JP6327085B2 - Thermal recording material - Google Patents
Thermal recording material Download PDFInfo
- Publication number
- JP6327085B2 JP6327085B2 JP2014191137A JP2014191137A JP6327085B2 JP 6327085 B2 JP6327085 B2 JP 6327085B2 JP 2014191137 A JP2014191137 A JP 2014191137A JP 2014191137 A JP2014191137 A JP 2014191137A JP 6327085 B2 JP6327085 B2 JP 6327085B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- heat
- anchor layer
- sizing agent
- sensitive recording
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- -1 aziridine compound Chemical class 0.000 claims description 40
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- 230000000740 bleeding effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- OGOLFXXLPKTFEO-UHFFFAOYSA-N calcium;oxaldehydic acid Chemical compound [Ca].OC(=O)C=O.OC(=O)C=O OGOLFXXLPKTFEO-UHFFFAOYSA-N 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- OJLOUXPPKZRTHK-UHFFFAOYSA-N dodecan-1-ol;sodium Chemical compound [Na].CCCCCCCCCCCCO OJLOUXPPKZRTHK-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZSYJMXLJNPEAGP-UHFFFAOYSA-N methyl n-cyanocarbamate Chemical compound COC(=O)NC#N ZSYJMXLJNPEAGP-UHFFFAOYSA-N 0.000 description 1
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- RQAQWBFHPMSXKR-UHFFFAOYSA-N n-(4-chlorophenyl)-3-(phosphonooxy)naphthalene-2-carboxamide Chemical compound OP(O)(=O)OC1=CC2=CC=CC=C2C=C1C(=O)NC1=CC=C(Cl)C=C1 RQAQWBFHPMSXKR-UHFFFAOYSA-N 0.000 description 1
- MJGLMEMIYDUEHA-UHFFFAOYSA-N n-(4-methylphenyl)-3-oxobutanamide Chemical compound CC(=O)CC(=O)NC1=CC=C(C)C=C1 MJGLMEMIYDUEHA-UHFFFAOYSA-N 0.000 description 1
- JHOKTNSTUVKGJC-UHFFFAOYSA-N n-(hydroxymethyl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCO JHOKTNSTUVKGJC-UHFFFAOYSA-N 0.000 description 1
- 125000002004 n-butylamino group Chemical group [H]N(*)C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DVVFBRPYROBXHJ-UHFFFAOYSA-N n-octadecanoylbenzamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NC(=O)C1=CC=CC=C1 DVVFBRPYROBXHJ-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229940083254 peripheral vasodilators imidazoline derivative Drugs 0.000 description 1
- CPJSUEIXXCENMM-UHFFFAOYSA-N phenacetin Chemical compound CCOC1=CC=C(NC(C)=O)C=C1 CPJSUEIXXCENMM-UHFFFAOYSA-N 0.000 description 1
- QHDYIMWKSCJTIM-UHFFFAOYSA-N phenyl 1-hydroxynaphthalene-2-carboxylate Chemical compound C1=CC2=CC=CC=C2C(O)=C1C(=O)OC1=CC=CC=C1 QHDYIMWKSCJTIM-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000010232 propyl p-hydroxybenzoate Nutrition 0.000 description 1
- QELSKZZBTMNZEB-UHFFFAOYSA-N propylparaben Chemical compound CCCOC(=O)C1=CC=C(O)C=C1 QELSKZZBTMNZEB-UHFFFAOYSA-N 0.000 description 1
- 229960003415 propylparaben Drugs 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- ZCTQGTTXIYCGGC-UHFFFAOYSA-N salicylic acid benzyl ester Natural products OC1=CC=CC=C1C(=O)OCC1=CC=CC=C1 ZCTQGTTXIYCGGC-UHFFFAOYSA-N 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- SOEVVANXSDKPIY-UHFFFAOYSA-M sodium glyoxylate Chemical compound [Na+].[O-]C(=O)C=O SOEVVANXSDKPIY-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920005792 styrene-acrylic resin Polymers 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- JVFFWGJAAQAIBS-UHFFFAOYSA-K trisodium 2,2-dioctyl-3-sulfonatobutanedioate Chemical compound [Na+].C(CCCCCCC)C(C(C(=O)[O-])S(=O)(=O)[O-])(C(=O)[O-])CCCCCCCC.[Na+].[Na+] JVFFWGJAAQAIBS-UHFFFAOYSA-K 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
- Laminated Bodies (AREA)
Description
本発明は、ロイコ染料と呈色剤との発色反応を利用した感熱記録体に関するものである。 The present invention relates to a heat-sensitive recording material utilizing a color development reaction between a leuco dye and a colorant.
一般に、感熱記録体は、通常無色乃至淡色のロイコ染料と呈色剤とを、それぞれ微細な粒子に分散した後、両者を混合し、接着剤、顔料、増感剤、その他滑剤等の助剤を添加して得られた塗液を、紙、合成紙、またはプラスチックフィルム等のシート状の支持体上に塗布したものである。感熱記録体は、サーマルヘッド、ホットスタンプ、熱ペン、レーザー光等の加熱による瞬時の化学反応により発色し、記録画像が得られる。感熱記録体は、ファクシミリ、コンピューターの端末プリンター、自動券売機、計測用レコーダー等、広範囲に使用されている。近年、裏面に粘着加工を施した感熱記録ラベル用途が増加している。これらPOS用ラベルや工程管理剤用ラベルは、粘着加工した後、使用されるまでの期間が長い。このため、保存時に裏面に塗布された粘着剤に含まれる可塑剤や乳化剤といった成分が支持体を通過して、感熱記録面に達し、発色反応の阻害(糊減感)を起こして記録発色性や記録画質といった記録性能を著しく低下させたり、印字の白抜けを発生させたりする等の問題がある。 Generally, a heat-sensitive recording material is usually a colorless to light leuco dye and a colorant dispersed in fine particles, and then mixed together to produce an auxiliary agent such as an adhesive, a pigment, a sensitizer, and other lubricants. The coating liquid obtained by adding is applied onto a sheet-like support such as paper, synthetic paper, or plastic film. The heat-sensitive recording material is colored by an instantaneous chemical reaction by heating with a thermal head, hot stamp, thermal pen, laser beam or the like, and a recorded image is obtained. Thermosensitive recording media are used in a wide range such as facsimiles, computer terminal printers, automatic ticket vending machines, and measurement recorders. In recent years, the use of thermal recording labels in which the back surface is subjected to adhesive processing is increasing. These POS labels and process control agent labels have a long period until they are used after being subjected to adhesive processing. For this reason, components such as plasticizers and emulsifiers contained in the adhesive applied to the back surface during storage pass through the support and reach the heat-sensitive recording surface, causing color reaction inhibition (glue desensitization) and recording color development. There are problems such as remarkably degrading recording performance such as image quality and recording, and white spots in printing.
上記の問題を解決するために、支持体と粘着剤層との間に鹸化度の高いポリビニルアルコールと顔料を含んだバリア層を設けること(特許文献1参照)、支持体裏面にスチレン−ブタジエン共重合体と顔料を含有するバックコート層を設けること(特許文献2参照)、支持体の感熱記録層とは反対側の面に水溶性アクリル樹脂を主成分として含んだ裏面層を設けること(特許文献3参照)、バックコート層にガラス転移点10℃以下で且つ0.01重量%水溶液の280nmにおける透過率が2.0%以下であるスチレン−アクリル系樹脂を含有させること(特許文献4参照)等が提案されているが、必ずしも満足すべき結果が得られていないのが現状である。 In order to solve the above problem, a barrier layer containing polyvinyl alcohol and a pigment having a high saponification degree and a pigment is provided between the support and the pressure-sensitive adhesive layer (see Patent Document 1), and a styrene-butadiene copolymer is provided on the back of the support. A back coat layer containing a polymer and a pigment is provided (see Patent Document 2), and a back layer containing a water-soluble acrylic resin as a main component is provided on the side of the support opposite to the thermosensitive recording layer (patent) Reference 3), and a back coat layer containing a styrene-acrylic resin having a glass transition point of 10 ° C. or less and a 0.01% by weight aqueous solution having a transmittance at 280 nm of 2.0% or less (see Patent Document 4) ) Etc. have been proposed, but at present, satisfactory results have not been obtained.
本発明は、記録発色性と記録画質に優れ、また、感熱記録ラベルに加工した後の粘着剤成分による発色反応の阻害(糊減感)がなく、長期保存にも耐えて記録性能に優れた感熱記録体を提供することを主な目的とする。 The present invention is excellent in recording color development and recording image quality, and has no hindrance to coloring reaction (glue desensitization) by the adhesive component after being processed into a thermal recording label, and has excellent recording performance withstanding long-term storage. The main purpose is to provide a thermal recording medium.
本発明者等は、鋭意検討の結果、サイズ剤及び耐水化剤を含有するアンカー層を備えることにより、上記の課題が解決されることを見出し、本発明を完成するに至った。即ち、本発明は下記の感熱記録体に係る。 As a result of intensive studies, the present inventors have found that the above problem can be solved by providing an anchor layer containing a sizing agent and a water-resistant agent, and have completed the present invention. That is, the present invention relates to the following thermal recording material.
項1:紙支持体よりなる支持体上に少なくとも、サイズ剤及び耐水化剤を含有するアンカー層、アンカー層上にロイコ染料と呈色剤を含有する感熱記録層を備えたことを特徴とする感熱記録体。 Item 1: At least an anchor layer containing a sizing agent and a water-resistant agent is provided on a support made of a paper support, and a thermosensitive recording layer containing a leuco dye and a colorant is provided on the anchor layer. Thermal recording material.
項2:前記サイズ剤を耐水化剤1質量部に対して固形分換算で0.5〜5質量部含有させた、項1に記載の感熱記録体。 Item 2: The heat-sensitive recording material according to Item 1, wherein the sizing agent is contained in an amount of 0.5 to 5 parts by mass in terms of solid content with respect to 1 part by mass of the water-resistant agent.
項3:前記耐水化剤がアジリジン化合物、ブロックイソシアネート化合物、カルボン酸ジヒドラジド系化合物、グリオキザール、ホルマリン、グリシン、グリシジルエステル、グリシジルエーテル、ジメチロール尿素、メラミン樹脂、ポリアミド樹脂、ポリアミドポリアミン−エピクロルヒドリン樹脂、ケトン−アルデヒド樹脂、過硫酸アンモニウム、塩化第二鉄、塩化マグネシウム、炭酸ジルコニウムアンモニウム塩、硼砂、硼酸、四硼酸ソーダ、硼酸トリエステル、硼素系ポリマー、四硼酸カリウム、炭酸ジルコニウムアンモニウム、エポキシ系化合物、ヒドラジド化合物、オキサゾリン基含有化合物、グリオキシル酸塩よりなる群から選ばれる少なくとも1種である、項1または2に記載の感熱記録体。 Item 3: The water resistant agent is an aziridine compound, a blocked isocyanate compound, a carboxylic acid dihydrazide compound, glyoxal, formalin, glycine, glycidyl ester, glycidyl ether, dimethylol urea, melamine resin, polyamide resin, polyamide polyamine-epichlorohydrin resin, ketone- Aldehyde resin, ammonium persulfate, ferric chloride, magnesium chloride, zirconium carbonate ammonium salt, borax, boric acid, sodium tetraborate, boric acid triester, boron polymer, potassium tetraborate, ammonium zirconium carbonate, epoxy compound, hydrazide compound, Item 3. The thermal recording material according to Item 1 or 2, which is at least one selected from the group consisting of an oxazoline group-containing compound and glyoxylate.
項4:前記アンカー層が更に顔料を含有する顔料塗工層である、請求項1〜3のいずれか1項に記載の感熱記録体。 Item 4: The heat-sensitive recording material according to any one of claims 1 to 3, wherein the anchor layer is a pigment coating layer further containing a pigment.
項5:前記アンカー層に含有されるサイズ剤がスチレン−アクリル系サイズ剤及びスチレン−マレイン酸系サイズ剤からなる群から選ばれる少なくとも1種である、請求項1〜4のいずれか1項に記載の感熱記録体。 Item 5: The sizing agent contained in the anchor layer is at least one selected from the group consisting of a styrene-acrylic sizing agent and a styrene-maleic acid sizing agent. The heat-sensitive recording material described.
項6:前記アンカー層が更に顔料を含有し、前記顔料として吸油性顔料及びプラスチック中空粒子からなる群から選ばれる少なくとも1種を含有し、アンカー層中の吸油性顔料/プラスチック中空粒子の質量比率が100/0〜40/60である、請求項1〜5のいずれか1項に記載の感熱記録体。 Item 6: The anchor layer further contains a pigment, and the pigment contains at least one selected from the group consisting of an oil-absorbing pigment and plastic hollow particles, and the mass ratio of the oil-absorbing pigment / plastic hollow particles in the anchor layer The heat-sensitive recording material according to claim 1, wherein is 100/0 to 40/60.
項7:前記アンカー層に含有されるサイズ剤の含有割合がアンカー層の全固形量中、固形分換算で1〜9質量%である、請求項1〜6のいずれか1項に記載の感熱記録体。 Item 7: The heat-sensitive material according to any one of claims 1 to 6, wherein the content ratio of the sizing agent contained in the anchor layer is 1 to 9% by mass in terms of solid content in the total solid amount of the anchor layer. Recorded body.
