cannot be obtained, and if it is too large, the viscosity of the coating liquid will increase and gelation will cause problems in operability.
- Leuco dyes, color formers, and materials to be added as needed are atomized by a crusher such as a ball mill, attritor, sand glider, or an appropriate emulsifying device to a particle size of several microns or less, and various types are used according to the purpose.
- a crusher such as a ball mill, attritor, sand glider, or an appropriate emulsifying device to a particle size of several microns or less, and various types are used according to the purpose.
- Add the additive material of to make a coating liquid Water, alcohol, or the like can be used as the solvent used in this coating liquid, and the solid content thereof is about 20 to 40% by weight.
- Each coating layer arbitrarily provided other than the heat-sensitive recording layer can use the above-mentioned binder, pigment, cross-linking agent, and other components as long as the desired effect is not impaired.
- the coating method of the heat-sensitive recording layer and other coating layers is not particularly limited, and is a curtain coating method, an air knife coating method, a bar blade coating method, a rod blade coating method, a vent blade coating method, and a bevel blade coating method.
- a conventionally known method such as a roll coating method and a spray coating method can be adopted.
- the coating amount of the heat-sensitive recording layer and other coating layers is determined according to the required performance and recording suitability, and is not particularly limited.
- the general coating amount of the heat-sensitive recording layer is the solid content. It is about 2 to 12 g / m 2 .
- various known techniques in the field of thermal recording materials can be added as necessary, such as performing a smoothing treatment such as super calendar hanging after coating each layer.
- a coating solution for an undercoat layer was prepared by stirring and dispersing a formulation consisting of the following formulations.
- color developer dispersions A1 to A2 solutions
- leuco dye dispersions B solution
- sensitizer dispersions C solution
- Color developer dispersion liquid (A1 liquid ) 4,4'-Dihydroxydiphenylsulfone (manufactured by NICCA CHEMICAL CO., LTD.)
- Product name BPS-P 6.0 parts Completely saponified polyvinyl alcohol aqueous solution (manufactured by Kuraray, product name: PVA117, solid content 10%) 5.0 parts Water 1.5 parts
- each dispersion was mixed at the following ratio to prepare a coating liquid for a heat-sensitive recording layer.
- Example 1 After applying the coating liquid for the undercoat layer to one side of the support (high-quality paper with a basis weight of 47 g / m 2 ) by the vent blade method so that the coating amount is 10.0 g / m 2 in terms of solid content. It was dried to obtain an undercoat layer coated paper. On the undercoat layer of this undercoat layer coating paper, the coating liquid for the thermal recording layer is applied by the rod blade method so that the coating amount is 6.0 g / m 2 in terms of solid content, and then dried. A heat-sensitive recorder was prepared by processing with a super calendar so that the smoothness was 500 to 1000 seconds.
- Example 2 The same as in Example 1 except that the acrylic resin of the coating liquid for the thermal recording layer was changed to 4.3 parts of an acrylic resin (manufactured by Johnson Polymer Co., Ltd., A537, solid content 45%, Tg 49 ° C., MFT 42 ° C.). A heat-sensitive recording body was prepared.
- Example 3 A heat-sensitive recording body was produced in the same manner as in Example 1 except that the acrylic resin of the coating liquid for the heat-sensitive recording layer was changed to 2.5 parts and the carboxy-modified polyvinyl alcohol aqueous solution was changed to 40.0 parts.
- Example 4 A heat-sensitive recording body was produced in the same manner as in Example 1 except that the acrylic resin of the coating liquid for the heat-sensitive recording layer was changed to 8.0 parts and the carboxy-modified polyvinyl alcohol aqueous solution was changed to 10.0 parts.
- Example 1 The same as in Example 1 except that the acrylic resin (manufactured by Aika Kogyo Co., Ltd., trade name: A25) of the coating liquid for the heat-sensitive recording layer was not blended and the carboxy-modified polyvinyl alcohol aqueous solution was changed to 40.0 parts. A thermal recorder was prepared.
- Example 4 A heat-sensitive recording body was produced in the same manner as in Example 1 except that the carboxy-modified polyvinyl alcohol aqueous solution, the polyamide resin, and the polyamide epichlorohydrin resin of the coating liquid for the heat-sensitive recording layer were not blended.
- Example 5 A heat-sensitive recording body was produced in the same manner as in Example 1 except that the carboxy-modified polyvinyl alcohol aqueous solution of the coating liquid for the heat-sensitive recording layer was not blended.
- Example 6 Example 1 and Example 1 except that 1.5 parts of glioxal aqueous solution (solid content 40%) was not blended with the carboxy-modified polyvinyl alcohol aqueous solution, polyamide resin, and polyamide epichlorohydrin resin of the coating liquid for the heat-sensitive recording layer.
- a heat-sensitive recorder was prepared in the same manner.
- Comparative Example 7 A heat-sensitive recorder in the same manner as in Example 1 except that 1.5 parts of an aqueous glioxal solution (solid content 40%) was not blended with the polyamide resin and polyamide epichlorohydrin resin of the coating liquid for the heat-sensitive recording layer. was produced.
- the prepared heat-sensitive recorder was evaluated as follows. ⁇ Color development performance (print density)>
- TH-PMD manufactured by Okura Electric Co., Ltd. (with a heat-sensitive recording paper printing tester and a thermal head manufactured by Kyocera) was used, and the applied energy was 0.35 mJ / dot and 0.41 mJ / dot, and the printing speed.
- a checkerboard pattern was printed at 50 mm / sec.
- the print density of the print section was measured with a Macbeth densitometer (RD-914, using an amber filter), and the color development performance (print density) was evaluated.
- TH-PMD thermal recording paper printing tester, manufactured by Okura Electric Co., Ltd.
- a checkerboard pattern was printed at an applied energy of 0.41 mJ / dot and a printing speed of 50 mm / sec using a thermal head manufactured by Kyocera Corporation.
- the printed thermal recorder is attached to a paper tube with PVC wrap (Mitsui Chemicals High Wrap KMA) wrapped once, and then wrapped with PVC wrap three times, at 23 ° C, 50% RH environmental conditions. It was allowed to stand underneath for 24 hours.
- PVC wrap Mitsubishi Chemicals High Wrap KMA
- Residual rate (%) (print density of printed area after processing / print density of printed area before processing) x 100
- the manufactured heat-sensitive recording body is solid-printed using TH-PMD manufactured by Okura Electric Co., Ltd. (with a heat-sensitive recording paper printing tester and a thermal head manufactured by Kyocera), and the surface texture (uniformity) of the heat-sensitive recording layer coated surface is performed. Sex) was visually evaluated according to the following criteria. Excellent: No foreign matter on the coated surface and uniform printed surface Possible: There is a slight foreign matter on the coated surface, but the printed surface is almost uniform and there is no problem in practical use. Impossible: There is foreign matter on the coated surface and the printed surface is Non-uniformity Photographs of the surfaces of the printed matter of Example 1 and Comparative Example 3 are shown in FIG. 1 (A: Example 1, B: Comparative Example 3).
- the heat-sensitive recording bodies of Examples 1, 3 and 4 had extremely excellent water resistance, and had no foreign matter on the coated surface, and the printed surface during solid printing was uniform and had excellent surface properties.
- the heat-sensitive recording material of Example 2 was slightly inferior to Examples 1, 3 and 4 in both water resistance and surface properties, but there was no problem in practical use. These results show the excellent performance of the thermal recording body having the thermal recording layer having the configuration of the present invention.
- the heat-sensitive recording material of Comparative Example 1 lacking the acrylic resin of the present invention in the heat-sensitive recording layer had excellent surface properties, but was inferior in immersion friction in water resistance.
- the heat-sensitive recording bodies of Comparative Examples 2 and 3 in which Tg and MFT are different from the acrylic resin of the present invention are generally inferior in water resistance and have foreign substances on the coated surface. White spots and unevenness occurred during solid printing, and the surface quality was also inferior.