項8:前記アンカー層がスチレン−アクリル系サイズ剤を含有する、請求項1〜7のいずれか1項に記載の感熱記録体。 Item 8: The heat-sensitive recording material according to any one of claims 1 to 7, wherein the anchor layer contains a styrene-acrylic sizing agent.
項9:前記アンカー層がスチレン−アクリル系エマルジョン型サイズ剤を含有する、請求項1〜8のいずれか1項に記載の感熱記録体。 Item 9: The heat-sensitive recording material according to any one of Items 1 to 8, wherein the anchor layer contains a styrene-acrylic emulsion type sizing agent.
項10:前記支持体表面のマイクロトポグラフによる20kg/cm2加圧下での表面粗さが6μm以上である、請求項1〜9のいずれか1項に記載の感熱記録体。 Claim 10: wherein microtopograph surface roughness at 20 kg / cm 2 pressure by the graph of the support surface is 6μm or more heat-sensitive recording material according to any one of claims 1 to 9.
項11:前記支持体のステキヒトサイズ度が15秒以下である、請求項1〜10のいずれか1項に記載の感熱記録体。 Item 11: The heat-sensitive recording material according to any one of Items 1 to 10, wherein the support has a Steecht sizing degree of 15 seconds or less.
項12:前記感熱記録層とは反対側の支持体上に粘着剤層を備えた、請求項1〜11のいずれか1項に記載の感熱記録体。 Item 12: The heat-sensitive recording material according to any one of claims 1 to 11, wherein a pressure-sensitive adhesive layer is provided on a support opposite to the heat-sensitive recording layer.
項13:少なくとも前記感熱記録層がカーテン塗布法により形成された層である、請求項1〜12のいずれか1項に記載の感熱記録体。 Item 13: The heat-sensitive recording material according to any one of claims 1 to 12, wherein at least the heat-sensitive recording layer is a layer formed by a curtain coating method.
本発明の感熱記録体は、記録発色性と記録画質に優れ、感熱記録ラベルに加工した後の粘着剤成分による発色反応の阻害(糊減感)がなく、長期保存にも耐えて記録性能に優れる。 The thermal recording material of the present invention is excellent in recording color development and recording image quality, has no inhibition of color development reaction (adhesive desensitization) due to the adhesive component after being processed into a thermal recording label, and withstands long-term storage and improves recording performance. Excellent.
本発明の感熱記録体は、支持体上に少なくとも、サイズ剤及び耐水化剤を含有するアンカー層を備えている。これにより、優れた記録発色性と記録画質を得ることができる。また、感熱記録ラベルに加工した後も粘着剤層に含まれる可塑剤や乳化剤等の感熱記録層への浸透を防ぎ、長期保存後の記録性能に優れる。 The heat-sensitive recording material of the present invention includes an anchor layer containing at least a sizing agent and a water-resistant agent on a support. Thereby, excellent recording color development and recording image quality can be obtained. Further, even after processing into a heat-sensitive recording label, penetration of the plasticizer, emulsifier and the like contained in the pressure-sensitive adhesive layer into the heat-sensitive recording layer is prevented, and the recording performance after long-term storage is excellent.
サイズ剤は、皮膜自体の耐水性が強く、一度乾燥すると水と接触しても再び溶け出すことがない。本発明では、支持体と感熱記録層との間に、アンカー層を備えることにより、サイズ剤及び耐水化剤を均一に分布させてバリア性を高めていると考えられる。この結果、発色反応を阻害する成分が支持体を通過することなく、アンカー層への感熱記録層用塗液の浸透が抑えられ、均一な塗工層を形成して記録性能に優れる。 The sizing agent has high water resistance of the coating itself, and once dried, it does not dissolve again even if it comes into contact with water. In the present invention, it is considered that by providing an anchor layer between the support and the heat-sensitive recording layer, the sizing agent and the water-resistant agent are uniformly distributed to enhance the barrier property. As a result, the component that inhibits the color development reaction does not pass through the support, and the penetration of the coating solution for the heat-sensitive recording layer into the anchor layer is suppressed, so that a uniform coating layer is formed and the recording performance is excellent.
本発明におけるサイズ剤としては、例えば、ロジン系サイズ剤、アルキルケテンダイマーサイズ剤、アルケニル無水コハク酸、カチオンポリマーサイズ剤、ロジン系中性サイズ剤、スチレン−アクリル系サイズ剤、オレフィン系サイズ剤、ワックス系サイズ剤、スチレン−マレイン酸系サイズ剤等が挙げられる。一般的には、製紙用サイズ剤と称され、分子構造に親水基と疎水基を有しているものである。サイズ剤の形態としては、溶液型でもよく、またエマルジョン型でもよい。これらは、単独または2種以上を組み合わせて使用することができる。なお、本発明では、例えばスチレン−アクリル系サイズ剤とは、スチレン及びアクリルの共重合体を主成分とするサイズ剤のことである。 As the sizing agent in the present invention, for example, rosin sizing agent, alkyl ketene dimer sizing agent, alkenyl succinic anhydride, cationic polymer sizing agent, rosin neutral sizing agent, styrene-acrylic sizing agent, olefin sizing agent, Examples thereof include a wax sizing agent and a styrene-maleic acid sizing agent. Generally, it is called a sizing agent for papermaking and has a hydrophilic group and a hydrophobic group in its molecular structure. The form of the sizing agent may be a solution type or an emulsion type. These can be used alone or in combination of two or more. In the present invention, for example, a styrene-acrylic sizing agent is a sizing agent having a styrene and acrylic copolymer as a main component.
本発明では、一般に表面サイズ剤として使用されている、アルキルケテンダイマーサイズ剤、オレフィン系サイズ剤、ワックス系サイズ剤等が好ましく、スチレン−アクリル系サイズ剤、オレフィン−マレイン酸系サイズ剤、スチレン−マレイン酸系サイズ剤等の合成樹脂系サイズ剤を使用することがより好ましい。これらの中でも、スチレンを含有する共重合体を主成分とするサイズ剤が好ましい。スチレン−マレイン酸系サイズ剤には、スチレン−無水マレイン酸系サイズ剤が含まれる。なお、スチレン−アクリル系サイズ剤には、スチレン−アクリル酸共重合体塩も含まれ、塩としてはナトリウム塩、カリウム塩、アンモニウム塩、あるいはこれらの塩の共存したもの等も含まれる。また、スチレン−無水マレイン酸系サイズ剤には、スチレン−無水マレイン酸共重合体塩も含まれ、塩としてはナトリウム塩、カリウム塩、アンモニウム塩、あるいはこれらの塩の共存したもの等も含まれる。更にスチレン−無水マレイン酸系サイズ剤としては、スチレン−無水マレイン酸共重合体のエステル類も含まれ、スチレン−無水マレイン酸共重合体のブチルエステルが特に好ましい。 In the present invention, alkyl ketene dimer sizing agent, olefin sizing agent, wax sizing agent and the like, which are generally used as a surface sizing agent, are preferable, and styrene-acrylic sizing agent, olefin-maleic acid sizing agent, styrene- It is more preferable to use a synthetic resin sizing agent such as a maleic acid sizing agent. Among these, a sizing agent having a styrene-containing copolymer as a main component is preferable. The styrene-maleic acid sizing agent includes a styrene-maleic anhydride sizing agent. The styrene-acrylic sizing agent includes a styrene-acrylic acid copolymer salt, and the salt includes a sodium salt, a potassium salt, an ammonium salt, or a mixture of these salts. In addition, the styrene-maleic anhydride sizing agent includes styrene-maleic anhydride copolymer salts, which include sodium salts, potassium salts, ammonium salts, or those in which these salts coexist. . Further, the styrene-maleic anhydride sizing agent includes esters of styrene-maleic anhydride copolymer, and butyl ester of styrene-maleic anhydride copolymer is particularly preferable.
アンカー層に含まれるサイズ剤としては、特に制限されないが、スチレン−アクリル系サイズ剤及びスチレン−マレイン酸系サイズ剤からなる群から選ばれる少なくとも1種が好ましく、スチレン−アクリル系サイズ剤がより好ましく、スチレン−アクリル系エマルジョン型サイズ剤が更に好ましい。エマルジョン型を用いることにより、アンカー層の乾燥過程でブリードを生じて上方に被膜を形成し、表面の粗い支持体に対して被覆性を高めて、記録発色性と記録画質に優れ、糊減感を抑えて記録性能にも優れるものと考えられる。 The sizing agent contained in the anchor layer is not particularly limited, but is preferably at least one selected from the group consisting of a styrene-acrylic sizing agent and a styrene-maleic sizing agent, and more preferably a styrene-acrylic sizing agent. A styrene-acrylic emulsion type sizing agent is more preferable. By using the emulsion type, bleeding occurs during the drying process of the anchor layer, forming a film on the upper side, enhancing the coverage of the support with a rough surface, excellent recording color development and recording image quality, and desensitization. It is considered that the recording performance is excellent by suppressing the above.
アンカー層に含有されるサイズ剤の含有割合としては、固形分換算でアンカー層の全固形量中、1〜9質量%程度が好ましく、2〜8質量%程度がより好ましく、2.5〜5質量%程度が更に好ましい。1質量%以上とすることにより、感熱記録ラベルに加工した後の長期保存に十分耐えて、記録発色性を高めて記録画質を向上できる。一方、9質量%以下とすることにより、記録発色性を高めて、感熱記録層の感度を向上できる。 The content ratio of the sizing agent contained in the anchor layer is preferably about 1 to 9% by mass, more preferably about 2 to 8% by mass, and more preferably 2.5 to 5% in the total solid content of the anchor layer in terms of solid content. About mass% is more preferable. By setting it to 1% by mass or more, it can sufficiently withstand long-term storage after being processed into a thermosensitive recording label, and can improve recording color quality and improve recording image quality. On the other hand, when the content is 9% by mass or less, it is possible to improve the recording colorability and improve the sensitivity of the thermosensitive recording layer.
本発明におけるアンカー層には、本発明の効果を損なわない限り、その他の水性樹脂、助剤等を含有させることもできる。その他の水性樹脂としては、例えば、ポリビニルアルコール、変性ポリビニルアルコール、澱粉、変性澱粉、澱粉−酢酸ビニルグラフト共重合体、カゼイン、ゼラチン、ポリアクリルアミド、ポリアミド、ヒドロキシエチルセルロース、メチルセルロース、カルボキシメチルセルロース、スチレン−ブタジエン系ラテックス、ポリウレタン系ラテックス、アクリル系ラテックス等が挙げられる。これらその他の水性樹脂は、2種併用してもよく、合計の含有割合は、特に制限されないが、アンカー層の全固形量中、5〜30質量%程度が好ましく、8〜20質量%程度がより好ましく、10〜20質量%程度が更に好ましい。 The anchor layer in the present invention may contain other aqueous resins, auxiliaries and the like as long as the effects of the present invention are not impaired. Examples of other aqueous resins include polyvinyl alcohol, modified polyvinyl alcohol, starch, modified starch, starch-vinyl acetate graft copolymer, casein, gelatin, polyacrylamide, polyamide, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, and styrene-butadiene. System latex, polyurethane latex, acrylic latex and the like. These other aqueous resins may be used in combination, and the total content is not particularly limited, but is preferably about 5 to 30% by mass, and about 8 to 20% by mass in the total solid content of the anchor layer. More preferably, about 10-20 mass% is still more preferable.
助剤としては、例えば、ジオクチルスルホコハク酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム、ラウリルアルコール硫酸エステルナトリウム、脂肪酸金属塩等の分散剤、消泡剤等が挙げられる。 Examples of auxiliary agents include sodium dioctylsulfosuccinate, sodium dodecylbenzenesulfonate, sodium lauryl alcohol sulfate, a fatty acid metal salt and the like, and antifoaming agents.
アンカー層は、顔料を含有する顔料塗工層であることが好ましい。顔料を含有することにより、表面の粗い支持体の凹凸を充填して、記録発色性と記録画質を向上することができる。また、アンカー層に含有されるサイズ剤の支持体中への浸透を抑えて被覆性を向上し、糊減感を抑えて記録性能を高めることができる。 The anchor layer is preferably a pigment coating layer containing a pigment. By containing the pigment, the unevenness of the support having a rough surface can be filled to improve the recording color development and the recording image quality. Further, the penetration of the sizing agent contained in the anchor layer into the support can be suppressed to improve the covering property, and the desensitization can be suppressed to improve the recording performance.
アンカー層に含有される顔料は、特に制限されないが、吸油量が70ml/100g以上、特に80〜150ml/100g程度の吸油性顔料及び/またはプラスチック中空粒子及び/または熱膨張性粒子が好ましい。ここで、上記吸油量は、JIS K 5101の方法に従い、求められる値である。 The pigment contained in the anchor layer is not particularly limited, but oil absorbing pigments and / or plastic hollow particles and / or thermally expandable particles having an oil absorption of 70 ml / 100 g or more, particularly about 80 to 150 ml / 100 g are preferable. Here, the oil absorption is a value determined according to the method of JIS K 5101.
アンカー層に含有される吸油性顔料としては、各種のものが使用できるが、具体例としては、焼成カオリン、無定形シリカ、軽質炭酸カルシウム、タルク等の無機顔料が挙げられる。これらの中でも記録性能を向上する観点から焼成カオリンが好ましい。これら吸油性顔料の1次粒子の平均粒子径は0.01〜5μm程度、特に0.02〜3μm程度であるのが好ましい。吸油性顔料の含有割合は、特に制限されないが、アンカー層の全固形量中、2〜90質量%程度が好ましく、5〜90質量%程度がより好ましく、30〜80質量%程度が更に好ましい。 Various types of oil-absorbing pigments contained in the anchor layer can be used, and specific examples include inorganic pigments such as calcined kaolin, amorphous silica, light calcium carbonate, and talc. Of these, calcined kaolin is preferred from the viewpoint of improving recording performance. The average particle diameter of the primary particles of these oil-absorbing pigments is preferably about 0.01 to 5 μm, particularly preferably about 0.02 to 3 μm. The content of the oil-absorbing pigment is not particularly limited, but is preferably about 2 to 90% by mass, more preferably about 5 to 90% by mass, and still more preferably about 30 to 80% by mass in the total solid content of the anchor layer.
アンカー層に含有されるプラスチック中空粒子としては、従来公知なもの、例えば、膜材がアクリル系樹脂、スチレン系樹脂、塩化ビニリデン系樹脂等からなる中空率が50〜99%程度の粒子が例示できる。ここで中空率は、次の式(d/D)×100で求められる値である。式中、dはプラスチック中空粒子の内径を表し、Dはプラスチック中空粒子の外径を表す。プラスチック中空粒子の平均粒子径は、0.5〜10μm程度が好ましく、1〜3μm程度がより好ましい。上記プラスチック中空粒子の含有割合は、特に制限されないが、アンカー層の全固形量中、2〜90質量%程度が好ましく、5〜70質量%程度がより好ましく、10〜50質量%程度が更に好ましい。 Examples of the plastic hollow particles contained in the anchor layer include conventionally known particles, for example, particles having a hollow ratio of about 50 to 99% in which the film material is made of an acrylic resin, a styrene resin, a vinylidene chloride resin, or the like. . Here, the hollowness is a value obtained by the following formula (d / D) × 100. In the formula, d represents the inner diameter of the plastic hollow particle, and D represents the outer diameter of the plastic hollow particle. The average particle size of the plastic hollow particles is preferably about 0.5 to 10 μm, more preferably about 1 to 3 μm. The content ratio of the plastic hollow particles is not particularly limited, but is preferably about 2 to 90% by mass, more preferably about 5 to 70% by mass, and further preferably about 10 to 50% by mass in the total solid content of the anchor layer. .
本発明では、アンカー層に吸油性顔料を含有させることが好ましく、吸油性顔料とプラスチック中空粒子とを含有させることがより好ましい。吸油性顔料とプラスチック中空粒子とは、上記含有割合の範囲で使用し、且つ吸油性顔料とプラスチック中空粒子の合計の含有割合は、アンカー層の全固形量中、5〜93質量%程度が好ましく、10〜85質量%程度がより好ましい。 In the present invention, the anchor layer preferably contains an oil-absorbing pigment, and more preferably contains an oil-absorbing pigment and plastic hollow particles. The oil-absorbing pigment and the plastic hollow particles are used within the above-mentioned content ratio, and the total content ratio of the oil-absorbing pigment and the plastic hollow particles is preferably about 5 to 93% by mass in the total solid amount of the anchor layer. 10 to 85% by mass is more preferable.
本発明では、アンカー層中の吸油性顔料/プラスチック中空粒子の質量比率は、100/0〜40/60の範囲が好ましく、90/10〜60/40の範囲がより好ましく、85/15〜70/30の範囲が更に好ましい。吸油性顔料の質量比率を100以下とすることにより、アンカー層のクッション性を高めて、記録発色性、記録画質を向上できる。一方、40以上とすることにより、アンカー層の吸油性を十分に発揮でき、ヘッド粕等による画像欠陥を減らして記録画質を向上できる。また、この範囲とすることにより、バリア性をより一層高めて、感熱記録ラベルに加工した後の長期保存に十分に耐えることができる。 In the present invention, the mass ratio of the oil absorbing pigment / plastic hollow particles in the anchor layer is preferably in the range of 100/0 to 40/60, more preferably in the range of 90/10 to 60/40, and 85/15 to 70. The range of / 30 is more preferable. By setting the mass ratio of the oil-absorbing pigment to 100 or less, the cushioning property of the anchor layer can be improved, and the recording color development property and the recording image quality can be improved. On the other hand, by setting it to 40 or more, the oil absorption of the anchor layer can be sufficiently exerted, and the image quality due to the head wrinkles can be reduced and the recording image quality can be improved. Moreover, by setting it as this range, barrier property can be improved further and it can fully endure long-term storage after processing into a thermosensitive recording label.
アンカー層には耐水化剤が含有されている。耐水化剤としては、アジリジン化合物、ブロックイソシアネート化合物、アジピン酸ジヒドラジド等のカルボン酸ジヒドラジド系化合物、グリオキザール、ホルマリン、グリシン、グリシジルエステル、グリシジルエーテル、ジメチロール尿素、メラミン樹脂、ポリアミド樹脂、ポリアミドポリアミン−エピクロルヒドリン樹脂、ケトン−アルデヒド樹脂、過硫酸アンモニウム、塩化第二鉄、塩化マグネシウム、炭酸ジルコニウムアンモニウム塩、硼砂、硼酸、四硼酸ソーダ、硼酸トリエステル、硼素系ポリマー、四硼酸カリウム、炭酸ジルコニウムアンモニウム、エポキシ系化合物、ヒドラジド化合物、オキサゾリン基含有化合物、グリオキシル酸ナトリウム、ジ(グリオキシル酸)カルシウム、グリオキシル酸アンモニウム等のグリオキシル酸塩等が挙げられる。これらは、1種単独又は2種以上を併用して使用することができる。これらの耐水化剤は、アンカー層の全固形量中、0.1〜10質量%の範囲で用いることが好ましく、1〜5質量%程度がより好ましい。 The anchor layer contains a waterproofing agent. Water resistance agents include aziridine compounds, blocked isocyanate compounds, carboxylic acid dihydrazide compounds such as adipic acid dihydrazide, glyoxal, formalin, glycine, glycidyl ester, glycidyl ether, dimethylol urea, melamine resin, polyamide resin, polyamide polyamine-epichlorohydrin resin , Ketone-aldehyde resin, ammonium persulfate, ferric chloride, magnesium chloride, zirconium carbonate ammonium salt, borax, boric acid, sodium tetraborate, borate triester, boron polymer, potassium tetraborate, ammonium zirconium carbonate, epoxy compound, Glyoxy compounds such as hydrazide compounds, oxazoline group-containing compounds, sodium glyoxylate, di (glyoxylic acid) calcium and ammonium glyoxylic acid Le acid salts. These can be used alone or in combination of two or more. These waterproofing agents are preferably used in the range of 0.1 to 10% by mass, more preferably about 1 to 5% by mass in the total solid content of the anchor layer.
アンカー層に含有される耐水化剤としては、バリア性を向上し、感熱記録層用塗液のアンカー層への不均一な浸透を抑えて発色性を高める観点から、アジリジン化合物、カルボン酸ジヒドラジド系化合物、グリオキザール、グリシン、グリシジルエステル、グリシジルエーテル、ジメチロール尿素、メラミン樹脂、ポリアミド樹脂、ポリアミドポリアミン−エピクロルヒドリン樹脂、ケトン−アルデヒド樹脂、炭酸ジルコニウムアンモニウム塩、硼砂、硼酸、硼素系ポリマー、オキサゾリン基含有化合物、及びグリオキシル酸塩よりなる群から選ばれる少なくとも1種が好ましい。これらの耐水化剤により、アンカー層上に形成される感熱記録層及び保護層との密着性を高め、表面強度を向上させる効果も得られる。耐水化剤の含有量としては、特に限定されないが、サイズ剤を耐水化剤の1質量部に対して、固形分換算で0.5〜5質量部程度含有させることが好ましく、1〜4質量部程度含有させることがより好ましい。 As a water-resistant agent contained in the anchor layer, an aziridine compound and a carboxylic acid dihydrazide are used from the viewpoint of improving the barrier property and suppressing the uneven penetration of the coating liquid for the thermosensitive recording layer into the anchor layer to enhance the color development. Compound, Glyoxal, Glycine, Glycidyl ester, Glycidyl ether, Dimethylol urea, Melamine resin, Polyamide resin, Polyamide polyamine-epichlorohydrin resin, Ketone-aldehyde resin, Zirconium ammonium carbonate, Borax, Boric acid, Boron-based polymer, Oxazoline group-containing compound, And at least one selected from the group consisting of glyoxylate is preferred. By these water-proofing agents, it is possible to enhance the adhesion between the heat-sensitive recording layer and the protective layer formed on the anchor layer and to improve the surface strength. Although it does not specifically limit as content of a water-resistant agent, It is preferable to contain about 0.5-5 mass parts in conversion of solid content with respect to 1 mass part of a water-resistant agent, and 1-4 mass. It is more preferable to contain about part.
アンカー層は、一般に水を分散媒体とし、サイズ剤及び耐水化剤、必要により顔料、その他の水性樹脂、助剤等を混合することにより調製されたアンカー層用塗液を用いて塗布した後、乾燥されて支持体上に形成される。アンカー層の塗布量は、特に制限されないが、乾燥重量で3〜20g/m2程度が好ましく、5〜15g/m2程度がより好ましい。 The anchor layer is generally applied using a coating liquid for an anchor layer prepared by mixing water as a dispersion medium and mixing a sizing agent and a water-proofing agent, if necessary, a pigment, other aqueous resin, an auxiliary agent, and the like. Dried to form on the support. The application amount of the anchor layer is not particularly limited, but is preferably about 3 to 20 g / m 2 by dry weight, and more preferably about 5 to 15 g / m 2 .
本発明における感熱記録層は、各種公知のロイコ染料と呈色剤を含有することができる。その他、必要に応じて、増感剤、保存性改良剤、顔料、各種助剤等を含有してもよい。かかる感熱記録層は、アンカー層上に備えられている。 The heat-sensitive recording layer in the present invention can contain various known leuco dyes and colorants. In addition, you may contain a sensitizer, a preservability improving agent, a pigment, various adjuvants, etc. as needed. Such a heat-sensitive recording layer is provided on the anchor layer.
ロイコ染料の具体例としては、例えば、3−ジエチルアミノ−6−メチル−7−アニリノフルオラン、3−ジ(n−ブチル)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−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−アリニノフルオラン、3−(N−エチル−p−トルイジノ)−6−メチル−7−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−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−(N−イソアミル−N−エチルアミノ)−7−(o−クロロアニリノ)フルオラン、3−(N−エチル−N−2−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−ジエチルアミノ−6−クロロ−7−アニリノフルオラン、3−(N−n−ヘキシル−N−エチルアミノ)−6−メチル−7−アニリノフルオラン、3−〔N−(3−エトキシプロピル)−N−エチルアミノ〕−6−メチル−7−アニリノフルオラン、3−〔N−(3−エトキシプロピル)−N−メチルアミノ〕−6−メチル−7−アニリノフルオラン、3−ジエチルアミノ−7−(2−クロロアニリノ)フルオラン、3−ジ(n−ブチルアミノ)−7−(2−クロロアニリノ)フルオラン等が挙げられる。これらのロイコ染料は、単独、または2種以上を併用して用いることができる。かかるロイコ染料の含有割合は、特に制限されず、感熱記録層の全固形量中、3〜30質量%程度が好ましい。 Specific examples of the leuco dye include 3-diethylamino-6-methyl-7-anilinofluorane, 3-di (n-butyl) amino-6-methyl-7-anilinofluorane, 3-di ( n-pentyl) amino-6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isoamylamino) -6-methyl-7-arininofluorane, 3- (N-ethyl-p-) Toluidino) -6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-diethylamino-7- (m-trifluoromethylanilino) fluorane, 3- (N -Isoamyl-N-ethylamino) -7- (o-chloroanilino) fluorane, 3- (N-ethyl-N-2-tetrahydrofurfurylamino) -6-methyl-7-anilinofluorane 3-diethylamino-6-chloro-7-anilinofluorane, 3- (Nn-hexyl-N-ethylamino) -6-methyl-7-anilinofluorane, 3- [N- (3-ethoxy Propyl) -N-ethylamino] -6-methyl-7-anilinofluorane, 3- [N- (3-ethoxypropyl) -N-methylamino] -6-methyl-7-anilinofluorane, 3 -Diethylamino-7- (2-chloroanilino) fluorane, 3-di (n-butylamino) -7- (2-chloroanilino) fluorane and the like. These leuco dyes can be used alone or in combination of two or more. The content ratio of the leuco dye is not particularly limited, and is preferably about 3 to 30% by mass in the total solid content of the heat-sensitive recording layer.