- the thermal recording materials of Comparative Examples 4 to 7 lacking any or all of carboxy-modified polyvinyl alcohol, epichlorohydrin-based resin and polyamine / polyamide-based resin are generally inferior in water resistance and are generally inferior in water resistance and Comparative Examples 4 to 4.
- the heat-sensitive recording material of No. 6 was inferior in plasticizer resistance
- the heat-sensitive recording material of Comparative Example 5 had foreign matter on the coated surface, causing white spots and unevenness during solid printing, and the surface property was also inferior.
Landscapes
- 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
このような用途の拡大に伴い、近年、感熱記録体の品質も、基本性能として従来以上に高度な表面性(面感ともいう)が求められ、さらに、ラベル、チケット、ハンディターミナル用紙、配送伝票など屋外で使用される用途においては、例えば、降雨時の手荒な扱いにも耐えることの出来る、高度な耐水性が求められている。
耐水性などの耐久性を改良するために、感熱記録層上に保護層を設け、保護層に種々のアクリル系樹脂を含有させることが行われているが(特許文献1~3等)、保護層を有すると、感熱記録体の発色性能は低下する。
一方、感熱記録体の発色性能を落とさずに耐水性等を向上させるため、このような保護層を有さずに、感熱記録層にカルボキシル基含有樹脂、エピクロロヒドリン系樹脂及びポリアミン/アミド系樹脂を含有させることが知られている(特許文献4、5)。
この支持体は、所望する感熱記録体の品質に合わせて、紙、再生紙、合成紙、フィルム、プラスチックフィルム、発泡プラスチックフィルム、不織布など、従来公知の支持体から適宜選択可能であり、特に限定されるものではない。また、これらを組み合わせた複合シートを支持体として使用してもよい。
このようなアクリル系樹脂として、例えば、A537(ジョンソンポリマー社製、Tg49℃、MFT42℃)、A25(アイカ工業株式会社製、Tg47℃、MFT70℃)などが挙げられる。
このようなアクリル系樹脂として、例えば、A25(アイカ工業株式会社製、MMA60%以上含有)などが挙げられる。
また、本発明で用いるアクリル系樹脂は、単量体成分としてスチレンを含まないことが好ましく、非コアシェル型のアクリル系樹脂であることが好ましい。このようなアクリル系樹脂として、例えば、A25(アイカ工業株式会社製) などが挙げられる。
本発明の該感熱記録層のバインダーは、全量カルボキシ変性ポリビニルアルコールであることが好ましいが、カルボキシ変性ポリビニルアルコール以外のバインダーを併用する場合には、その量は、バインダー全量に対して、好ましくは40重量%以下、より好ましくは30重量%以下である。
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〔別名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〔別名マラカイトグリーンラクトン〕
3-ジエチルアミノ-6-メチルフルオラン; 3-ジエチルアミノ-6-メチル-7-アニリノフルオラン; 3-ジエチルアミノ-6-メチル-7-(o,p-ジメチルアニリノ)フルオラン; 3-ジエチルアミノ-6-メチル-7-クロロフルオラン; 3-ジエチルアミノ-6-メチル-7-(m-トリフルオロメチルアニリノ)フルオラン; 3-ジエチルアミノ-6-メチル-7-(o-クロロアニリノ)フルオラン; 3-ジエチルアミノ-6-メチル-7-(p-クロロアニリノ)フルオラン; 3-ジエチルアミノ-6-メチル-7-(o-フルオロアニリノ)フルオラン; 3-ジエチルアミノ-6-メチル-7-(m-メチルアニリノ)フルオラン; 3-ジエチルアミノ-6-メチル-7-n-オクチルアニリノフルオラン; 3-ジエチルアミノ-6-メチル-7-n-オクチルアミノフルオラン; 3-ジエチルアミノ-6-メチル-7-ベンジルアミノフルオラン; 3-ジエチルアミノ-6-メチル-7-ジベンジルアミノフルオラン;3-ジエチルアミノ-6-クロロ-7-メチルフルオラン; 3-ジエチルアミノ-6-クロロ-7-アニリノフルオラン; 3-ジエチルアミノ-6-クロロ-7-p-メチルアニリノフルオラン; 3-ジエチルアミノ-6-エトキシエチル-7-アニリノフルオラン; 3-ジエチルアミノ-7-メチルフルオラン; 3-ジエチルアミノ-7-クロロフルオラン; 3-ジエチルアミノ-7-(m-トリフルオロメチルアニリノ)フルオラン; 3-ジエチルアミノ-7-(o-クロロアニリノ)フルオラン; 3-ジエチルアミノ-7-(p-クロロアニリノ)フルオラン; 3-ジエチルアミノ-7-(o-フルオロアニリノ)フルオラン; 3-ジエチルアミノ-ベンゾ〔a〕フルオラン; 3-ジエチルアミノ-ベンゾ〔c〕フルオラン; 3-ジブチルアミノ-6-メチル-フルオラン; 3-ジブチルアミノ-6-メチル-7-アニリノフルオラン; 3-ジブチルアミノ-6-メチル-7-(o,p-ジメチルアニリノ)フルオラン; 3-ジブチルアミノ-6-メチル-7-(o-クロロアニリノ)フルオラン; 3-ジブチルアミノ-6-メチル-7-(p-クロロアニリノ)フルオラン; 