呈色剤の具体例としては、例えば、4−tert−ブチルフェノール、4−アセチルフェノール、4−tert−オクチルフェノール、4,4’−sec−ブチリデンジフェノール、4−フェニルフェノール、4,4’−ジヒドロキシジフェニルメタン、4,4’−イソプロピリデンジフェノール、4,4’−シクロヘキシリデンジフェノール、1,1−ビス(4−ヒドロキシフェニル)−1−フェニルエタン、4,4’−ジヒドロキシジフェニルスルフィド、4,4’−チオビス(3−メチル−6−tert−ブチルフェノール)、4,4’−ジヒドロキシジフェニルスルホン、2,4’−ジヒドロキシジフェニルスルホン、4−ヒドロキシ−4’−イソプロポキシジフェニルスルホン、4−ヒドロキシ−4’−n−プロポキシジフェニルスルホン、4−ヒドロキシ−4’−アリルオキシジフェニルスルホン、3,3’−ジアリル−4,4’−ジヒドロキシジフェニルスルホン、ビス(p−ヒドロキシフェニル)酢酸ブチル、ビス(p−ヒドロキシフェニル)酢酸メチル等のフェノール性化合物、4−ヒドロキシベンゾフェノン、4−ヒドロキシフタル酸ジメチル、4−ヒドロキシ安息香酸メチル、4−ヒドロキシ安息香酸プロピル、4−ヒドロキシ安息香酸−sec−ブチル、4−ヒドロキシ安息香酸フェニル、4−ヒドロキシ安息香酸ベンジル、4−ヒドロキシ安息香酸トリル、4−ヒドロキシ安息香酸クロロフェニル、4,4’−ジヒドロキシジフェニルエーテル等のフェノール性化合物、または安息香酸、p−tert−ブチル安息香酸、トリクロル安息香酸、テレフタル酸、サリチル酸、3−tert−ブチルサリチル酸、3−イソプロピルサリチル酸、3−ベンジルサリチル酸、3−(α−メチルベンジル)サリチル酸、3,5−ジ−tert−ブチルサリチル酸等の芳香族カルボン酸、及びこれらフェノール性化合物、芳香族カルボン酸と例えば亜鉛、マグネシウム、アルミニウム、カルシウム等の多価金属との塩等の有機酸性物質、N−p−トルエンスルホニル−N’−3−(p−トルエンスルホニルオキシ)フェニルウレア、N−p−トルエンスルホニル−N’−p−ブトキシカルボニルフェニルウレア、N−p−トリルスルホニル−N’−フェニルウレア、4,4’−ビス(p−トルエンスルホニルアミノカルボニルアミノ)ジフェニルメタン、4,4’−ビス[(4−メチル−3−フェノキシカルボニルアミノフェニル)ウレイド]ジフェニルスルホン等のウレア化合物が挙げられる。これらの呈色剤は、単独、または2種以上を併用して用いることができる。かかる呈色剤の含有量は、特に制限されず、使用されるロイコ染料に応じて調整すればよく、一般にロイコ染料1質量部に対して0.5〜10質量部程度が好ましく、0.8〜10質量部程度がより好ましく、1〜10質量部程度が更に好ましく、1.5〜5質量部程度が特に好ましい。 Specific examples of the colorant include, for example, 4-tert-butylphenol, 4-acetylphenol, 4-tert-octylphenol, 4,4′-sec-butylidene diphenol, 4-phenylphenol, 4,4′-dihydroxy Diphenylmethane, 4,4′-isopropylidene diphenol, 4,4′-cyclohexylidene diphenol, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 4,4′-dihydroxydiphenyl sulfide, 4, 4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-dihydroxydiphenylsulfone, 2,4′-dihydroxydiphenylsulfone, 4-hydroxy-4′-isopropoxydiphenylsulfone, 4-hydroxy- 4'-n-propoxydiphenyl Lufone, 4-hydroxy-4′-allyloxydiphenylsulfone, 3,3′-diallyl-4,4′-dihydroxydiphenylsulfone, butyl bis (p-hydroxyphenyl) acetate, methyl bis (p-hydroxyphenyl) acetate, etc. Phenolic compounds, 4-hydroxybenzophenone, dimethyl 4-hydroxyphthalate, methyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, 4-hydroxybenzoate-sec-butyl, phenyl 4-hydroxybenzoate, 4- Phenolic compounds such as benzyl hydroxybenzoate, tolyl 4-hydroxybenzoate, chlorophenyl 4-hydroxybenzoate, 4,4′-dihydroxydiphenyl ether, or benzoic acid, p-tert-butylbenzoic acid, trichlorobenzoic acid, terephthalate Aromatic carboxylic acids such as acid, salicylic acid, 3-tert-butylsalicylic acid, 3-isopropylsalicylic acid, 3-benzylsalicylic acid, 3- (α-methylbenzyl) salicylic acid, 3,5-di-tert-butylsalicylic acid, and the like Phenolic compounds, organic acidic substances such as salts of aromatic carboxylic acids and polyvalent metals such as zinc, magnesium, aluminum, calcium, etc., Np-toluenesulfonyl-N′-3- (p-toluenesulfonyloxy) Phenylurea, Np-toluenesulfonyl-N′-p-butoxycarbonylphenylurea, Np-tolylsulfonyl-N′-phenylurea, 4,4′-bis (p-toluenesulfonylaminocarbonylamino) diphenylmethane, 4,4′-bis [(4-methyl-3-phenoxycal Sulfonyl aminophenyl) ureido] urea compounds such as diphenyl sulfone. These colorants can be used alone or in combination of two or more. The content of the colorant is not particularly limited and may be adjusted according to the leuco dye to be used, and is generally preferably about 0.5 to 10 parts by mass with respect to 1 part by mass of the leuco dye, 0.8 About 10 mass parts is more preferable, About 1-10 mass parts is still more preferable, About 1.5-5 mass parts is especially preferable.
増感剤の具体例としては、例えば、ステアリン酸アミド、メトキシカルボニル−N−ステアリン酸ベンズアミド、N−ベンゾイルステアリン酸アミド、N−エイコサン酸アミド、エチレンビステアリン酸アミド、ベヘン酸アミド、メチレンビスステアリン酸アミド、N−メチロールステアリン酸アミド、テレフタル酸ジベンジル、テレフタル酸ジメチル、テレフタル酸ジオクチル、p−ベンジルオキシ安息香酸ベンジル、1−ヒドロキシ−2−ナフトエ酸フェニル、2−ナフチルベンジルエーテル、m−ターフェニル、シュウ酸ジベンジル、シュウ酸−ジ−p−メチルベンジル、シュウ酸−ジ−p−クロロベンジル、p−ベンジルビフェニル、トリルビフェニルエーテル、ジ(p−メトキシフェノキシエチル)エーテル、1,2−ジ(3−メチルフェノキシ)エタン、1,2−ジ(4−メチルフェノキシ)エタン、1,2−ジ(4−メトキシフェノキシ)エタン、1,2−ジ(4−クロロフェノキシ)エタン、1,2−ジフェノキシエタン、1−(4−メトキシフェノキシ)−2−(2−メチルフェノキシ)エタン、p−メチルチオフェニルベンジルエーテル、1,4−ジ(フェニルチオ)ブタン、p−アセトトルイジド、p−アセトフェネチジド、N−アセトアセチル−p−トルイジン、ジ(β−ビフェニルエトキシ)ベンゼン、p−ジ(ビニルオキシエトキシ)ベンゼン、1−イソプロピルフェニル−2−フェニルエタン、ジフェニルスルホン等が挙げられる。かかる増感剤の含有量は、特に制限されないが、一般に呈色剤1質量部に対して4質量部以下程度の範囲で調節するのが望ましい。 Specific examples of the sensitizer include, for example, stearic acid amide, methoxycarbonyl-N-stearic acid benzamide, N-benzoyl stearic acid amide, N-eicosanoic acid amide, ethylene bistearic acid amide, behenic acid amide, methylene bis stearin. Acid amide, N-methylol stearic acid amide, dibenzyl terephthalate, dimethyl terephthalate, dioctyl terephthalate, benzyl p-benzyloxybenzoate, phenyl 1-hydroxy-2-naphthoate, 2-naphthylbenzyl ether, m-terphenyl , Dibenzyl oxalate, oxalate-di-p-methylbenzyl, oxalate-di-p-chlorobenzyl, p-benzylbiphenyl, tolylbiphenyl ether, di (p-methoxyphenoxyethyl) ether, 1,2-di ( 3-me Ruphenoxy) ethane, 1,2-di (4-methylphenoxy) ethane, 1,2-di (4-methoxyphenoxy) ethane, 1,2-di (4-chlorophenoxy) ethane, 1,2-diphenoxy Ethane, 1- (4-methoxyphenoxy) -2- (2-methylphenoxy) ethane, p-methylthiophenylbenzyl ether, 1,4-di (phenylthio) butane, p-acetoluidide, p-acetophenetide, N -Acetoacetyl-p-toluidine, di (β-biphenylethoxy) benzene, p-di (vinyloxyethoxy) benzene, 1-isopropylphenyl-2-phenylethane, diphenylsulfone and the like. The content of such a sensitizer is not particularly limited, but it is generally desirable to adjust it in a range of about 4 parts by mass or less with respect to 1 part by mass of the colorant.
保存性改良剤の具体例としては、例えば、2,2’−メチレンビス(4−メチル−6−tert−ブチルフェノール)、2,2’−エチレンビス(4−メチル−6−tert−ブチルフェノール)、2,2’−メチレンビス(4−エチル−6−tert−ブチルフェノール)、2,2’−メチレンビス(4,6−ジ−tert−ブチルフェノール)、2,2’−エチリデンビス(4,6−ジ−tert−ブチルフェノール)、2,2’−エチリデンビス(4−メチル−6−tert−ブチルフェノール)、2,2’−エチリデンビス(4−エチル−6−tert−ブチルフェノール)、2,2’−(2,2−プロピリデン)ビス(4,6−ジ−tert−ブチルフェノール)、2,2’−メチレンビス(4−メトキシ−6−tert−ブチルフェノール)、2,2’−メチレンビス(6−tert−ブチルフェノール)、4,4’−チオビス(3−メチル−6−tert−ブチルフェノール)、4,4’−チオビス(2−メチル−6−tert−ブチルフェノール)、4,4’−チオビス(5−メチル−6−tert−ブチルフェノール)、4,4’−チオビス(2−クロロ−6−tert−ブチルフェノール)、4,4’−チオビス(2−メトキシ−6−tert−ブチルフェノール)、4,4’−チオビス(2−エチル−6−tert−ブチルフェノール)、4,4’−ブチリデンビス(6−tert−ブチル−m−クレゾール)、1−〔α−メチル−α−(4’−ヒドロキシフェニル)エチル〕−4−〔α’,α’−ビス(4”−ヒドロキシフェニル)エチル〕ベンゼン、1,1,3−トリス(2−メチル−4−ヒドロキシ−5−シクロヘキシルフェニル)ブタン、1,1,3−トリス(2−メチル−4−ヒドロキシ−5−tert−ブチルフェニル)ブタン、4,4’−チオビス(3−メチルフェノール)、4,4’−ジヒドロキシ−3,3’,5,5’−テトラブロモジフェニルスルホン、4,4’−ジヒドロキシ−3,3’,5,5’−テトラメチルジフェニルスルホン、2,2−ビス(4−ヒドロキシ−3,5−ジブロモフェニル)プロパン、2,2−ビス(4−ヒドロキシ−3,5−ジクロロフェニル)プロパン、2,2−ビス(4−ヒドロキシ−3,5−ジメチルフェニル)プロパン等のヒンダードフェノール化合物、N,N’−ジ−2−ナフチル−p−フェニレンジアミン、2,2’−メチレンビス(4,6−ジ−tert−ブチルフェニル)リン酸ソーダ等が挙げられる。 Specific examples of the preservability improver include, for example, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-ethylenebis (4-methyl-6-tert-butylphenol), 2 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert) -Butylphenol), 2,2'-ethylidenebis (4-methyl-6-tert-butylphenol), 2,2'-ethylidenebis (4-ethyl-6-tert-butylphenol), 2,2 '-(2, 2-propylidene) bis (4,6-di-tert-butylphenol), 2,2′-methylenebis (4-methoxy-6-tert-butyl) Enol), 2,2′-methylenebis (6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (2-methyl-6-tert- Butylphenol), 4,4′-thiobis (5-methyl-6-tert-butylphenol), 4,4′-thiobis (2-chloro-6-tert-butylphenol), 4,4′-thiobis (2-methoxy-) 6-tert-butylphenol), 4,4′-thiobis (2-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (6-tert-butyl-m-cresol), 1- [α-methyl- α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene, 1,1 , 3-Tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4,4′- Thiobis (3-methylphenol), 4,4′-dihydroxy-3,3 ′, 5,5′-tetrabromodiphenyl sulfone, 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethyldiphenyl Sulfone, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3) , 5-dimethylphenyl) propane, a hindered phenol compound, N, N′-di-2-naphthyl-p-phenylenediamine, 2,2′-methylenebis (4 6- di -tert- butylphenyl) phosphate sodium, and the like.