3-ジブチルアミノ-6-メチル-7-(o-フルオロアニリノ)フルオラン; 3-ジブチルアミノ-6-メチル-7-(m-トリフルオロメチルアニリノ)フルオラン; 3-ジブチルアミノ-6-メチル-クロロフルオラン; 3-ジブチルアミノ-6-エトキシエチル-7-アニリノフルオラン; 3-ジブチルアミノ-6-クロロ-7-アニリノフルオラン; 3-ジブチルアミノ-6-メチル-7-p-メチルアニリノフルオラン; 3-ジブチルアミノ-7-(o-クロロアニリノ)フルオラン; 3-ジブチルアミノ-7-(o-フルオロアニリノ)フルオラン; 3-ジ-n-ペンチルアミノ-6-メチル-7-アニリノフルオラン; 3-ジ-n-ペンチルアミノ-6-メチル-7-(p-クロロアニリノ)フルオラン; 3-ジ-n-ペンチルアミノ-7-(m-トリフルオロメチルアニリノ)フルオラン; 3-ジ-n-ペンチルアミノ-6-クロロ-7-アニリノフルオラン; 3-ジ-n-ペンチルアミノ-7-(p-クロロアニリノ)フルオラン; 3-ピロリジノ-6-メチル-7-アニリノフルオラン; 3-ピペリジノ-6-メチル-7-アニリノフルオラン; 3-(N-メチル-N-プロピルアミノ)-6-メチル-7-アニリノフルオラン; 3-(N-メチル-N-シクロヘキシルアミノ)-6-メチル-7-アニリノフルオラン; 3-(N-エチル-N-シクロヘキシルアミノ)-6-メチル-7-アニリノフルオラン; 3-(N-エチル-N-キシルアミノ)-6-メチル-7-(p-クロロアニリノ)フルオラン; 3-(N-エチル-p-トルイディノ)-6-メチル-7-アニリノフルオラン; 3-(N-エチル-N-イソアミルアミノ)-6-メチル-7-アニリノフルオラン; 3-(N-エチル-N-イソアミルアミノ)-6-クロロ-7-アニリノフルオラン; 3-(N-エチル-N-テトラヒドロフルフリルアミノ)-6-メチル-7-アニリノフルオラン; 3-(N-エチル-N-イソブチルアミノ)-6-メチル-7-アニリノフルオラン; 3-(N-エチル-N-エトキシプロピルアミノ)-6-メチル-7-アニリノフルオラン; 3-シクロヘキシルアミノ-6-クロロフルオラン; 2-(4-オキサヘキシル)-3-ジメチルアミノ-6-メチル-7-アニリノフルオラン; 2-(4-オキサヘキシル)-3-ジエチルアミノ-6-メチル-7-アニリノフルオラン; 2-(4-オキサヘキシル)-3-ジプロピルアミノ-6-メチル-7-アニリノフルオラン; 2-メチル-6-p-(p-ジメチルアミノフェニル)アミノアニリノフルオラン; 2-メトキシ-6-p-(p-ジメチルアミノフェニル)アミノアニリノフルオラン; 2-クロロ-3-メチル-6-p-(p-フェニルアミノフェニル)アミノアニリノフルオラン; 2-クロロ-6-p-(p-ジメチルアミノフェニル)アミノアニリノフルオラン; 2-ニトロ-6-p-(p-ジエチルアミノフェニル)アミノアニリノフルオラン; 2-アミノ-6-p-(p-ジエチルアミノフェニル)アミノアニリノフルオラン; 2-ジエチルアミノ-6-p-(p-ジエチルアミノフェニル)アミノアニリノフルオラン; 2-フェニル-6-メチル-6-p-(p-フェニルアミノフェニル)アミノアニリノフルオラン; 2-ベンジル-6-p-(p-フェニルアミノフェニル)アミノアニリノフルオラン; 2-ヒドロキシ-6-p-(p-フェニルアミノフェニル)アミノアニリノフルオラン; 3-メチル-6-p-(p-ジメチルアミノフェニル)アミノアニリノフルオラン; 3-ジエチルアミノ-6-p-(p-ジエチルアミノフェニル)アミノアニリノフルオラン; 3-ジエチルアミノ-6-p-(p-ジブチルアミノフェニル)アミノアニリノフルオラン; 2,4-ジメチル-6-〔(4-ジメチルアミノ)アニリノ〕-フルオラン
3,6,6'-トリス(ジメチルアミノ)スピロ〔フルオレン-9,3'-フタリド〕; 3,6,6'-トリス(ジエチルアミノ)スピロ〔フルオレン-9,3'-フタリド〕
<ジビニル系ロイコ染料>
3,3-ビス-〔2-(p-ジメチルアミノフェニル)-2-(p-メトキシフェニル)エテニル〕-4,5,6,7-テトラブロモフタリド; 3,3-ビス-〔2-(p-ジメチルアミノフェニル)-2-(p-メトキシフェニル)エテニル〕-4,5,6,7-テトラクロロフタリド; 3,3-ビス-〔1,1-ビス(4-ピロリジノフェニル)エチレン-2-イル〕-4,5,6,7-テトラブロモフタリド; 3,3-ビス-〔1-(4-メトキシフェニル)-1-(4-ピロリジノフェニル)エチレン-2-イル〕-4,5,6,7-テトラクロロフタリド
3-(4-ジエチルアミノ-2-エトキシフェニル)-3-(1-エチル-2-メチルインドール-3-イル)-4-アザフタリド; 3-(4-ジエチルアミノ-2-エトキシフェニル)-3-(1-オクチル-2-メチルインドール-3-イル)-4-アザフタリド; 3-(4-シクロヘキシルエチルアミノ-2-メトキシフェニル)-3-(1-エチル-2-メチルインドール-3-イル)-4-アザフタリド; 3,3-ビス(1-エチル-2-メチルインドール-3-イル)フタリド; 3,6-ビス(ジエチルアミノ)フルオラン-γ-(3'-ニトロ)アニリノラクタム; 3,6-ビス(ジエチルアミノ)フルオラン-γ-(4'-ニトロ)アニリノラクタム; 1,1-ビス-〔2',2',2'',2''-テトラキス-(p-ジメチルアミノフェニル)-エテニル〕-2,2-ジニトリルエタン; 1,1-ビス-〔2',2',2'',2''-テトラキス-(p-ジメチルアミノフェニル)-エテニル〕-2-β-ナフトイルエタン; 1,1-ビス-〔2',2',2'',2''-テトラキス-(p-ジメチルアミノフェニル)-エテニル〕-2,2-ジアセチルエタン; ビス-〔2,2,2',2'-テトラキス-(p-ジメチルアミノフェニル)-エテニル〕-メチルマロン酸ジメチルエステル
このほかにベンゾフェノン系やトリアゾール系の紫外線吸収剤、分散剤、消泡剤、酸化防止剤、蛍光染料等を使用することができる。
その他の任意成分である、バインダー、顔料、滑剤、架橋剤、画像安定剤、その他の成分の種類及び量は、要求される性能及び記録適性に従って決定され、特に限定されるものではないが、通常、バインダーは感熱記録層(固形分)100重量部に対し固形分で5~50重量部程度、顔料は感熱記録層(固形分)100重量部に対し固形分で0~50重量部程度が適当である。滑剤を使用する場合には、滑剤の含有量は感熱記録層(固形分)100重量部に対し固形分で5~10重量部程度が適当である。