感熱記録層に含有される顔料の具体例としては、例えば、カオリン、炭酸カルシウム、炭酸マグネシウム、水酸化アルミニウム、硫酸バリウム、タルク、焼成カオリン、酸化チタン、酸化亜鉛、珪藻土、微粒子状無水シリカ、活性白土等の無機顔料、スチレンマイクロボール、ナイロンパウダー、ポリエチレンパウダー、尿素−ホルマリン樹脂フィラー、スチレン−メタクリル酸共重合樹脂、ポリスチレン樹脂、生澱粉粒子等の有機顔料が挙げられる。顔料の含有量は、発色濃度を低下させない程度の量、即ち感熱記録層の全固形量中、50質量%以下が好ましい。 Specific examples of pigments contained in the heat-sensitive recording layer include, for example, kaolin, calcium carbonate, magnesium carbonate, aluminum hydroxide, barium sulfate, talc, calcined kaolin, titanium oxide, zinc oxide, diatomaceous earth, particulate anhydrous silica, active Inorganic pigments such as clay, organic pigments such as styrene microballs, nylon powder, polyethylene powder, urea-formalin resin filler, styrene-methacrylic acid copolymer resin, polystyrene resin, and raw starch particles. The pigment content is preferably 50% by mass or less in an amount that does not lower the color density, that is, in the total solid content of the heat-sensitive recording layer.
感熱記録層は、一般に水を分散媒体とし、ロイコ染料と呈色剤、必要により増感剤と保存性改良剤を一緒に、または別々にボールミル、アトライター、サンドミル等の撹拌・粉砕機により平均粒子径が2μm以下となるように分散して得た分散液を用いて、必要により顔料、接着剤、助剤等を混合することにより調製された感熱記録層用塗液を塗布した後、乾燥されてアンカー層上に形成される。感熱記録層の塗布量は、特に制限されず、乾燥後の塗布量で1〜12g/m2程度が好ましく、2〜10g/m2がより好ましく、2.5〜5.5g/m2が特に好ましい。なお、感熱記録層は必要に応じて2層以上に分けて形成することができ、各層の組成と塗布量は、同一であってもよく、また異なっていてもよい。 The heat-sensitive recording layer is generally averaged by a stirrer / crusher such as a ball mill, an attritor, or a sand mill, with water as a dispersion medium, and a leuco dye and a colorant, and if necessary, a sensitizer and a preservative improver. Using a dispersion obtained by dispersing so that the particle diameter is 2 μm or less, and applying a coating solution for a thermal recording layer prepared by mixing pigments, adhesives, auxiliaries, etc., if necessary, drying To be formed on the anchor layer. The coating amount of the heat-sensitive recording layer is not particularly limited, is preferably about 1~12g / m 2 of the coating amount after drying, more preferably 2~10g / m 2, 2.5~5.5g / m 2 is Particularly preferred. The thermosensitive recording layer can be formed by dividing into two or more layers as necessary, and the composition and application amount of each layer may be the same or different.
感熱記録層用塗液に使用される接着剤としては、例えば、水溶性接着剤及び水分散性接着剤のいずれの水性接着剤も使用できる。水溶性接着剤としては、例えば、ポリビニルアルコール、変性ポリビニルアルコール、澱粉及びその誘導体、メトキシセルロース、カルボキシメチルセルロース、ヒドロキシプロピルメチルセルロース、メチルセルロース、及びエチルセルロース等のセルロース誘導体、ポリアクリル酸ソーダ、ポリビニルピロリドン、アクリル酸アミド−アクリル酸エステル共重合体、アクリル酸アミド−アクリル酸エステル−メタクリル酸共重合体、ポリアクリルアミド、アルギン酸ソーダ、ゼラチン、及びカゼイン等が挙げられる。水分散性接着剤としては、ポリ酢酸ビニル、ポリウレタン、スチレン−ブタジエン共重合体、スチレン−ブタジエン−アクリロニトリル共重合体、アクリロニトリル−ブタジエン共重合体、ポリアクリル酸、ポリアクリル酸エステル、塩化ビニル−酢酸ビニル共重合体、ポリブチルメタクリレート、エチレン−酢酸ビニル共重合体、シリル化ウレタン、アクリル−シリコン複合体、及びアクリル−シリコン−ウレタン複合体等の水不溶性重合体のラテックス等が挙げられる。これらは、1種単独または2種以上を併用して使用することができる。 As the adhesive used for the heat-sensitive recording layer coating liquid, for example, any of a water-soluble adhesive and a water-dispersible adhesive can be used. Examples of the water-soluble adhesive include polyvinyl alcohol, modified polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as methoxycellulose, carboxymethylcellulose, hydroxypropylmethylcellulose, methylcellulose, and ethylcellulose, polyacrylic acid soda, polyvinylpyrrolidone, and acrylic acid. Examples include amide-acrylic acid ester copolymers, acrylic acid amide-acrylic acid ester-methacrylic acid copolymers, polyacrylamide, sodium alginate, gelatin, and casein. Water dispersible adhesives include polyvinyl acetate, polyurethane, styrene-butadiene copolymer, styrene-butadiene-acrylonitrile copolymer, acrylonitrile-butadiene copolymer, polyacrylic acid, polyacrylic acid ester, vinyl chloride-acetic acid Examples thereof include latex of water-insoluble polymers such as vinyl copolymer, polybutyl methacrylate, ethylene-vinyl acetate copolymer, silylated urethane, acrylic-silicon composite, and acrylic-silicon-urethane composite. These can be used alone or in combination of two or more.
感熱記録層用塗液中には、必要に応じて分散剤、耐水化剤、ワックス類、金属石鹸、有色染料、有色顔料、蛍光染料、撥油剤、消泡剤及び粘度調節剤等の助剤を含有させることができる。 In the heat-sensitive recording layer coating liquid, auxiliary agents such as dispersants, water-proofing agents, waxes, metal soaps, colored dyes, colored pigments, fluorescent dyes, oil repellents, antifoaming agents, and viscosity modifiers as necessary. Can be contained.
耐水化剤としては、例えばグリオキザール等のアルデヒド系化合物、ポリエチレンイミン等のポリアミン系化合物、エポキシ系化合物、ポリアミド樹脂、メラミン樹脂、ジメチロールウレア化合物、アジリジン化合物、ブロックイソシアネート化合物、アジピン酸ジヒドラジド等のカルボン酸ジヒドラジド系化合物、グリオキシル酸塩、並びに過硫酸アンモニウム、塩化第二鉄、塩化マグネシウム、四硼酸ソーダ、四硼酸カリウム及び硼酸等の無機化合物、硼酸トリエステル、硼素系ポリマー等が挙げられる。これらは、1種単独または2種以上を併用して使用することができる。これらの耐水化剤は、感熱記録層の全固形量中、0.1〜10質量%の範囲で用いることが好ましい。 Examples of water-resistant agents include aldehyde compounds such as glyoxal, polyamine compounds such as polyethyleneimine, epoxy compounds, polyamide resins, melamine resins, dimethylol urea compounds, aziridine compounds, blocked isocyanate compounds, and adipic acid dihydrazides. Examples thereof include acid dihydrazide compounds, glyoxylate salts, and inorganic compounds such as ammonium persulfate, ferric chloride, magnesium chloride, sodium tetraborate, potassium tetraborate, and boric acid, boric acid triesters, boron polymers, and the like. These can be used alone or in combination of two or more. These waterproofing agents are preferably used in the range of 0.1 to 10% by mass in the total solid content of the heat-sensitive recording layer.
本発明では、感熱記録層上に必要に応じて保護層を備えることもできる。保護層は、顔料と接着剤を含有することが好ましい。更に保護層には、サーマルヘッドに対するスティッキングを防止する目的で、ポリオレフィンワックス、ステアリン酸亜鉛のような滑剤を含有させることが好ましく、紫外線吸収剤を含有させることもできる。また、光沢を有する保護層を設けることにより、製品の付加価値を高めることもできる。 In the present invention, a protective layer can be provided on the heat-sensitive recording layer as necessary. The protective layer preferably contains a pigment and an adhesive. Furthermore, the protective layer preferably contains a lubricant such as polyolefin wax or zinc stearate for the purpose of preventing sticking to the thermal head, and can also contain an ultraviolet absorber. In addition, the added value of the product can be increased by providing a glossy protective layer.
保護層に含有される接着剤としては、特に制限されず、水溶性接着剤及び水分散性接着剤のいずれの水性接着剤も使用できる。接着剤は、感熱記録層に使用できるものの中から適宜選択することができる。水溶性接着剤として重合度1000〜3000のポリビニルアルコールを、保護層の全固形量中、15〜50質量%含有することにより、本発明の効果をより一層高めることができる。重合度1000〜3000のポリビニルアルコールとしては、例えば、完全鹸化または部分鹸化ポリビニルアルコール、アセトアセチル変性ポリビニルアルコール、ジアセトン変性ポリビニルアルコール、カルボキシ変性ポリビニルアルコール及び珪素変性ポリビニルアルコール等が挙げられる。これらの中でも、アセトアセチル変性ポリビニルアルコール及びジアセトン変性のポリビニルアルコールは、保護層表面のバリア性を向上させ、耐薬品性等の保存性を向上させることができ、好ましい。 The adhesive contained in the protective layer is not particularly limited, and any water-based adhesive such as a water-soluble adhesive and a water-dispersible adhesive can be used. The adhesive can be appropriately selected from those that can be used for the heat-sensitive recording layer. By containing 15 to 50% by mass of polyvinyl alcohol having a polymerization degree of 1000 to 3000 as a water-soluble adhesive in the total solid content of the protective layer, the effects of the present invention can be further enhanced. Examples of the polyvinyl alcohol having a polymerization degree of 1000 to 3000 include fully saponified or partially saponified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, and silicon-modified polyvinyl alcohol. Among these, acetoacetyl-modified polyvinyl alcohol and diacetone-modified polyvinyl alcohol are preferable because they can improve the barrier property of the surface of the protective layer and improve the storage stability such as chemical resistance.
保護層に含有される水性接着剤の含有割合は、合計で保護層の全固形量中、10〜80質量%程度が好ましく、20〜75質量%程度がより好ましい。10質量%以上とすることにより、優れたバリア性を得ることができ、しかも、表面強度を高めて紙粉の発生を防ぐことができる。一方、80質量%以下とすることにより、記録障害であるスティッキングを抑制できる。 The total content of the aqueous adhesive contained in the protective layer is preferably about 10 to 80% by mass and more preferably about 20 to 75% by mass in the total solid content of the protective layer. By setting it as 10 mass% or more, the outstanding barrier property can be obtained, and also generation | occurrence | production of paper dust can be prevented by improving surface strength. On the other hand, by setting it to 80% by mass or less, sticking that is a recording failure can be suppressed.
保護層中の顔料としては、例えば、炭酸カルシウム、酸化亜鉛、酸化アルミニウム、二酸化チタン、無定形シリカ、合成マイカ、水酸化アルミニウム、硫酸バリウム、タルク、カオリン、焼成カオリン等の無機顔料、ナイロン樹脂フィラー、尿素−ホルマリン樹脂フィラー、生澱粉粒子等の有機顔料が挙げられる。これらの中でも、カオリン、水酸化アルミニウムは可塑剤や油等の薬品に対するバリア性の低下が少なく、しかも記録濃度の低下も小さいため、好ましい。 Examples of the pigment in the protective layer include calcium carbonate, zinc oxide, aluminum oxide, titanium dioxide, amorphous silica, synthetic mica, aluminum hydroxide, barium sulfate, talc, kaolin, calcined kaolin and other inorganic pigments, nylon resin filler And organic pigments such as urea-formalin resin filler and raw starch particles. Among these, kaolin and aluminum hydroxide are preferable because they have a small decrease in barrier properties against chemicals such as plasticizers and oils and a small decrease in recording density.
保護層中の顔料の含有割合は、保護層の全固形量中、5〜80質量%程度が好ましく、10〜70質量%程度がより好ましい。5質量%以上とすることにより、サーマルヘッドとの滑りを良くして、スティッキングやヘッド粕を抑制できる。一方、80質量%以下とすることにより、バリア性を向上できる。 The content ratio of the pigment in the protective layer is preferably about 5 to 80% by mass and more preferably about 10 to 70% by mass in the total solid content of the protective layer. By setting the content to 5% by mass or more, the sliding with the thermal head can be improved, and sticking and head wrinkles can be suppressed. On the other hand, by setting it to 80% by mass or less, the barrier property can be improved.
保護層は、一般に水を分散媒体とし、顔料と接着剤、必要により助剤等を混合することにより調製された保護層用塗液を用いて塗布した後、乾燥されて感熱記録層上に形成される。保護層用塗液の塗布量は、特に制限されず、乾燥重量で0.3〜15g/m2程度が好ましく、0.3〜10g/m2程度がより好ましく、0.5〜8g/m2程度が更に好ましく、1.0〜8g/m2程度が特に好ましい。なお、保護層は、必要に応じて2層以上に分けて形成することができ、各層の組成と塗工量は、同一であってもよく、また異なっていてもよい。 The protective layer is generally formed on the heat-sensitive recording layer after coating using a protective layer coating solution prepared by mixing water, a dispersion medium, and a pigment, an adhesive, and, if necessary, an auxiliary agent. Is done. The coating amount of the coating liquid for the protective layer is not particularly limited, and is preferably about 0.3 to 15 g / m 2 , more preferably about 0.3 to 10 g / m 2 by dry weight, and 0.5 to 8 g / m. About 2 is more preferable, and about 1.0 to 8 g / m 2 is particularly preferable. In addition, a protective layer can be divided and formed in two or more layers as needed, and the composition and coating amount of each layer may be the same or different.