本発明で用いるカルボキシ変性ポリビニルアルコールとアクリル系樹脂の重量比(カルボキシ変性ポリビニルアルコール/アクリル系樹脂)は、好ましくは80/20~20/80、より好ましくは70/30~30/70、更に好ましくは60/40~40/60である。
本発明に用いられるエピクロロヒドリン系樹脂及びポリアミン/ポリアミド系樹脂(エピクロロヒドリン系樹脂に含まれるものを除く。)の含有量は、カルボキシ変性ポリビニルアルコール100重量部に対してそれぞれ好ましくは1~100重量部、より好ましくは5~50重量部である。含有量が少なすぎると架橋反応が不十分となり良好な耐水性が得られず、多すぎると塗工液の粘度増加やゲル化により操業性の問題が生じる。
また、各層の塗工後にスーパーカレンダー掛けなどの平滑化処理を施すなど、感熱記録体分野における各種公知の技術を必要適宜付加することができる。
<下塗り層用塗工液>
焼成カオリン(BASF社製、商品名:アンシレックス90)
100.0部
スチレン・ブタジエン共重合体ラテックス(日本ゼオン株式会社製、
商品名:ST5526、固形分48%) 10.0部
水 50.0部
4,4'-ジヒドロキシジフェニルスルホン(日華化学株式会社製、
商品名BPS-P) 6.0部
完全ケン化型ポリビニルアルコール水溶液(クラレ社製、商品名:
PVA117、固形分10%) 5.0部
水 1.5部
3-ジブチルアミノ-6-メチル-7-アニリノフルオラン(山本化成
株式会社製、商品名:ODB-2) 6.0部
完全ケン化型ポリビニルアルコール水溶液(PVA117) 5.0部
水 1.5部
増感剤分散液(C液)
ジフェニルスルホン(Volant社製、商品名:DPS) 6.0部
完全ケン化型ポリビニルアルコール水溶液(PVA117) 5.0部
水 1.5部
<感熱記録層用塗工液>
顕色剤分散液(A液) 30.0部
ロイコ染料分散液(B液) 15.0部
増感剤分散液(C液) 30.0部
シリカ分散液(水澤化学社製、商品名:P527、固形分25%)
40.0部
カルボキシ変性ポリビニルアルコール水溶液(クラレ社製:商品名:
KL318、固形分10%) 20.0部
アクリル系樹脂(アイカ工業社製:商品名:A25、固形分48%、
Tg45℃、MFT70℃) 4.0部
ポリアミド樹脂(住友化学社製:商品名:スミレーズレジンSPI-
106N、固形分45%) 1.25部
ポリアミドエピクロロヒドリン樹脂(星光PMC社製、商品名:
WS4030、固形分25%) 2.5部
ステアリン酸亜鉛(中京油脂社製、商品名:ハイドリンZ-7-30、
固形分30%) 2.0部
支持体(坪量47g/m2の上質紙)の片面に、下塗り層用塗工液を、固形分で塗工量10.0g/m2となるようにベントブレード法で塗工した後、乾燥を行ない、下塗り層塗工紙を得た。
この下塗り層塗工紙の下塗り層上に、感熱記録層用塗工液を、固形分で塗工量6.0g/m2となるようにロッドブレード法で塗工した後、乾燥を行い、スーパーカレンダーで平滑度が500~1000秒になるように処理して感熱記録体を作製した。
感熱記録層用塗工液のアクリル系樹脂を アクリル系樹脂(ジョンソンポリマー社製、A537、固形分45%、Tg49℃、MFT42℃)4.3部に変更した以外は、実施例1と同様にして感熱記録体を作製した。
[実施例3]
感熱記録層用塗工液のアクリル系樹脂を2.5部に変更し、カルボキシ変性ポリビニルアルコール水溶液を40.0部に変更した以外は、実施例1と同様にして感熱記録体を作製した。
[実施例4]
感熱記録層用塗工液のアクリル系樹脂を8.0部に変更し、カルボキシ変性ポリビニルアルコール水溶液を10.0部に変更した以外は、実施例1と同様にして感熱記録体を作製した。
感熱記録層用塗工液のアクリル系樹脂(アイカ工業社製、商品名:A25)を配合せず、カルボキシ変性ポリビニルアルコール水溶液を40.0部に変更した以外は、実施例1と同様にして感熱記録体を作製した。
[比較例2]
感熱記録層用塗工液のアクリル系樹脂(アイカ工業社製、商品名:A25)4.0部を、アクリル系樹脂(三井化学社製、商品名:ASN1004K、固形分18%、Tg55℃、MFT18℃)10.7部に変更した以外は、実施例1と同様にして感熱記録体を作製した。
[比較例3]
感熱記録層用塗工液のアクリル系樹脂(アイカ工業社製、商品名:A25)4.0部を、アクリル系樹脂(三井化学社製、商品名:B697B、固形分18%、Tg45℃、MFT20℃)10.7部に変更した以外は、実施例1と同様にして感熱記録体を作製した。
感熱記録層用塗工液のカルボキシ変性ポリビニルアルコール水溶液、ポリアミド樹脂、ポリアミドエピクロロヒドリン樹脂を配合しない以外は、実施例1と同様にして感熱記録体を作製した。
[比較例5]
感熱記録層用塗工液のカルボキシ変性ポリビニルアルコール水溶液を配合しない以外は、実施例1と同様にして感熱記録体を作製した。
感熱記録層用塗工液のカルボキシ変性ポリビニルアルコール水溶液、ポリアミド樹脂、ポリアミドエピクロロヒドリン樹脂を配合せず、グリオキザール水溶液(固形分40%)を1.5部配合した以外は、実施例1と同様にして感熱記録体を作製した。
[比較例7]
感熱記録層用塗工液のポリアミド樹脂、ポリアミドエピクロロヒドリン樹脂を配合せず、グリオキザール水溶液(固形分40%)を1.5部配合した以外は、実施例1と同様にして感熱記録体を作製した。
<発色性能(印字濃度)>
作製した感熱記録体について、大倉電機社製のTH-PMD(感熱記録紙印字試験機、京セラ社製サーマルヘッドを装着)を用い、印加エネルギー0.35mJ/dot及び0.41mJ/dot、印字速度50mm/secで市松模様を印字した。
印字部の印字濃度をマクベス濃度計(RD-914、アンバーフィルター使用)で測定し、発色性能(印字濃度)を評価した。
作製した感熱記録体について、大倉電機社製のTH-PMD(感熱記録紙印字試験機、
京セラ社製サーマルヘッドを装着)を用い、印加エネルギー0.41mJ/dot、印字
速度50mm/secで市松模様を印字した。
印字した感熱記録体を、紙管に塩ビラップ(三井化学製ハイラップKMA)を1回巻き付けた上に貼り付け、更にその上に塩ビラップを3重に巻き付けて、23℃、50%RH環境条件下で24時間静置した。
印字部の印字濃度をマクベス濃度計(RD-914、アンバーフィルター使用)で測定し、処理前後の値から残存率を算出して、耐可塑剤性を評価した。
残存率(%)=(処理後の印字部の印字濃度/処理前の印字部の印字濃度)×100