保護層用塗液に使用される助剤としては、例えばステアリン酸亜鉛、ステアリン酸カルシウム、ポリエチレンワックス、カルナバロウ、パラフィンワックス、エステルワックス等の滑剤、アルキルベンゼンスルホン酸ナトリウム、ジオクチルスルホコハク酸ナトリウム、スルホン酸変性ポリビニルアルコール、アセチレングリコール系、フッ素系、シリコン系、リン酸エステル系、エーテル型等の界面活性剤、あるいはベタイン、アミノカルボン酸塩、イミダゾリン誘導体等の両性系界面活性剤等の界面活性剤、グリオキザール、硼酸、ジアルデヒド澱粉、メチロール尿素、グリオキシル酸塩、エポキシ系化合物、ヒドラジン系化合物等の耐水化剤、疎水性ポリカルボン酸共重合体、紫外線吸収剤、蛍光染料、着色染料、離型剤、酸化防止剤等が挙げられる。助剤の使用量は、広い範囲から適宜設定することができる。 Auxiliaries used in the coating liquid for the protective layer include, for example, lubricants such as zinc stearate, calcium stearate, polyethylene wax, carnauba wax, paraffin wax, ester wax, sodium alkylbenzene sulfonate, sodium dioctyl sulfosuccinate, sulfonic acid-modified polyvinyl. Surfactants such as alcohol, acetylene glycol-based, fluorine-based, silicon-based, phosphate-based, ether-type surfactants, or amphoteric surfactants such as betaine, aminocarboxylate, imidazoline derivatives, glyoxal, Water resistance agents such as boric acid, dialdehyde starch, methylol urea, glyoxylate, epoxy compounds, hydrazine compounds, hydrophobic polycarboxylic acid copolymers, UV absorbers, fluorescent dyes, coloring dyes, release agents, oxidation Inhibitor And the like. The usage-amount of auxiliary agent can be suitably set from a wide range.
本発明において、アンカー層、感熱記録層及び保護層を形成する方法としては、特に制限されず、エアナイフ法、ブレード法、グラビア法、ロールコーター法、カーテン法、スプレー法、ディップ法、バー法、エクストルージョン法等の既知の塗布方法を採用することができる。本発明では、各層を形成し終えた後、または特定の層を形成し終えた後の任意の過程でスーパーカレンダーによる平滑化処理を施すことができる。 In the present invention, the method for forming the anchor layer, the thermosensitive recording layer, and the protective layer is not particularly limited, and air knife method, blade method, gravure method, roll coater method, curtain method, spray method, dip method, bar method, A known coating method such as an extrusion method can be employed. In the present invention, a smoothing process using a super calendar can be performed in an arbitrary process after the formation of each layer or after the formation of a specific layer.
本発明では、少なくとも感熱記録層がカーテン塗布法により形成された層であることが好ましい。カーテン塗布法における塗液は、カーテン膜の安定性を高めるために低粘度に調整される。低粘度の感熱記録層用塗液は、アンカー層に浸透し易く、均一な塗膜を形成し難い。本発明におけるアンカー層は、バリア性に優れるため、このような浸透を抑えることができ、カーテン塗布法において効果を遺憾なく発揮するものである。 In the present invention, it is preferable that at least the heat-sensitive recording layer is a layer formed by a curtain coating method. The coating liquid in the curtain coating method is adjusted to a low viscosity in order to enhance the stability of the curtain film. The low-viscosity coating solution for heat-sensitive recording layer easily penetrates into the anchor layer, and it is difficult to form a uniform coating film. Since the anchor layer in the present invention is excellent in barrier properties, such penetration can be suppressed, and the effect is fully exhibited in the curtain coating method.
また、感熱記録層と保護層は、同時多層カーテン塗布法により形成された層であることがより好ましい。これにより、層間混合を防止して保護層のバリア性を著しく向上でき、生産効率を高め、製造時の消費エネルギーをより低減させることができる。同時多層カーテン塗布法は、各層を形成する塗液を積層した後、塗布し、その後、乾燥させて各層を形成してもよいし、下層を形成する下層用塗液を塗布した後、乾燥することなく下層塗布面が湿潤状態のうちに、下層塗布面上に上層を形成する上層用塗液を塗布し、その後、乾燥させて各層を形成してもよい。 The heat-sensitive recording layer and the protective layer are more preferably layers formed by a simultaneous multilayer curtain coating method. Thereby, interlayer mixing can be prevented and the barrier property of the protective layer can be remarkably improved, production efficiency can be increased, and energy consumption during production can be further reduced. In the simultaneous multilayer curtain coating method, the coating liquid for forming each layer is laminated and then applied, and then dried to form each layer, or the lower layer coating liquid for forming the lower layer is applied and then dried. Alternatively, while the lower layer coating surface is wet, an upper layer coating solution for forming an upper layer may be applied on the lower layer coating surface and then dried to form each layer.
カーテン塗布法とは、塗液の自由落下カーテン膜を形成し、塗液を走行する支持体に衝突させて塗布する方法である。具体的には、スライドカーテン塗布法、カップルカーテン塗布法、ツインカーテン塗布法等の公知のものを採用することができ、特に制限されるものではない。また、例えば、カーテンヘッドから塗液を下向きに噴出させて斜面上で塗液層を形成させ、斜面の終端部の下向きのカーテンガイド部から塗液のカーテンを形成して支持体上に塗液層を移行させる多段式カーテンコーターによる方法も採用できる。多段式カーテンコーターによる方法としては、特開2006−247611号公報に記載された方法が挙げられる。 The curtain coating method is a method in which a free-falling curtain film of a coating liquid is formed, and the coating liquid is applied by colliding with a support that travels. Specifically, known methods such as a slide curtain coating method, a couple curtain coating method, a twin curtain coating method, and the like can be employed, and are not particularly limited. Further, for example, the coating liquid is ejected downward from the curtain head to form a coating liquid layer on the slope, and a coating liquid curtain is formed from the downward curtain guide portion at the end of the slope to form the coating liquid on the support. A method using a multi-stage curtain coater for transferring the layers can also be adopted. Examples of the method using a multistage curtain coater include the method described in JP-A-2006-247611.
なお、塗液濃度、塗布速度、カーテン膜幅、落下角度等の諸条件は、各々のカーテン塗布法及び塗布装置に合わせ、適宜調整して行うことが望ましい。これらのカーテン塗布法は、非接触方式の輪郭塗工であるため、均一な厚さの層を得ることができる。一方、ブレード塗布法、バー塗布法、ロッド塗布法等の接触方式の塗布法では、支持体の表面性(凹凸)の影響を受けるため、膜厚が不均一となる。このため、同一塗布量では、カーテン塗布法で形成された感熱記録層の方が記録感度を向上でき、良好な画質を得ることができるうえ、より少ない塗布量で記録画像の保存性を向上することもできる。 It should be noted that various conditions such as coating solution concentration, coating speed, curtain film width, and drop angle are desirably adjusted as appropriate in accordance with each curtain coating method and coating apparatus. Since these curtain coating methods are non-contact contour coating, a layer having a uniform thickness can be obtained. On the other hand, a contact coating method such as a blade coating method, a bar coating method, or a rod coating method is affected by the surface properties (unevenness) of the support, and therefore the film thickness becomes non-uniform. For this reason, with the same coating amount, the thermal recording layer formed by the curtain coating method can improve the recording sensitivity, obtain a good image quality, and improve the storability of the recorded image with a smaller coating amount. You can also.
カーテン塗布法に用いる塗布装置としては、特に限定されないが、エクストルージョンホッパー型カーテン塗布装置、スライドホッパー型カーテン塗布装置、あるいは前述の特開2006−247611号公報に記載の多段式カーテンコーター等が挙げられる。 The coating apparatus used in the curtain coating method is not particularly limited, and examples thereof include an extrusion hopper type curtain coating apparatus, a slide hopper type curtain coating apparatus, or the multistage curtain coater described in Japanese Patent Application Laid-Open No. 2006-247611. It is done.
本発明における支持体は、紙支持体よりなる。紙支持体としては、特に制限されず、例えば、上質紙(酸性紙、中性紙)、中質紙、コート紙、アート紙、キャストコート紙等の紙類が挙げられる。また、支持体を構成する繊維としては、広葉樹パルプ、針葉樹パルプのいずれも使用できる。かかるパルプとしては、例えば、LBKP、NBKP等の化学パルプ、GP、TMP等の機械パルプ、DIP等の古紙パルプが挙げられる。必要に応じてガラス繊維、各種合成パルプを併用することもできる。 The support in the present invention is a paper support. The paper support is not particularly limited, and examples thereof include high-quality paper (acidic paper, neutral paper), medium-quality paper, coated paper, art paper, cast-coated paper, and the like. Moreover, as a fiber which comprises a support body, both hardwood pulp and conifer pulp can be used. Examples of such pulp include chemical pulp such as LBKP and NBKP, mechanical pulp such as GP and TMP, and waste paper pulp such as DIP. If necessary, glass fiber and various synthetic pulps can be used in combination.
本発明では、支持体表面のマイクロトポグラフによる20kg/cm2加圧下での表面粗さが6μm以上である支持体において、より印字品質の向上効果がみられ、好ましい。本発明におけるアンカー層と下塗り層を備えることにより、感熱記録層の被覆性が向上し、表面粗さが6μm以上、より好ましくは8μm以上、更に好ましくは10μm以上の粗い表面を有する支持体であっても記録発色性と記録画質を高めることができる。一方、表面粗さを15μm以下程度とすることにより、十分な記録性能を得ることができる。ここで、表面粗さは、東洋精機製作所製の表面試験機「マイクロトポグラフ」により、5.5cm径の加圧接触子を用いて、接触時間990msの条件で、5箇所の測定値から最大値及び最小値を除いた3箇所の平均値を求めたものである。 In the present invention, a support having a surface roughness of 6 μm or more under a pressure of 20 kg / cm 2 by microtopography on the surface of the support is preferable because the effect of improving the printing quality is further observed. By providing the anchor layer and the undercoat layer in the present invention, the coverage of the thermosensitive recording layer is improved, and the support has a rough surface with a surface roughness of 6 μm or more, more preferably 8 μm or more, and even more preferably 10 μm or more. However, it is possible to improve recording color development and recording image quality. On the other hand, when the surface roughness is about 15 μm or less, sufficient recording performance can be obtained. Here, the surface roughness is the maximum value from the measured values at five locations using a surface contactor “Microtopograph” manufactured by Toyo Seiki Seisakusho using a 5.5 cm diameter pressure contact with a contact time of 990 ms. And the average value of three locations excluding the minimum value.
本発明では、支持体のステキヒトサイズ度が15秒以下であることが好ましい。より好ましくは10秒以下である。本発明におけるアンカー層を備えることにより、支持体中への塗液の浸透を抑えて、均一な感熱記録層を形成することができ、サイズ度の低い支持体であっても記録発色性と記録画質を高めることができる。ステキヒトサイズ度の下限としては、特に制限されないが、アンカー層の
形成に際して塗液の塗布適性を向上する観点から1秒以上が好ましく、5秒以上がより好ましい。なお、ステキヒトサイズ度は、JIS P 8122に準じて測定される。なお、支持体の坪量としては、特に制限されないが、40〜70g/m2程度が好ましい。
In the present invention, it is preferred that the support has a sizing degree of 15 seconds or less. More preferably, it is 10 seconds or less. By providing the anchor layer in the present invention, it is possible to suppress the penetration of the coating liquid into the support and to form a uniform heat-sensitive recording layer. The image quality can be improved. The lower limit of the Steecht sizing degree is not particularly limited, but is preferably 1 second or longer and more preferably 5 seconds or longer from the viewpoint of improving the coating suitability of the coating liquid when forming the anchor layer. Note that the degree of steechtite is measured according to JIS P 8122. As the basis weight of the support is not particularly limited, about 40~70g / m 2 is preferred.
本発明では、感熱記録層とは反対側の支持体上に粘着剤層を備えた感熱記録体として好適に用いることができる。本発明に使用される粘着剤としては、例えば、天然ゴム、スチレン−ブタジエンゴム、ポリイソブチレンゴム、イソプレンゴム等によるゴム系物質を主成分とするもの、ビニルエーテル系物質を主成分とするもの、2−エチルヘキシルアクリレートを主モノマーとする共重合ポリマー等のアクリル系物質を主成分とするもの、ゴム状シロキサンと樹脂状シロキサンとを主成分とするもの等が挙げられる。これらは、エマルジョン、溶剤、または無溶剤型の各種粘着剤として用いることができる。粘着剤成分として可塑剤や乳化剤を含有することができる。 In this invention, it can use suitably as a thermal recording body provided with the adhesive layer on the support body on the opposite side to a thermal recording layer. Examples of the pressure-sensitive adhesive used in the present invention include those mainly composed of rubber-based materials such as natural rubber, styrene-butadiene rubber, polyisobutylene rubber, and isoprene rubber, and those mainly composed of vinyl ether-based materials. -The thing which has acrylic materials, such as a copolymer polymer which has ethylhexyl acrylate as a main monomer, as a main component, and the thing which has rubbery siloxane and resinous siloxane as a main component are mentioned. These can be used as various adhesives of emulsion, solvent, or solventless type. A plasticizer and an emulsifier can be contained as an adhesive component.
剥離シートを用いる場合、粘着剤は、支持体上に直接塗布して粘着剤層を設けてもよいし、剥離シートの剥離剤表面に粘着剤を塗布して粘着剤層を設けた後、支持体の感熱記録層とは反対側に貼着し、粘着剤層を転写して設けてもよい。いずれも場合も、粘着剤層は使用時以外での不要な粘着を防ぐために剥離シートを貼合し、所望により剥がして使用することが望ましい。一方、剥離シートを用いないノーセパレートタイプにおいては、感熱記録層と粘着剤層とが、それらの間に離形層等を挟んで積層されており、巻き取り状態で支持体と粘着剤層とが接触して粘着剤成分の影響が及ぶため、本発明の効果を遺憾なく発揮させることができる。 When using a release sheet, the adhesive may be applied directly on the support to provide an adhesive layer, or the adhesive is applied to the release sheet surface of the release sheet to provide an adhesive layer, and then supported. It may be attached to the opposite side of the body to the thermosensitive recording layer, and the adhesive layer may be transferred and provided. In either case, it is desirable that the pressure-sensitive adhesive layer is used by sticking a release sheet and peeling it off as desired in order to prevent unnecessary adhesion except during use. On the other hand, in the no-separate type that does not use a release sheet, the heat-sensitive recording layer and the pressure-sensitive adhesive layer are laminated with a release layer or the like sandwiched between them, and the support and the pressure-sensitive adhesive layer are wound in a wound state. The effect of the present invention can be exhibited without regret because the pressure-sensitive adhesive component is affected by contact.
剥離シートとしては、グラシン紙のような高密度原紙、クレーコート紙、クラフト紙や、または上質紙等にポリエチレン等をラミネートしたポリラミネート紙等の剥離基紙に、剥離剤としてフッ素樹脂やシリコーン樹脂等が乾燥重量で0.05〜3g/m2程度の範囲で付着された剥離面を有するものが好ましい。粘着剤の塗布方法としては、例えばロールコーター、ナイフコーター、バーコーター、スロットダイコーター等が使用され、塗布量は、乾燥重量で5〜50g/m2程度の範囲で調節される。 The release sheet is a high-density base paper such as glassine paper, clay-coated paper, kraft paper, or release base paper such as polylaminate paper in which polyethylene is laminated on high-quality paper, etc., and fluorine resin or silicone resin as a release agent And the like having a peel surface attached in a range of about 0.05 to 3 g / m 2 by dry weight. For example, a roll coater, a knife coater, a bar coater, a slot die coater or the like is used as a method for applying the pressure-sensitive adhesive, and the coating amount is adjusted in a range of about 5 to 50 g / m 2 in terms of dry weight.
以下に実施例を挙げて具体的に説明するが、本発明はこれらに制限されるものではない。なお、例中の「部」及び「%」は、特に断らない限り「質量部」及び「質量%」を示す。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In the examples, “parts” and “%” indicate “parts by mass” and “% by mass” unless otherwise specified.
実施例及び比較例で使用した分散液の平均粒子径は、レーザー回折式粒度分布測定装置SALD2200(島津製作所社製)によってメジアン径を測定した。 The average particle diameter of the dispersions used in Examples and Comparative Examples was measured by a median diameter using a laser diffraction particle size distribution analyzer SALD2200 (manufactured by Shimadzu Corporation).
実施例1
・アンカー層用塗液の調製
焼成カオリン(商品名:アンシレックス93、BASF社製)の50%水分散液130部、プラスチック中空粒子分散液(商品名:ローペイクSN−1055、中空率:55%、平均粒子径1.0μm、ダウコーティングマテリアルズ社製、固形分濃度26.5%)48部、スチレン−ブタジエン系ラテックス(商品名:L−1571、旭化成ケミカルズ社製、固形分濃度48%)29部、スチレン−アクリル系エマルジョン型サイズ剤(商品名:ポリマロンE−100、荒川化学工業社製、固形分濃度30%)12.8部、カルボキシメチルセルロース(商品名:セロゲンAGガム、第一工業製薬社製)2.3部、ジオクチルスルホコハク酸ナトリウム塩(商品名:SNウェットOT−70、サンノプコ社製)の10%水溶液0.2部、天然油脂系消泡剤(商品名:ノプコ1407H、サンノプコ社製)の5%エマルジョン1部、炭酸ジルコニウムアンモニウム塩(商品名:ベイコート20、日本軽金属社製)の45%水溶液4部、及び水73部からなる組成物を混合攪拌し、アンカー層用塗液を得た。
Example 1
-Preparation of coating solution for anchor layer 130 parts of 50% aqueous dispersion of calcined kaolin (trade name: Ansilex 93, manufactured by BASF), plastic hollow particle dispersion (trade name: Ropaque SN-1055, hollow ratio: 55% , 48 parts by average particle size, 1.0 μm, manufactured by Dow Coating Materials, solid content concentration 26.5%), styrene-butadiene latex (trade name: L-1571, manufactured by Asahi Kasei Chemicals, solid content concentration 48%) 29 parts, 12.8 parts of styrene-acrylic emulsion type sizing agent (trade name: POLYMALON E-100, manufactured by Arakawa Chemical Industry Co., Ltd., solid content concentration 30%), carboxymethyl cellulose (trade name: Serogen AG gum, Daiichi Kogyo) 2.3 parts of dioctyl sulfosuccinic acid sodium salt (trade name: SN wet OT-70, manufactured by San Nopco) 0.2 part of 0% aqueous solution, 1 part of 5% emulsion of natural oil and fat-based antifoaming agent (trade name: Nopco 1407H, manufactured by San Nopco), 45 parts of ammonium zirconium carbonate (trade name: Baycoat 20, manufactured by Nippon Light Metal Co., Ltd.) A composition comprising 4 parts of a% aqueous solution and 73 parts of water was mixed and stirred to obtain an anchor layer coating solution.
・A液調製(ロイコ染料分散液の調製)
3−ジ(n−ブチル)−6−メチル−7−アニリノフルオラン100部、スルホン変性ポリビニルアルコール(商品名:ゴーセランL−3266、日本合成化学社製)の20%水溶液50部、天然油脂系消泡剤(商品名:ノプコ1407H、前出)の5%エマルジョン10部、及び水90部からなる組成物を、サンドミルで平均粒子径が0.5μmとなるまで粉砕してA液を得た。
-Solution A preparation (preparation of leuco dye dispersion)
100 parts of 3-di (n-butyl) -6-methyl-7-anilinofluorane, 50 parts of a 20% aqueous solution of sulfone-modified polyvinyl alcohol (trade name: Gocelan L-3266, manufactured by Nippon Synthetic Chemical Co., Ltd.), natural fats and oils A composition comprising 10 parts of a 5% emulsion of a series antifoaming agent (trade name: Nopco 1407H, supra) and 90 parts of water is pulverized with a sand mill until the average particle size becomes 0.5 μm to obtain liquid A It was.
・B液調製(呈色剤分散液の調製)
4,4’−ジヒドロキシジフェニルスルホン100部、スルホン変性ポリビニルアルコール(商品名:ゴーセランL−3266、前出)の20%水溶液50部、天然油脂系消泡剤(商品名:ノプコ1407H、前出)の5%エマルジョン10部、及び水90部からなる組成物を、サンドミルで平均粒子径が1.0μmとなるまで粉砕してB液を得た。
・ B liquid preparation (preparation of colorant dispersion)
100 parts of 4,4′-dihydroxydiphenylsulfone, 50 parts of a 20% aqueous solution of sulfone-modified polyvinyl alcohol (trade name: Gocelan L-3266, supra), natural fat-based antifoaming agent (trade name: Nopco 1407H, supra) A composition comprising 10 parts of a 5% emulsion and 90 parts of water was pulverized with a sand mill until the average particle size became 1.0 μm to obtain a liquid B.
・C液調製(増感剤分散液の調製)
ジフェニルスルホン100部、スルホン変性ポリビニルアルコール(商品名:ゴーセランL−3266、前出)の20%水溶液50部、天然油脂系消泡剤(商品名:ノプコ1407H、前出)の5%エマルジョン10部、及び水90部からなる組成物を、サンドミルで平均粒子径が1.0μmとなるまで粉砕してC液を得た。
・ C liquid preparation (preparation of sensitizer dispersion)
100 parts of diphenylsulfone, 50 parts of a 20% aqueous solution of sulfone-modified polyvinyl alcohol (trade name: Gocelan L-3266, supra), 10 parts of a 5% emulsion of a natural fat-based antifoaming agent (trade name: Nopco 1407H, supra) And the composition which consists of 90 parts of water was grind | pulverized until the average particle diameter was set to 1.0 micrometer with the sand mill, and C liquid was obtained.
・D液調製(保存性改良剤分散液の調製)
4,4’−ビス[(4−メチル−3−フェノキシカルボニルアミノフェニル)ウレイド]ジフェニルスルホン100部、珪酸マグネシウム5部、スルホン変性ポリビニルアルコール(商品名:ゴーセランL−3266、前出)の20%水溶液50部、天然油脂系消泡剤(商品名:ノプコ1407H、前出)の5%エマルジョン10部、及び水90部からなる組成物を、サンドミルで平均粒子径が1.0μmとなるまで粉砕してD液を得た。
・ D liquid preparation (preparation of preservative improver dispersion)
4,4′-bis [(4-methyl-3-phenoxycarbonylaminophenyl) ureido] diphenylsulfone 100 parts, magnesium silicate 5 parts, sulfone-modified polyvinyl alcohol (trade name: Gocelan L-3266, supra) A composition comprising 50 parts of an aqueous solution, 10 parts of a 5% emulsion of a natural fat / oil defoaming agent (trade name: Nopco 1407H, supra) and 90 parts of water is pulverized with a sand mill until the average particle size becomes 1.0 μm. As a result, liquid D was obtained.
・感熱記録層用塗液の調製
A液38部、B液106部、C液30部、D液11部、カオリン(商品名:HG90、KaMin LLC社製)の50%水分散液11部、軽質炭酸カルシウム(商品名:ブリリアントS−15、白石工業社製)の60%水分散液6部、ポリビニルアルコール(PVA−124、クラレ社製、重合度2400)の8%水溶液42部、スチレン−ブタジエン系ラテックス(商品名:L−1571、前出)3.9部、アジピン酸ジヒドラジドの35%水分散液7.5部、ジオクチルスルホコハク酸ナトリウム塩(商品名:SNウェットOT−70、前出)の10%水溶液2.6部、天然油脂系消泡剤(商品名:ノプコ1407H、前出)の5%エマルジョン1.4部、及び水70部からなる組成物を混合撹拌して感熱記録層用塗液を得た。
-Preparation of coating solution for heat-sensitive recording layer A part 38 parts, B part 106 parts, C part 30 parts, D part 11 parts, kaolin (trade name: HG90, manufactured by KaMin LLC) 11 parts, 6 parts of 60% aqueous dispersion of light calcium carbonate (trade name: Brilliant S-15, manufactured by Shiraishi Kogyo Co., Ltd.), 42 parts of 8% aqueous solution of polyvinyl alcohol (PVA-124, manufactured by Kuraray Co., Ltd., degree of polymerization 2400), styrene Butadiene latex (trade name: L-1571, supra) 3.9 parts, adipic acid dihydrazide 35% aqueous dispersion 7.5 parts, dioctylsulfosuccinate sodium salt (trade name: SN wet OT-70, supra) ), A composition consisting of 2.6 parts of a 10% aqueous solution of oil, 1.4 parts of a 5% emulsion of a natural oil and fat antifoaming agent (trade name: Nopco 1407H, supra), and 70 parts of water. To obtain a layer coating solution.
・保護層用塗液の調製
カオリン(商品名:HG90、前出)の50%水分散液108部、水酸化アルミニウム(商品名:ハイジライトH−42、昭和電工社製)7.4部、ジアセトン変性ポリビニルアルコール(商品名:DF−20、日本酢ビ・ポバール社製、重合度2000)の10%水溶液270部、ポリビニルアルコール(商品名:JC−40、日本酢ビ・ポバール社製、重合度4000)の6%水溶液112部、ステアリン酸亜鉛の水分散物(商品名:ハイドリンZ−8−36、固形分濃度36%、中京油脂社製)4.7部、ポリエチレンディスパージョン(商品名:ケミパールW400、三井化学社製、固形分濃度40%)2.6部、疎水性ポリカルボン酸共重合体のアンモニウム塩(商品名:オロタン165A、ダウコーティングマテリアルズ社製、固形分濃度21.8%)、ジオクチルスルホコハク酸ナトリウム塩(商品名:SNウェットOT−70、前出)の10%水溶液1.1部、及び天然油脂系消泡剤(商品名:ノプコ1407H、前出)の5%エマルジョン20部を混合攪拌して保護層用塗液を得た。
-Preparation of coating solution for protective layer 108 parts of kaolin (trade name: HG90, supra) 50% aqueous dispersion, 7.4 parts of aluminum hydroxide (trade name: Heidilite H-42, Showa Denko) 270 parts of a 10% aqueous solution of diacetone-modified polyvinyl alcohol (trade name: DF-20, manufactured by Nihon Acetate / Poval, degree of polymerization 2000), polyvinyl alcohol (trade name: JC-40, manufactured by Nihon Acetate / Poval, polymerized) 112 parts of a 6% aqueous solution having a degree of 4000), an aqueous dispersion of zinc stearate (trade name: Hydrin Z-8-36, solid content concentration 36%, manufactured by Chukyo Yushi Co., Ltd.), polyethylene dispersion (trade name) : Chemipearl W400, manufactured by Mitsui Chemicals, solid concentration 40%) 2.6 parts, ammonium salt of hydrophobic polycarboxylic acid copolymer (trade name: Orotan 165A, Dow Cotin Gmaterials, solid concentration 21.8%), dioctylsulfosuccinate sodium salt (trade name: SN Wet OT-70, supra) 1.1 parts of 10% aqueous solution, and natural fat and oil defoamer ( 20 parts of a 5% emulsion (trade name: Nopco 1407H, supra) was mixed and stirred to obtain a coating solution for a protective layer.
・感熱記録体の作製
坪量50g/m2、マイクロトポグラフによる20kg/cm2加圧下での表面粗さが8μmの紙支持体上に、乾燥後の塗布量が6.0g/m2となるようにアンカー層用塗液を塗布及び乾燥してアンカー層を形成した。得られたアンカー層上に乾燥後の塗布量が3.0g/m2となるように感熱記録層用塗液を塗布及び乾燥して感熱記録層を形成した。更に感熱記録層上に乾燥後の塗布量が2.5g/m2となるように保護層用塗液を塗布及び乾燥して保護層を形成した。その後、線圧78N/mの加圧条件でスーパーカレンダーによって平滑化処理し、感熱記録体を得た。なお、支持体のステキヒトサイズ度は、10秒であった。
-Preparation of thermosensitive recording material On a paper support having a basis weight of 50 g / m 2 and a surface roughness of 8 μm under pressure of 20 kg / cm 2 by microtopography, the coating amount after drying becomes 6.0 g / m 2. Thus, the anchor layer coating solution was applied and dried to form an anchor layer. A heat sensitive recording layer was formed by applying and drying a heat sensitive recording layer coating solution on the resulting anchor layer so that the coating amount after drying was 3.0 g / m 2 . Further, a protective layer was formed by applying and drying a protective layer coating solution on the heat-sensitive recording layer so that the coating amount after drying was 2.5 g / m 2 . Thereafter, smoothing was performed with a super calender under a pressure condition of linear pressure of 78 N / m to obtain a heat-sensitive recording material. In addition, the steadiness sizing degree of the support was 10 seconds.
実施例2
実施例1のアンカー層用塗液の調製において、焼成カオリンの量を130部に代えて155部とし、プラスチック中空粒子分散液を用いなかった以外は、実施例1と同様にして感熱記録体を得た。
Example 2
In the preparation of the anchor layer coating liquid of Example 1, the amount of calcined kaolin was changed to 155 parts instead of 130 parts, and the thermosensitive recording medium was prepared in the same manner as in Example 1 except that the plastic hollow particle dispersion was not used. Obtained.
実施例3
実施例1のアンカー層用塗液の調製において、焼成カオリンの量を130部に代えて62部とし、プラスチック中空粒子分散液の量を48部に代えて176部とした以外は、実施例1と同様にして感熱記録体を得た。
Example 3
Example 1 except that the amount of calcined kaolin was 62 parts instead of 130 parts and the amount of plastic hollow particle dispersion was 176 parts instead of 48 parts in the preparation of the anchor layer coating liquid of Example 1. In the same manner, a heat-sensitive recording material was obtained.
実施例4
実施例1のアンカー層用塗液の調製において、スチレン−アクリル系エマルジョン型サイズ剤の量を12.8部に代えて3.3部とした以外は、実施例1と同様にして感熱記録体を得た。
Example 4
In the preparation of the anchor layer coating liquid of Example 1, the heat-sensitive recording material was the same as Example 1 except that the amount of the styrene-acrylic emulsion type sizing agent was changed to 3.3 parts instead of 12.8 parts. Got.
実施例5
実施例1のアンカー層用塗液の調製において、スチレン−アクリル系エマルジョン型サイズ剤の量を12.8部に代えて30部とした以外は、実施例1と同様にして感熱記録体を得た。
Example 5
A thermosensitive recording material was obtained in the same manner as in Example 1 except that in the preparation of the anchor layer coating liquid of Example 1, the amount of the styrene-acrylic emulsion type sizing agent was changed to 30 parts instead of 12.8 parts. It was.
実施例6
実施例1の感熱記録体の作製において、坪量50g/m2、マイクロトポグラフによる20kg/cm2加圧下での表面粗さが8μmの紙支持体に代えて、坪量50g/m2、マイクロトポグラフによる20kg/cm2加圧下での表面粗さが15μmの紙支持体を用いた以外は、実施例1と同様にして感熱記録体を得た。なお、支持体のステキヒトサイズ度は、7秒であった。
Example 6
In the production of the heat-sensitive recording material of Example 1, the basis weight was 50 g / m 2 , the surface roughness under pressure of 20 kg / cm 2 by microtopography was 8 μm, and the basis weight was 50 g / m 2 . A heat-sensitive recording material was obtained in the same manner as in Example 1 except that a paper support having a surface roughness of 15 μm under a pressure of 20 kg / cm 2 by a topograph was used. In addition, the steadiness sizing degree of the support was 7 seconds.
実施例7
実施例1のアンカー層用塗液の調製において、スチレン−アクリル系エマルジョン型サイズ剤に代えて、スチレン−マレイン酸共重合体アンモニウム塩(商品名:ポリマロン385、荒川化学工業社製、固形分濃度25%)を用いた以外は、実施例1と同様にして感熱記録体を得た。
Example 7
In the preparation of the anchor layer coating liquid of Example 1, instead of the styrene-acrylic emulsion type sizing agent, a styrene-maleic acid copolymer ammonium salt (trade name: Polymeron 385, manufactured by Arakawa Chemical Industries, Ltd., solid content concentration) A heat-sensitive recording material was obtained in the same manner as in Example 1 except that 25%) was used.
実施例8
実施例1のアンカー層用塗液の調製において、焼成カオリンの量を130部に代えて110部とし、プラスチック中空粒子分散液の量を48部に代えて90部とした以外は、実施例1と同様にして感熱記録体を得た。
Example 8
Example 1 except that the amount of calcined kaolin was 110 parts instead of 130 parts and the amount of the plastic hollow particle dispersion was 90 parts instead of 48 parts in the preparation of the anchor layer coating liquid of Example 1. In the same manner, a heat-sensitive recording material was obtained.
実施例9
実施例1のアンカー層用塗液の調製において、炭酸ジルコニウムアンモニウム塩の45%水溶液4部に代えて、ジメチロールウレア化合物(商品名:Texapret R−S、BASF社製、固形分濃度100%)1.8部を用いた以外は、実施例1と同様にして感熱記録体を得た。
Example 9
In the preparation of the coating solution for anchor layer of Example 1, instead of 4 parts of 45% aqueous solution of zirconium carbonate ammonium salt, a dimethylol urea compound (trade name: Texapret RS, manufactured by BASF, solid content concentration 100%) A heat-sensitive recording material was obtained in the same manner as in Example 1 except that 1.8 parts was used.
比較例1
実施例1のアンカー層用塗液の調製において、スチレン−アクリル系エマルジョン型サイズ剤を用いなかった以外は、実施例1と同様にして感熱記録体を得た。
Comparative Example 1
A thermosensitive recording material was obtained in the same manner as in Example 1 except that the styrene-acrylic emulsion type sizing agent was not used in the preparation of the anchor layer coating solution of Example 1.
かくして得られた感熱記録体について、以下の評価を行なった。その結果は、表1に示す通りであった。 The thermosensitive recording material thus obtained was evaluated as follows. The results were as shown in Table 1.
(記録性能1:発色性)
ラベルプリンタ(商品名:L−2000、株式会社イシダ製)を用いて市松パターンを記録し、記録部の反射濃度(記録濃度)を分光測色型光学濃度計(商品名:X−rite 939型、X−rite社製)にて測定した。数値が大きい程、印字濃度が濃いことを示して好ましく、記録部については、実用上、1.20以上であることが好ましい。
(Recording performance 1: color development)
A checkered pattern is recorded using a label printer (trade name: L-2000, manufactured by Ishida Co., Ltd.), and the reflection density (recording density) of the recording portion is measured by a spectrophotometric optical densitometer (trade name: X-rite 939 type). , Manufactured by X-rite). It is preferable that the numerical value is large, indicating that the print density is high, and the recording portion is preferably 1.20 or more in practical use.
(記録性能1:画質1)
ラベルプリンタ(商品名:L−2000、株式会社イシダ製)を用いてバーコードを記録し、その記録画質を目視で観察し、下記の基準で評価した。
○:画質の白抜けやバーコードの太りがなく、全く問題ない。
△:画質の白抜けやバーコードの太りがほとんどなく、実用上問題ない。
×:画像の白抜けやバーコードの太りがあり、実用上問題となる。
(Recording performance 1: Image quality 1)
A bar code was recorded using a label printer (trade name: L-2000, manufactured by Ishida Co., Ltd.), the recorded image quality was visually observed, and evaluated according to the following criteria.
○: There are no white spots in the image quality and no thickening of the barcode, and there is no problem at all.
(Triangle | delta): There is almost no whiteness of image quality and the thickness of a barcode, and there is no problem practically.
X: There are white spots in the image and the barcode is thick, which is a practical problem.
(記録性能2:発色性) (Recording performance 2: color development)
各感熱記録体の感熱記録層とは反対側(裏面)の支持体上に、アクリル樹脂系粘着剤を20g/m2塗布して粘着剤層を設け、粘着剤層上に上質系剥離シートを貼り合わせて感熱記録ラベル加工(糊加工)を行った。更に糊減感を評価する加速試験として40℃,90%RH環境下に7日間保存した後、記録性能1と同様の方法により記録濃度を測定した。更に次式により印字再現率を求め、下記の基準で記録性能を評価した。ここで、「ラベル加工前の記録濃度」とは、前記「記録性能1:発色性」で得られた値である。
印字再現率(%)=(ラベル加工後に保存した後の記録濃度/ラベル加工前の記録濃度)×100
○:印字再現率が85%以上であれば全く問題ない。
△:印字再現率が70%以上85%未満であれば実用上問題ない。
×:印字再現率が70%未満であれば実用上問題となる。
An acrylic resin-based adhesive is applied at 20 g / m 2 on the support on the opposite side (back side) of the thermal recording layer of each thermal recording body to provide an adhesive layer, and a high-quality release sheet is provided on the adhesive layer. The heat-sensitive recording label processing (glue processing) was performed by bonding. Further, as an accelerated test for evaluating the desensitization, the film was stored in an environment of 40 ° C. and 90% RH for 7 days, and then the recording density was measured by the same method as in the recording performance 1. Further, the print reproducibility was obtained by the following formula, and the recording performance was evaluated according to the following criteria. Here, “recording density before label processing” is a value obtained by the above “recording performance 1: color development”.
Print reproducibility (%) = (recording density after storage after label processing / recording density before label processing) × 100
A: No problem at all if the print reproduction rate is 85% or more.
(Triangle | delta): If a printing reproduction rate is 70% or more and less than 85%, there is no problem practically.
X: If the print reproducibility is less than 70%, there is a practical problem.
(記録性能2:画質)
前記「記録性能2:発色性」と同様の方法によりラベル加工後に保存した後、前記「記録性能1:画質1」と同様の方法により評価した。
(Recording performance 2: Image quality)
After the label processing by the method similar to the “recording performance 2: color developability”, the image was stored and then evaluated by the method similar to the “recording performance 1: image quality 1”.
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EP14851026.6A EP3053753B1 (en) | 2013-10-04 | 2014-09-30 | Thermosensitive recording material |
US15/026,065 US9962980B2 (en) | 2013-10-04 | 2014-09-30 | Thermosensitive recording material |
CN201480053146.0A CN105579241B (en) | 2013-10-04 | 2014-09-30 | Thermosensitive recording body |
PCT/JP2014/075989 WO2015050098A1 (en) | 2013-10-04 | 2014-09-30 | Heat-sensitive recording material |
BR112016006417-8A BR112016006417B1 (en) | 2013-10-04 | 2014-09-30 | Thermosensitive recording material |
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