作製した感熱記録体について、水道水を指につけて、感熱記録層の塗工面を80往復摩擦し、感熱記録層の剥がれを以下の基準で目視評価した。
優:感熱記録層の剥がれが全くない
可:感熱記録層が僅かに剥がれる
不可:感熱記録層全体が剥がれる
作製した感熱記録体について、感熱記録層の塗工面に10mlの水道水を滴下し、感熱記録層の塗工面が内側になるように二つ折りにして、10gf/cm2の加重を掛けて24時間静置した後に剥がし、水を滴下した部分の感熱記録層の剥がれを以下の基準で目視評価した。
優:感熱記録層の剥がれが全くない
可:感熱記録層が僅かに剥がれる
不可:感熱記録層全体が剥がれる
作製した感熱記録体について、水道水に3分間浸漬し、感熱記録層の塗工面を指で10往復摩擦し、感熱記録層の剥がれを以下の基準で目視評価した。
優:感熱記録層の剥がれが全くない
可:感熱記録層が僅かに剥がれる
不可:感熱記録層全体が剥がれる
作製した感熱記録体について、大倉電機社製のTH-PMD(感熱記録紙印字試験機、京セラ社製サーマルヘッドを装着)を用いて、ベタ印字を行い、感熱記録層塗工面の面感(均一性)を以下の基準で目視評価した。
優:塗工面に異物がなく、印字面が均一
可:塗工面に僅かに異物があるが、印字面は概ね均一であり、実用上問題はない
不可:塗工面に異物があり、印字面が不均一
なお、実施例1及び比較例3の印字物の表面を撮影した写真を図1に示す(A:実施例1、B:比較例3)。
一方、感熱記録層に本願発明のアクリル樹脂を欠く比較例1の感熱記録体は、優れた表面性を有するが、耐水性の中で浸漬摩擦が劣った。また感熱記録層にアクリル樹脂を使用してもTgやMFTが本願発明のアクリル樹脂とは異なる比較例2、3の感熱記録体は、全般的に耐水性が劣ると共に、塗工面に異物がありベタ印字時に白抜けやムラが生じて表面性も劣った。
また、カルボキシ変性ポリビニルアルコール、エピクロロヒドリン系樹脂及びポリアミン/ポリアミド系樹脂のいずれか又はすべてを欠く比較例4~7の感熱記録体は、全般的に耐水性が劣ると共に、比較例4~6の感熱記録体は耐可塑剤性が劣り、更に比較例5の感熱記録体は塗工面に異物がありベタ印字時に白抜けやムラが生じて表面性も劣った。
Claims (7)
- 支持体上に、無色ないし淡色の電子供与性ロイコ染料及び電子受容性顕色剤を主成分として含有する感熱記録層を有し、該感熱記録層上に保護層を有さない感熱記録体において、該感熱記録層がバインダーとしてカルボキシ変性ポリビニルアルコールを含有し、更に架橋剤としてエピクロロヒドリン系樹脂及びポリアミン/ポリアミド系樹脂(エピクロロヒドリン系樹脂に含まれるものを除く。)を含有し、更にガラス転移点(Tg)が50℃以下、最低造膜温度(MFT)が40℃以上であるアクリル系樹脂を含有する感熱記録体。
- 前記アクリル系樹脂のガラス転移点(Tg)が40℃~50℃である請求項1に記載の感熱記録体。
- 前記アクリル系樹脂の最低造膜温度(MFT)が60℃~80℃である請求項1又は2に記載の感熱記録体。
- 前記アクリル系樹脂のメチルメタクリレート(MMA)の含有率が60%以上である請求項1~3のいずれか一項に記載の感熱記録体。
- 前記アクリル系樹脂が単量体成分としてスチレンを含まない請求項1~4のいずれか一項に記載の感熱記録体。
- 前記アクリル系樹脂が非コアシェル型のアクリル系樹脂である請求項1~5のいずれか一項に記載の感熱記録体。
- 前記カルボキシ変性ポリビニルアルコールと前記アクリル系樹脂の重量比が80/20~20/80である請求項1~6のいずれか一項に記載の感熱記録体。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17/441,059 US11945249B2 (en) | 2019-03-20 | 2020-02-25 | Thermosensitive recording medium |
JP2021507128A JP6937960B2 (ja) | 2019-03-20 | 2020-02-25 | 感熱記録体 |
KR1020217025878A KR102466923B1 (ko) | 2019-03-20 | 2020-02-25 | 감열 기록체 |
EP20774130.7A EP3919283A4 (en) | 2019-03-20 | 2020-02-25 | THERMOSENSITIVE RECORD BODY |
CN202080013804.9A CN113423583B (zh) | 2019-03-20 | 2020-02-25 | 热敏记录体 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019-053003 | 2019-03-20 | ||
JP2019053003 | 2019-03-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2020189183A1 true WO2020189183A1 (ja) | 2020-09-24 |
Family
ID=72520238
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2020/007308 WO2020189183A1 (ja) | 2019-03-20 | 2020-02-25 | 感熱記録体 |
Country Status (6)
Country | Link |
---|---|
US (1) | US11945249B2 (ja) |
EP (1) | EP3919283A4 (ja) |
JP (1) | JP6937960B2 (ja) |
KR (1) | KR102466923B1 (ja) |
CN (1) | CN113423583B (ja) |
WO (1) | WO2020189183A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2021146505A (ja) * | 2020-03-16 | 2021-09-27 | 日本製紙株式会社 | 感熱記録体 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115505337B (zh) * | 2022-08-24 | 2023-07-07 | 广东红日星实业有限公司 | 一种抛光浆的制备方法及其应用 |
Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5391995A (en) | 1977-01-24 | 1978-08-12 | Kuraray Co Ltd | Production of carboxyl group-modified polyvinyl alcohol |
JPH0859603A (ja) | 1994-08-19 | 1996-03-05 | Nippon Paper Ind Co Ltd | 新規なアミノベンゼンスルホンアミド誘導体及びそれらを使用した記録体 |
WO1997016420A1 (fr) | 1995-10-31 | 1997-05-09 | Nippon Soda Co., Ltd. | Composes du type a reticulation de diphenyle sulfone et materiaux d'enregistrement les utilisant |
JPH11314454A (ja) | 1998-05-01 | 1999-11-16 | Mitsui Chem Inc | 感熱記録材料用ラテックス、感熱記録材料およびその製造方法 |
JP2002301873A (ja) | 2001-04-04 | 2002-10-15 | Nippon Soda Co Ltd | 記録材料及び記録シート |
WO2002081229A1 (fr) | 2001-04-04 | 2002-10-17 | Nippon Soda Co., Ltd. | Matériau et feuille d'enregistrement |
JP2003154760A (ja) | 2001-11-21 | 2003-05-27 | Nippon Paper Industries Co Ltd | 感熱記録体 |
WO2007049621A1 (ja) | 2005-10-24 | 2007-05-03 | Mitsui Chemicals, Inc. | 感熱記録材料 |
WO2008139948A1 (ja) | 2007-05-10 | 2008-11-20 | Nippon Paper Industries Co., Ltd. | 感熱記録体 |
JP2009051049A (ja) * | 2007-08-24 | 2009-03-12 | Nippon Paper Industries Co Ltd | 感熱記録体 |
JP2010111037A (ja) | 2008-11-07 | 2010-05-20 | Nippon Paper Industries Co Ltd | 感熱記録体 |
JP2010115834A (ja) * | 2008-11-12 | 2010-05-27 | Nippon Paper Industries Co Ltd | 感熱記録体 |
WO2010110209A1 (ja) | 2009-03-24 | 2010-09-30 | 日本製紙株式会社 | 感熱記録体 |
WO2011145545A1 (ja) * | 2010-05-18 | 2011-11-24 | 日本製紙株式会社 | 感熱記録体 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3955083B2 (ja) * | 2005-01-13 | 2007-08-08 | 日本製紙株式会社 | 感熱記録体 |
JP2008006739A (ja) * | 2006-06-30 | 2008-01-17 | Nippon Paper Industries Co Ltd | 感熱記録体 |
EP2184175B1 (en) * | 2007-08-29 | 2015-05-20 | Nippon Paper Industries Co., Ltd. | Thermal recording medium |
JP5105496B2 (ja) * | 2008-03-27 | 2012-12-26 | 日本製紙株式会社 | 感熱記録体 |
JP5277884B2 (ja) * | 2008-11-12 | 2013-08-28 | 日本製紙株式会社 | 感熱記録体 |
CN105283316B (zh) * | 2013-05-22 | 2018-03-30 | 王子控股株式会社 | 热敏记录体 |
JP6255889B2 (ja) * | 2013-10-21 | 2018-01-10 | 日本製紙株式会社 | 感熱記録体 |
JP2015123702A (ja) * | 2013-12-27 | 2015-07-06 | 日本製紙株式会社 | 感熱記録体 |
-
2020
- 2020-02-25 CN CN202080013804.9A patent/CN113423583B/zh active Active
- 2020-02-25 WO PCT/JP2020/007308 patent/WO2020189183A1/ja unknown
- 2020-02-25 JP JP2021507128A patent/JP6937960B2/ja active Active
- 2020-02-25 KR KR1020217025878A patent/KR102466923B1/ko active IP Right Grant
- 2020-02-25 US US17/441,059 patent/US11945249B2/en active Active
- 2020-02-25 EP EP20774130.7A patent/EP3919283A4/en active Pending
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5391995A (en) | 1977-01-24 | 1978-08-12 | Kuraray Co Ltd | Production of carboxyl group-modified polyvinyl alcohol |
JPH0859603A (ja) | 1994-08-19 | 1996-03-05 | Nippon Paper Ind Co Ltd | 新規なアミノベンゼンスルホンアミド誘導体及びそれらを使用した記録体 |
WO1997016420A1 (fr) | 1995-10-31 | 1997-05-09 | Nippon Soda Co., Ltd. | Composes du type a reticulation de diphenyle sulfone et materiaux d'enregistrement les utilisant |
JPH11314454A (ja) | 1998-05-01 | 1999-11-16 | Mitsui Chem Inc | 感熱記録材料用ラテックス、感熱記録材料およびその製造方法 |
JP2002301873A (ja) | 2001-04-04 | 2002-10-15 | Nippon Soda Co Ltd | 記録材料及び記録シート |
WO2002081229A1 (fr) | 2001-04-04 | 2002-10-17 | Nippon Soda Co., Ltd. | Matériau et feuille d'enregistrement |
JP2003154760A (ja) | 2001-11-21 | 2003-05-27 | Nippon Paper Industries Co Ltd | 感熱記録体 |
WO2007049621A1 (ja) | 2005-10-24 | 2007-05-03 | Mitsui Chemicals, Inc. | 感熱記録材料 |
WO2008139948A1 (ja) | 2007-05-10 | 2008-11-20 | Nippon Paper Industries Co., Ltd. | 感熱記録体 |
JP2009051049A (ja) * | 2007-08-24 | 2009-03-12 | Nippon Paper Industries Co Ltd | 感熱記録体 |
JP2010111037A (ja) | 2008-11-07 | 2010-05-20 | Nippon Paper Industries Co Ltd | 感熱記録体 |
JP2010115834A (ja) * | 2008-11-12 | 2010-05-27 | Nippon Paper Industries Co Ltd | 感熱記録体 |
WO2010110209A1 (ja) | 2009-03-24 | 2010-09-30 | 日本製紙株式会社 | 感熱記録体 |
WO2011145545A1 (ja) * | 2010-05-18 | 2011-11-24 | 日本製紙株式会社 | 感熱記録体 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2021146505A (ja) * | 2020-03-16 | 2021-09-27 | 日本製紙株式会社 | 感熱記録体 |
JP7413098B2 (ja) | 2020-03-16 | 2024-01-15 | 日本製紙株式会社 | 感熱記録体 |
Also Published As
Publication number | Publication date |
---|---|
JP6937960B2 (ja) | 2021-09-22 |
CN113423583A (zh) | 2021-09-21 |
US11945249B2 (en) | 2024-04-02 |
KR20210114493A (ko) | 2021-09-23 |
KR102466923B1 (ko) | 2022-11-14 |
EP3919283A4 (en) | 2022-04-06 |
EP3919283A1 (en) | 2021-12-08 |
US20220161588A1 (en) | 2022-05-26 |
CN113423583B (zh) | 2022-09-27 |
JPWO2020189183A1 (ja) | 2021-10-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5025029B2 (ja) | 感熱記録体 | |
JP6960562B2 (ja) | 感熱記録体 | |
WO2010110209A1 (ja) | 感熱記録体 | |
JP6937960B2 (ja) | 感熱記録体 | |
JP6971434B1 (ja) | 感熱記録体 | |
CN111801225A (zh) | 热敏记录体 | |
JP5259347B2 (ja) | 感熱記録体 | |
JP2021123009A (ja) | 感熱記録体 | |
JP2007245362A (ja) | 感熱記録体及び感熱記録体ラベル | |
JP2007203580A (ja) | 感熱記録体 | |
JP7411510B2 (ja) | 感熱記録体 | |
JP7354483B1 (ja) | 感熱記録体 | |
JP7072130B1 (ja) | 感熱記録体 | |
JP7413098B2 (ja) | 感熱記録体 | |
JP7270431B2 (ja) | 感熱記録体 | |
JP2009083181A (ja) | 感熱記録体 | |
JP2010000640A (ja) | 感熱記録体 | |
JP2009061631A (ja) | 感熱記録体 | |
WO2013137243A1 (ja) | 感熱記録体 | |
WO2023190314A1 (ja) | 感熱記録体 | |
JP2022044310A (ja) | 感熱記録体 | |
JP2011156855A (ja) | 感熱記録体 | |
JP2023131480A (ja) | 感熱記録体 | |
JP2010115834A (ja) | 感熱記録体 | |
JP2007307781A (ja) | 感熱記録体 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20774130 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2021507128 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20217025878 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2020774130 Country of ref document: EP Effective date: 20210903 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |