JPH03193387A - Thermal recording body - Google Patents
Thermal recording bodyInfo
- Publication number
- JPH03193387A JPH03193387A JP1334273A JP33427389A JPH03193387A JP H03193387 A JPH03193387 A JP H03193387A JP 1334273 A JP1334273 A JP 1334273A JP 33427389 A JP33427389 A JP 33427389A JP H03193387 A JPH03193387 A JP H03193387A
- Authority
- JP
- Japan
- Prior art keywords
- pigment
- heat
- particle size
- sensitive recording
- primary particles
- 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.)
- Pending
Links
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- JJXVDRYFBGDXOU-UHFFFAOYSA-N dimethyl 4-hydroxybenzene-1,2-dicarboxylate Chemical compound COC(=O)C1=CC=C(O)C=C1C(=O)OC JJXVDRYFBGDXOU-UHFFFAOYSA-N 0.000 description 2
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- 229920000881 Modified starch Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ZKURGBYDCVNWKH-UHFFFAOYSA-N [3,7-bis(dimethylamino)phenothiazin-10-yl]-phenylmethanone Chemical compound C12=CC=C(N(C)C)C=C2SC2=CC(N(C)C)=CC=C2N1C(=O)C1=CC=CC=C1 ZKURGBYDCVNWKH-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 1
- 229920006222 acrylic ester polymer Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical class CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical group C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000314 lubricant 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
- 238000012423 maintenance Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 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
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
- 229960000990 monobenzone Drugs 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- MGNPLIACIXIYJE-UHFFFAOYSA-N n-fluoroaniline Chemical compound FNC1=CC=CC=C1 MGNPLIACIXIYJE-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- ZNSSPLQZSUWFJT-UHFFFAOYSA-N pentyl 4-hydroxybenzoate Chemical compound CCCCCOC(=O)C1=CC=C(O)C=C1 ZNSSPLQZSUWFJT-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 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
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229960003415 propylparaben Drugs 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003457 sulfones Chemical group 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000001016 thiazine dye Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- MLVWCBYTEFCFSG-UHFFFAOYSA-L zinc;dithiocyanate Chemical compound [Zn+2].[S-]C#N.[S-]C#N MLVWCBYTEFCFSG-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
【発明の詳細な説明】
「産業上の利用分野」
本発明はオーバーコート層を有する感熱記録体に関し、
特に捺印適性や筆記通性等に優れた感熱記録体に関する
ものである。Detailed Description of the Invention "Industrial Application Field" The present invention relates to a heat-sensitive recording material having an overcoat layer,
In particular, it relates to a heat-sensitive recording medium that is excellent in imprintability, writing ability, etc.
「従来の技術」
従来、無色ないしは淡色の塩基性染料と該塩基性染料と
接触して呈色する呈色剤との呈色反応を利用し、熱によ
り両光色物質を接触せしめて発色像を得るようにした感
熱記録体はよく知られている。``Prior art'' Conventionally, a coloring reaction between a colorless or light-colored basic dye and a coloring agent that develops color when it comes into contact with the basic dye is used to create a colored image by bringing both photochromic substances into contact with each other using heat. Thermosensitive recording materials designed to obtain the following are well known.
かかる感熱記録体は比較的安価であり、記録機器がコン
パクトで且つその保守も比較的容易である為、ファクシ
ミリや各種計算機等の記録媒体としてのみならず、巾広
い分野において使用されている。Such thermal recording media are relatively inexpensive, the recording device is compact, and maintenance is relatively easy, so they are used not only as recording media for facsimiles and various computers, but also in a wide range of fields.
近年、記録媒体として塗工されていない上質紙、所謂普
通紙を用いるファクシミリが登場し、用紙の手ざわり、
捺印適性、各種筆記適性等が従来の感熱記録体に比べ優
れている為、感熱記録体にもそのような特性を備えたも
のが要望されている。In recent years, facsimiles that use uncoated high-quality paper, so-called plain paper, have appeared as recording media, and the texture of the paper,
Since it is superior to conventional heat-sensitive recording materials in its suitability for stamping and various types of writing, there is a demand for heat-sensitive recording materials having such properties.
しかし、従来のオーバーコート層のない感熱記録体は、
有機の発色性物質や滑剤等が直接表面に出ているので、
爪で軽く引っ掻いた時に汚れ(スクラッチ汚れ)を生じ
、しかも捺印適性が不充分で、鉛筆筆記適性にも劣ると
いった欠点がある。However, conventional heat-sensitive recording materials without an overcoat layer
Organic coloring substances and lubricants are exposed directly to the surface, so
It also has the drawbacks of producing stains (scratch stains) when lightly scratched with a fingernail, and having insufficient aptitude for printing and poor aptitude for writing with a pencil.
一方、オーバーコート層を有する感熱記録体の場合には
、オーバーコート層を設ける主目的がバリヤー性の付与
にある為、スクラッチ汚れは改善されるものの鉛筆筆記
適性や捺印適性は改善されず、かえって朱肉の乾燥性が
低下するため捺印適性は一層悪化し、普通紙には程遠い
ものとなってしまう。On the other hand, in the case of a thermal recording material having an overcoat layer, the main purpose of providing the overcoat layer is to provide barrier properties, so although scratch stains are improved, pencil writing suitability and stamping suitability are not improved; Since the drying properties of the ink are reduced, the suitability for printing further deteriorates, and the paper is far from being suitable for plain paper.
これらの欠点を改善する目的で、例えば特開昭61−2
49789号公報には、オーバーコート層中にN−アシ
ルアミノ酸エステル等のアミノ酸系化合物を含有せしめ
インク受理性を改良した感熱記録体が提案されている。For the purpose of improving these drawbacks, for example, Japanese Patent Application Laid-Open No. 61-2
Japanese Patent No. 49789 proposes a heat-sensitive recording material in which the overcoat layer contains an amino acid compound such as N-acyl amino acid ester to improve ink receptivity.
しかし、かかる感熱記録体は鉛筆筆記性に劣り、必ずし
も満足しうる特性が得られない、また、特開昭62−5
5189号公報には、吸油量が50mj!/100g以
下で且つ粒子径が1μm〜5μmの無機顔料をオーバー
コート層中に含有せしめ、水性インキの滲みを改善する
方法が提案されているが、この様な粒子径の大きな顔料
をオーバーコート層中に含有せしめると、印字がこれら
の顔料粒子によって遮蔽された様になり(以下、白化現
象という)、画像濃度が著しく低下するという欠点があ
る。However, such heat-sensitive recording materials are inferior in pencil writability and do not necessarily provide satisfactory characteristics.
Publication No. 5189 states that the oil absorption amount is 50mj! A method has been proposed to improve the bleeding of water-based ink by incorporating an inorganic pigment with a particle size of 1 μm to 5 μm in the overcoat layer in an amount of /100 g or less. If these pigment particles are included in the pigment particles, the print will appear to be blocked by these pigment particles (hereinafter referred to as a whitening phenomenon), resulting in a disadvantage that the image density will be significantly reduced.
「発明が解決しようとする課題」
かかる現状に鑑み本発明者等は、捺印適性や各種筆記適
性に優れ、しかも印字部分の白化現象を伴わない感熱記
録体を得るべく鋭意研究の結果、−次粒子の平均粒子径
が0.2μm以下の顔料をオーバーコート層中に含有せ
しめると目的とする感熱記録体が得られることを見出し
、本発明を完成するに至った。"Problems to be Solved by the Invention" In view of the current situation, the inventors of the present invention have conducted intensive research to obtain a thermal recording medium that has excellent sealability and various writing aptitudes, and is free from whitening of the printed portion. The present inventors have discovered that the desired heat-sensitive recording material can be obtained by incorporating a pigment having an average particle size of 0.2 μm or less into the overcoat layer, and have completed the present invention.
「課題を解決するための手段」
本発明は、無色ないしは淡色の塩基性染料と該塩基性染
料と接触して呈色しうる呈色剤を含有する感熱記録層上
にオーバーコート層を設けた感熱記録体において、該オ
ーバーコート層中に一次粒子の平均粒子径が0.2μm
以下の顔料を含有せしめたことを特徴とする感熱記録体
である。"Means for Solving the Problems" The present invention provides an overcoat layer on a heat-sensitive recording layer containing a colorless or light-colored basic dye and a coloring agent capable of coloring when in contact with the basic dye. In the heat-sensitive recording material, the average particle diameter of primary particles in the overcoat layer is 0.2 μm.
This is a heat-sensitive recording material characterized by containing the following pigments.
「作用」
本発明の感熱記録体は、オーバーコート層中に一次粒子
の平均粒子径が0.2μm以下の顔料を含有せしめたと
ころに重大な特徴を有するものである。ちなみに、−次
粒子の平均粒子径が0.2μmを越える顔料を用いた場
合には、光の散乱傾向が強くなり、印字部分の白化現象
を招き、その結果画像濃度を著しく低下させてしまう、
また、−次粒子の平均粒子径が4μm前後以上になると
、逆に光の散乱傾向が弱まり白化現象は改善されるもの
の、顔料粒子間の空隙が少なくなり、しかも粗大顔料表
面に付着した朱肉はいつまでも吸い取られることがない
ため、印鑑を押した所を指で触ると印影が判読不能とな
ってしまう。"Function" The heat-sensitive recording material of the present invention has an important feature in that the overcoat layer contains a pigment whose primary particle average particle diameter is 0.2 μm or less. Incidentally, if a pigment with an average particle size of secondary particles exceeding 0.2 μm is used, the tendency of light scattering becomes strong, leading to a whitening phenomenon in the printed area, and as a result, the image density is significantly reduced.
In addition, when the average particle diameter of the secondary particles becomes around 4 μm or more, the tendency of light scattering becomes weaker and the whitening phenomenon is improved, but the voids between the pigment particles decrease and the vermilion attached to the surface of the coarse pigment decreases. Since it will not be absorbed forever, if you touch the place where the seal was stamped with your finger, the impression will become illegible.
このため本発明では、オーバーコート層中に配合する顔
料として、−次粒子の平均粒子径が0.2μm以下とい
った極めて微細な顔料を選択的に使用することで、光の
散乱傾向を大巾に抑制すると同時に高い空隙率を保持し
、印字部分の白化現象を伴うことなく捺印適性及び各種
筆記通性に優れた感熱記録体を得ているものである。For this reason, in the present invention, by selectively using extremely fine pigments with an average particle diameter of 0.2 μm or less as pigments to be blended into the overcoat layer, the tendency of light scattering can be greatly reduced. The present invention provides a heat-sensitive recording material which maintains a high porosity while suppressing the amount of porosity, and has excellent printing suitability and various writing passability without causing any whitening phenomenon in the printed portion.
かかるオーバーコート層に配合する顔料は、−次粒子の
平均粒子径が0.2μm以下のものであれば特に限定さ
れるものではなく、例えば、クレー炭酸カルシウム、炭
酸マグネシウム、水酸化アルミニウム、タルク、酸化チ
タン、酸化珪素、酸化亜鉛、尿素−ホルマリン樹脂微粉
末等が挙げられる。勿論、必要に応じて2種以上の顔料
の併用も可能である。The pigment to be added to the overcoat layer is not particularly limited as long as the average particle size of the secondary particles is 0.2 μm or less, and examples include clay calcium carbonate, magnesium carbonate, aluminum hydroxide, talc, Examples include titanium oxide, silicon oxide, zinc oxide, urea-formalin resin fine powder, and the like. Of course, it is also possible to use two or more pigments in combination, if necessary.
なお、これらの顔料のうちでも一次粒子の平均粒子径が
0.15μm以下の顔料は、とりわけ白化現象が改善さ
れ、画像濃度の高い感熱記録体が得られるため好ましい
。Among these pigments, pigments whose primary particles have an average particle diameter of 0.15 μm or less are particularly preferable because the whitening phenomenon is improved and a heat-sensitive recording medium with high image density can be obtained.
また、高感度の感熱記録体を得る為にオーバーコート層
のコート量を少なくする場合には、感熱層中の発色物質
がオーバーコート層上に滲み出し、サーマルヘッドとの
スティッキングを生じ易くなるため、これを防止する目
的で一次粒子の平均粒子径が1.0μm以上の顔料を併
用するのが望ましい。かかる−次粒子の平均粒子径が1
.0μm以上の顔料としては、その種類を特に限定する
ものではなく、上記の如き顔料のうちから適宜選択して
使用することができる。Furthermore, when reducing the coating amount of the overcoat layer in order to obtain a highly sensitive heat-sensitive recording medium, the color-forming substance in the heat-sensitive layer oozes onto the overcoat layer, which tends to cause sticking with the thermal head. In order to prevent this, it is desirable to use a pigment whose primary particles have an average particle diameter of 1.0 μm or more. The average particle diameter of such -order particles is 1
.. The type of pigment having a diameter of 0 μm or more is not particularly limited, and can be appropriately selected from the pigments listed above.
なお、−次粒子の平均粒子径が1.0μm以上の顔料を
併用する場合には、本願の所望の効果を阻害しない範囲
にとどめる必要があり、その使用量は一次粒子の平均粒
子径が0.2μm以下の顔料の50重量%以下、好まし
くは30重量%以下とするのが望ましい。In addition, when using a pigment with an average particle diameter of primary particles of 1.0 μm or more, it is necessary to keep it within a range that does not inhibit the desired effect of the present application, and the amount used is such that the average particle diameter of primary particles is 0 μm or more. It is desirable that the amount of the pigment be 50% by weight or less, preferably 30% by weight or less of the pigment having a diameter of .2 μm or less.
因みに、本発明で言及した一次粒子の平均粒子径は、顔
料粉体を走査型電子顕微鏡(JSM−T−300)で3
5000倍に拡大して粒子径を決定した。Incidentally, the average particle diameter of the primary particles mentioned in the present invention is determined by measuring the pigment powder with a scanning electron microscope (JSM-T-300).
The particle size was determined under 5000x magnification.
上記の如き顔料と共にオーバーコート層を構成するバイ
ンダーとしては、−船釣な水溶性高分子が挙げられ、例
えば、酸化澱粉、酵素変性澱粉、カチオン澱粉、エステ
ル化澱粉、エーテル化澱粉などの澱粉類、メチルセルロ
ース、エチルセルロース、カルボキシメチルセルロース
、メトキシセルロース、ヒドロキシエチルセルロースな
どのセルロース誘導体、完全(又は不完全)鹸化ポリビ
ニルアルコール、カルボキシ変性ポリビニルアルコール
、アセトアセチル化ポリビニルアルコールなどのポリビ
ニルアルコール類、ポリアク’J/L’酸ソーダ、ポリ
アクリルアミド、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、スチレ
ン/無水マレイン酸共重合体アルカリ塩、イソブチレン
/無水マレイン酸共重合体アルカリ塩、アルギン酸ソー
ダ、ゼラチン、カゼイン等の水溶性高分子等が例示され
る。勿論これらに限定されるものではなく、また必要に
応じて2種類以上を併用することもできる。The binder constituting the overcoat layer together with the above pigments includes water-soluble polymers, such as starches such as oxidized starch, enzyme-modified starch, cationic starch, esterified starch, and etherified starch. , cellulose derivatives such as methylcellulose, ethylcellulose, carboxymethylcellulose, methoxycellulose, hydroxyethylcellulose, polyvinyl alcohols such as completely (or incompletely) saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, polyac 'J/L' Acid soda, polyacrylamide, polyvinylpyrrolidone, acrylic amide/acrylic ester copolymer, acrylic amide/acrylic ester/methacrylic acid copolymer, styrene/maleic anhydride copolymer alkali salt, isobutylene/maleic anhydride Examples include copolymer alkali salts, water-soluble polymers such as sodium alginate, gelatin, and casein. Of course, it is not limited to these, and two or more types can be used in combination if necessary.
尚、これらのバインダーの使用量は、オーバーコート開
用塗料の全固形分に対し20〜50重量%の範囲で調節
するのが望ましい。The amount of these binders used is desirably adjusted within the range of 20 to 50% by weight based on the total solid content of the overcoat opening paint.
又、このオーバーコート層には、必要に応じてサーマル
ヘッドとの滑りを改良するための各種離型剤、分散剤、
蛍光染料、消泡剤等の感熱記録層用塗料の調製時に使用
される各種助剤を併用することができる。In addition, this overcoat layer may contain various release agents, dispersants,
Various auxiliary agents used in preparing coatings for heat-sensitive recording layers, such as fluorescent dyes and antifoaming agents, can be used in combination.
オーバーコート開用塗料は、水を分散媒体として特定の
顔料及びバインダーなどを分散して調製され、感熱記録
層上に塗布されるのであるが、その塗工方法については
特に限定されるものではな(
く、従来から周知慣用の技術に従って形成することがで
き、例えばエアーナイフコーター、プレードコーター、
バーコーター、グラビアコーターカーテンコーター等の
適当な塗布装置が用いられる。また、塗液の塗布量につ
いても特に限定されるものではないが、サーマルヘッド
からのジュール熱をより有効に感熱記録層に伝達するた
めに5g/n(以下、好ましくは3g/%以下の塗布量
が良く、逆にスクラッチ適性、捺印適性および筆記適性
の改善効果を出す為には、0.8g/rrf以上の塗布
量が良く、従って適性塗布量としては0.8〜3g/ボ
の範囲が望ましい。Overcoat opening paints are prepared by dispersing specific pigments, binders, etc. using water as a dispersion medium, and are applied onto the heat-sensitive recording layer, but there are no particular limitations on the coating method. (It can be formed according to conventionally well-known and commonly used techniques, such as an air knife coater, a blade coater,
A suitable coating device such as a bar coater, gravure coater, curtain coater, etc. is used. The coating amount of the coating liquid is also not particularly limited, but in order to more effectively transfer the Joule heat from the thermal head to the heat-sensitive recording layer, the coating amount is preferably 5 g/n (hereinafter, preferably 3 g/% or less). On the other hand, in order to achieve the effect of improving scratch aptitude, imprint aptitude, and writing aptitude, a coating amount of 0.8 g/rrf or more is good, so the appropriate coating amount is in the range of 0.8 to 3 g/rrf. is desirable.
本発明の感熱記録体において、記録層を構成する塩基性
染料としては、公知の無色ないしは淡色の塩基性染料が
使用でき、具体的には例えば下記が例示される。In the heat-sensitive recording material of the present invention, known colorless or light-colored basic dyes can be used as basic dyes constituting the recording layer, and specific examples include the following.
3.3−ビス(p−ジメチルアミノフェニル)6−シメ
チルアミノフタリド、3,3−ビス(p−ジメチルアミ
ノフェニル)フタリド、3−(p−ジメチルアミノフェ
ニル)−3−(1,2−ジメチルインドール−3−イル
)フタリド、3−(P−ジメチルアミノフェニル)−3
−(2−メチルインドール−3−イルフタリド、3,3
−ビス(l、2−ジメチルインドール−3−イル)−5
=ジメチルアミノフタリド、3.3−ビス(1゜2−ジ
メチルインドール−3−イル)−6−シメチルアミノフ
タリド、3.3−ビス(9−エチルカルバゾール−3−
イル)−6−シメチルアミノフタリド、3,3−ビス(
2−フェニルインドール−3−イル)−6−シメチルア
ミノフタリド、3−p−ジメチルアミノフェニル−3−
(1−メチルピロール−3−イル)−6−シメチルアミ
ノフタリド等のトリアリルメタン系染料、4,4′−ビ
ス−ジメチルアミノベンズヒドリルベンジルエーテル、
N−ハロフェニル−ロイコオーラミン、N−2,4,5
−)+7クロロフェニル口イコオーラミン等のジフェニ
ルメタン系染料、ベンゾイルロイコメチレンブルー、p
−ニトロベンゾイルロイコメチレンブルー等のチアジン
系染料、3−メチル−スピロ−ジナフトピラン、3−エ
チル−スピロ−ジナフトピラン、3−フェニル−スピロ
−ジナフトピラン、3−ベンジル−スピロ−ジナフトピ
ラン、3−メチル−ナフト(6′−メトキシベンゾ)ス
ピロピラン、3−プロビルースビロジヘンゾピラン等の
スピロ系染料、ローダミンB−アニリノラクタム、ロー
ダミン(p−ニトロアニリノ)ラクタム、ローダミン(
0−クロロアニリノ)ラクタム等のラクタム系染料、3
−ジメチルアミノ−7−メドキシフルオラン、3−ジエ
チルアミノ−6−メドキシフルオラン、3−ジエチルア
ミノ−7−メドキシフルオラン、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−6−メチ
ル−7−クロロフルオラン、3−ジエチルアミノ−6,
7−シメチルフルオラン、3−(N−エチル−p−)ル
イジノ)−7=メチルフルオラン、3−ジエチルアミノ
−7−N〜ルアセチルN−メチルアミノフルオラン、3
ジエチルアミノ−7−N−メチルアミノフルオラン、3
−ジエチルアミノ−7−ジベンジルアミノフルオラン、
3−ジエチルアミノ−7−N−メチル−N−ベンジルア
ミノフルオラン、3−ジエチルアミノ−7−N−クロロ
エチル−N−メチルアミノフルオラン、3−ジエチルア
ミノ−7−ジエチルアミノフルオラン、3−(N−エチ
ル−pトルイジノ)−6−メチル−7−フェニルアミノ
フルオラン、3−(N−エチル−p−)ルイジノ)−6
−メチル−7−(p−トルイジノ)フルオラン、3−ジ
エチルアミノ−6−メチル−7−フェニルアミノフルオ
ラン、3−ジブチルアミノ−6−メチル−7−フェニル
アミノフルオラン、3ジエチルアミノ−7−(2−カル
ボメトキシ−フェニルアミノ)フルオラン、3−(N−
シクロへキシル−N−メチルアミノ)−6−メチル−7
フエニルアミノフルオラン、3−ピロリジノ−6=メチ
ル−7−フェニルアミノフルオラン、3−ピペリジノ−
6−メチル−7−フェニルアミノフルオラン、3−ジエ
チルアミノ−6−メチル−7=キシリジノフルオラン、
3−ジエチルアミノ7−(o−クロロフェニルアミノ)
フルオラン、3−ジブチルアミノ−7−(o−クロロフ
ェニルアミノ)フルオラン、3−ピロリジノ−6−メチ
ル−7−P−7’チルフエニルアミノフルオラン、3−
(N−メチル−N−n−アミル)アミノ−6メチルー7
−フエニルアミノフルオラン、3−(N−エチル−N−
n−アミル)アミノ−6−メチル−7−フェニルアミノ
フルオラン、3−(Nエチル−N−イソアミル)アミノ
−6−メチルツーフェニルアミノフルオラン、3−(N
−メチル−N−n−ヘキシル)アミノ−6−メチル=7
−フェニルアミノフルオラン、3−(N−エチル−N−
n−ヘキシル)アミノ−6−メチル−7=フエニルアミ
ノフルオラン、3−(N−エチルN−β−エチルヘキシ
ル)アミノ−6−メチルツーフェニルアミノフルオラン
等のフルオラン系染料等。勿論、これらの染料に限定さ
れるものではなく、二種以上の染料の併用も可能である
。3.3-bis(p-dimethylaminophenyl)6-dimethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)phthalide, 3-(p-dimethylaminophenyl)-3-(1,2 -dimethylindol-3-yl)phthalide, 3-(P-dimethylaminophenyl)-3
-(2-methylindole-3-ylphthalide, 3,3
-bis(l,2-dimethylindol-3-yl)-5
=dimethylaminophthalide, 3.3-bis(1゜2-dimethylindol-3-yl)-6-dimethylaminophthalide, 3.3-bis(9-ethylcarbazol-3-
yl)-6-dimethylaminophthalide, 3,3-bis(
2-phenylindol-3-yl)-6-dimethylaminophthalide, 3-p-dimethylaminophenyl-3-
Triallylmethane dyes such as (1-methylpyrrol-3-yl)-6-dimethylaminophthalide, 4,4'-bis-dimethylaminobenzhydryl benzyl ether,
N-halophenyl-leukoolamine, N-2,4,5
-)+7 Diphenylmethane dyes such as chlorophenyl-coalamine, benzoylleucomethylene blue, p
- Thiazine dyes such as nitrobenzoylleucomethylene blue, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-phenyl-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphtho(6 '-Methoxybenzo) spiropyran, 3-probilous virodihenzopyran and other spiro dyes, rhodamine B-anilinolactam, rhodamine (p-nitroanilino)lactam, rhodamine (
Lactam dyes such as 0-chloroanilino)lactam, 3
-dimethylamino-7-medoxyfluoran, 3-diethylamino-6-medoxyfluoran, 3-diethylamino-7-medoxyfluoran, 3-diethylamino-
7-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-6,
7-dimethylfluorane, 3-(N-ethyl-p-)luidino)-7=methylfluorane, 3-diethylamino-7-N~acetyl N-methylaminofluorane, 3
diethylamino-7-N-methylaminofluorane, 3
-diethylamino-7-dibenzylaminofluorane,
3-diethylamino-7-N-methyl-N-benzylaminofluorane, 3-diethylamino-7-N-chloroethyl-N-methylaminofluorane, 3-diethylamino-7-diethylaminofluorane, 3-(N-ethyl -p-toluidino)-6-methyl-7-phenylaminofluorane, 3-(N-ethyl-p-)luidino)-6
-Methyl-7-(p-toluidino)fluorane, 3-diethylamino-6-methyl-7-phenylaminofluorane, 3-dibutylamino-6-methyl-7-phenylaminofluorane, 3-diethylamino-7-(2 -carbomethoxy-phenylamino)fluorane, 3-(N-
cyclohexyl-N-methylamino)-6-methyl-7
Phenylaminofluorane, 3-pyrrolidino-6=methyl-7-phenylaminofluorane, 3-piperidino-
6-methyl-7-phenylaminofluorane, 3-diethylamino-6-methyl-7=xylidinofluorane,
3-diethylamino 7-(o-chlorophenylamino)
Fluoran, 3-dibutylamino-7-(o-chlorophenylamino)fluoran, 3-pyrrolidino-6-methyl-7-P-7'tylphenylaminofluoran, 3-
(N-methyl-N-n-amyl)amino-6methyl-7
-phenylaminofluorane, 3-(N-ethyl-N-
n-amyl)amino-6-methyl-7-phenylaminofluorane, 3-(N-ethyl-N-isoamyl)amino-6-methyltwophenylaminofluorane, 3-(N
-Methyl-N-n-hexyl)amino-6-methyl=7
-phenylaminofluorane, 3-(N-ethyl-N-
Fluoran dyes such as n-hexyl)amino-6-methyl-7=phenylaminofluorane, 3-(N-ethylN-β-ethylhexyl)amino-6-methyltwophenylaminofluorane, and the like. Of course, the dyes are not limited to these dyes, and two or more types of dyes can be used in combination.
また、上記塩基性染料と組合せて使用される呈色剤につ
いても各種の化合物が知られており、例えば下記が例示
される。Furthermore, various compounds are known as coloring agents to be used in combination with the above basic dyes, for example, the following are exemplified.
4−tert−ブチルフェノール、α−ナフトール、β
−ナフトール、4−アセチルフェノール、4−tert
−オクチルフェノール、4.4’−5ec−ブチリデン
ジフェノール、4−フェニルフェノール、ハイドロキノ
ン、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、2,2−ビス(
4−ヒドロキシフェニル)−4−メチルペンタン、4.
4’ −シクロへキシリデンジフェノール、4.4’−
ジヒドロキシジフェニルサルファイド、4,4′−チオ
ビス(6−tert−ブチル−3−メチルフェノール)
、4.4′−ジヒドロキシジフェニルスルホン、4ヒド
ロキシ−4′−メチルジフェニルスルホン、4−ヒドロ
キシ−4′−メト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、ヒド
ロキノンモノベンジルエーテル、4−ヒドロキシベンゾ
フェノン、2,4−ジヒドロキシベンゾフェノン、2,
4.4’トリヒドロキシベンゾフエノン、2.2’、4
゜4′−テトラヒドロキシベンゾフェノン、2.2’メ
チレンビス(4−クロルフェノール)、1゜3−ジ(2
−(4−ヒドロキシフェニル)−2=プロピル〕ベンゼ
ン、ビス(3−アリル−4−ヒドロキシフェニル)スル
ホン、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エチル、4
−ヒドロキシ安息香酸プロピル、4−ヒドロキシ安息香
酸−5ec−ブチル、4−ヒドロキシ安息香酸ペンチル
、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−ヒドロキシ安
息香酸フェニルプロピル、4−ヒドロキシ安息香酸フェ
ネチル、4−ヒドロキシ安息香M−p−クロロベンジル
、4−ヒドロキシ安息香酸−p−メトキシベンジル、ノ
ボラック型フェノール樹脂、フェノール重合体等のフェ
ノール性化合物、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、3−5e
c −ブチル−4−ヒドロキシ安息香酸、3−シクロへ
キシル−4−ヒドロキシ安息香酸、3,5−ジメチル−
4−ヒドロキシ安息香酸、サリチル酸、3イソプロピル
サリチル酸、3−tert−ブチルサリチル酸、3,5
−ジーtert−ブチルサリチル酸、3−ベンジルサリ
チルM、3−(α−メチルベンジル)サリチル酸、3−
クロル−5−(α−メチルベンジル)サリチル酸、3−
フェニル−5−(α、α−ジメチルベンジル)サリチル
酸、3.5−ジ−α−メチルベンジルサリチル酸、4−
(3−p−トリルスルホニルプロピルオキシ)サリチル
酸の亜鉛塩等の芳香族カルボン酸、およびこれらフェノ
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、チタン、マンガン
、スズ、ニッケル等の多価金属との塩、さらにはチオシ
アン酸亜鉛のアンチピリン錯体等の有機錯化合物等。な
お、これらの呈色剤も必要に応じて2種以上を併用する
ことができる。4-tert-butylphenol, α-naphthol, β
-naphthol, 4-acetylphenol, 4-tert
-octylphenol, 4.4'-5ec-butylidene diphenol, 4-phenylphenol, hydroquinone, 4.4'-dihydroxy-diphenylmethane, 4,
4'-isopropylidenediphenol, 2,2-bis(
4-hydroxyphenyl)-4-methylpentane, 4.
4'-cyclohexylidene diphenol, 4.4'-
Dihydroxydiphenyl sulfide, 4,4'-thiobis(6-tert-butyl-3-methylphenol)
, 4.4'-dihydroxydiphenylsulfone, 4-hydroxy-4'-methyldiphenylsulfone, 4-hydroxy-4'-methoxydiphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, hydroquinone monobenzyl ether, 4- Hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,
4.4'trihydroxybenzophenone, 2.2',4
゜4'-tetrahydroxybenzophenone, 2.2'methylenebis(4-chlorophenol), 1゜3-di(2
-(4-hydroxyphenyl)-2=propyl]benzene, bis(3-allyl-4-hydroxyphenyl)sulfone, dimethyl 4-hydroxyphthalate, methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, 4
-propyl hydroxybenzoate, 5ec-butyl 4-hydroxybenzoate, pentyl 4-hydroxybenzoate, phenyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, tolyl 4-hydroxybenzoate, 4-
Chlorophenyl hydroxybenzoate, phenylpropyl 4-hydroxybenzoate, phenethyl 4-hydroxybenzoate, M-p-chlorobenzyl 4-hydroxybenzoate, p-methoxybenzyl 4-hydroxybenzoate, novolac type phenolic resin, phenol polymer Phenolic compounds such as benzoic acid, p-tert-butylbenzoic acid, trichlorobenzoic acid, terephthalic acid, 3-5e
c -Butyl-4-hydroxybenzoic acid, 3-cyclohexyl-4-hydroxybenzoic acid, 3,5-dimethyl-
4-hydroxybenzoic acid, salicylic acid, 3-isopropylsalicylic acid, 3-tert-butylsalicylic acid, 3,5
-di-tert-butylsalicylic acid, 3-benzylsalicyl M, 3-(α-methylbenzyl)salicylic acid, 3-
Chlor-5-(α-methylbenzyl)salicylic acid, 3-
Phenyl-5-(α,α-dimethylbenzyl)salicylic acid, 3,5-di-α-methylbenzylsalicylic acid, 4-
Aromatic carboxylic acids such as the zinc salt of (3-p-tolylsulfonylpropyloxy)salicylic acid, and these phenolic compounds, aromatic carboxylic acids such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, nickel, etc. Salts with polyvalent metals, and organic complexes such as antipyrine complexes of zinc thiocyanate. Note that two or more of these coloring agents can be used in combination as necessary.
かかる呈色剤のうち特に4−(3−p−)リルスルホニ
ルプロピルオキシ)サリチル酸の亜鉛塩及び4−ヒドロ
キシ−4′−イソプロポキシジフェニルスルホンを併用
せしめると記録画像の安定性が優れる為好ましい。Among these coloring agents, it is particularly preferable to use zinc salt of 4-(3-p-)lylsulfonylpropyloxy)salicylic acid and 4-hydroxy-4'-isopropoxydiphenylsulfone in combination because the stability of recorded images is excellent.
尚、塩基性染料と呈色剤の使用比率は用いる塩基性染料
や呈色剤の種類に応じて適宜選択されるもので、特に限
定するものではないが、一般に塩基性染料100重量部
に対して100〜700重量部、好ましくは150〜4
00重量部程度の呈色剤が使用される。The ratio of the basic dye and coloring agent to be used is appropriately selected depending on the type of basic dye and coloring agent used, and is not particularly limited. 100 to 700 parts by weight, preferably 150 to 4 parts by weight
About 0.00 parts by weight of coloring agent is used.
これらを含む感熱記録層用塗液の調製は、一般に水を分
散媒体とし、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、染料と呈色剤とを一緒に又は別々
に分散するなどして調製される。The coating liquid for the heat-sensitive recording layer containing these is generally prepared by using water as a dispersion medium and dispersing the dye and coloring agent together or separately using a stirring/pulverizing machine such as a ball mill or attritor sand mill. prepared.
かかる塗液中には、通常バインダーとしてデンプン類、
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、ゼラチン、カゼイン、アラビ
アガム、ポリビニルアルコール、カルボキシ基変性・ス
ルホン基変性・アセトアセチル基変性・シリコン変性等
の各種変性ポリビニルアルコール、スチレン・無水マレ
イン酸共重合体塩、スチレン・アクリル酸共重合体塩、
スチレン・ブタジェン共重合体エマルジョン等が全固形
分の2〜40重量%、好ましくは5〜25重量%重量%
台される。勿論、これらのバインダー類は2種類以上を
併用することも可能である。Such coating liquids usually contain starches and binders as binders.
Hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, gum arabic, polyvinyl alcohol, various modified polyvinyl alcohols such as carboxyl group-modified, sulfone group-modified, acetoacetyl group-modified, and silicone-modified polyvinyl alcohols, styrene/maleic anhydride copolymer salts, Styrene/acrylic acid copolymer salt,
Styrene-butadiene copolymer emulsion etc. is 2 to 40% by weight of the total solids, preferably 5 to 25% by weight.
It is set up. Of course, two or more of these binders can also be used in combination.
さらに、本発明の所望の効果を阻害しない範囲で例えば
ステアリン酸アミド、ステアリン酸メチレンビスアミド
、オレイン酸アミド、パルミチン酸アミド、ヤシ脂肪酸
アミド等の脂肪酸アミド、2゜2′−メチレンビス(4
−メチル−6tert−ブチルフェノール)、4.4’
−ブチリデンビス(6tert−ブチル−3−メチルフ
ェノール)、■。Further, fatty acid amides such as stearic acid amide, stearic acid methylene bisamide, oleic acid amide, palmitic acid amide, coconut fatty acid amide, 2゜2'-methylene bis(4
-methyl-6tert-butylphenol), 4.4'
-Butylidenebis(6tert-butyl-3-methylphenol), ■.
1、 3−1−リス(2−メチル−4−ヒドロキシ5
tert−ブチルフェニル)ブタン等のヒンダードフ
ェノール類、p−ベンジルビフェニル、1゜2−ビス(
フェノキシ)エタン、1.2−ビス(4−メチルフェノ
キシ)エタン、1.2−ビス(3−メチルフェノキシ)
エタン、1−(2−メチルフェノキシ)−2−(4−メ
トキシフェノキシ)エタン、2−ナフトールベンジルエ
ーテル、ヘンシル−4−メチルチオフェニルエーテル等
のエーテル類、ジベンジルテレフタレート、l−ヒドロ
キシ−2ナフトエ酸フエニルエステル等のエステル類、
2− (2’−ヒドロキシ−5′−メチルフェニル)ベ
ンゾトリアゾール、2−ヒドロキシ4−ベンジルオキシ
ベンゾフェノン等の紫外線吸収剤、および各種公知の熱
可融性物質を増感剤として添加することもできる。1, 3-1-lis(2-methyl-4-hydroxy5
Hindered phenols such as tert-butylphenyl)butane, p-benzylbiphenyl, 1゜2-bis(
phenoxy)ethane, 1.2-bis(4-methylphenoxy)ethane, 1.2-bis(3-methylphenoxy)
Ethers such as ethane, 1-(2-methylphenoxy)-2-(4-methoxyphenoxy)ethane, 2-naphtholbenzyl ether, hensyl-4-methylthiophenyl ether, dibenzyl terephthalate, l-hydroxy-2-naphthoic acid Esters such as phenyl ester,
Ultraviolet absorbers such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-hydroxy4-benzyloxybenzophenone, and various known thermofusible substances can also be added as sensitizers. .
かかる増感剤の内でも1−(2−メチルフェノキシ)〜
2−(4−メトキシフェノキシ)エタンは特に増感効果
が優れているため好ましい。Among such sensitizers, 1-(2-methylphenoxy) ~
2-(4-methoxyphenoxy)ethane is particularly preferred since it has an excellent sensitizing effect.
また、オーバーコート層のカス付着改善効果を助ける目
的で、感熱記録層へもカオリン、クレータルク、炭酸カ
ルシウム、焼成りレー、酸化チタン、珪藻土、微粒子状
無水シリカ、活性白土等の無機顔料を添加することがで
きる。In addition, inorganic pigments such as kaolin, clay talc, calcium carbonate, calcined clay, titanium oxide, diatomaceous earth, fine particulate anhydrous silica, and activated clay are added to the heat-sensitive recording layer in order to help improve the adhesion of residue in the overcoat layer. be able to.
本発明において、感熱記録層の形成方法については特に
限定されるものではなく、従来から周知慣用の技術に従
って形成することができ、例えばエアーナイフコーター
、ブレードコーター、バーコーター、グラビアコーター
、カーテンコーター等の適当な塗布装置が用いられる。In the present invention, the method for forming the heat-sensitive recording layer is not particularly limited, and it can be formed using conventionally well-known and commonly used techniques, such as an air knife coater, blade coater, bar coater, gravure coater, curtain coater, etc. Appropriate coating equipment is used.
また、塗液の塗布量についても特に限定されるものでは
なく、一般に乾燥重量で2〜12g/rr?、好ましく
は3〜10g/rrfの範囲で調節される。Furthermore, the amount of coating liquid to be applied is not particularly limited, and is generally 2 to 12 g/rr in terms of dry weight. , preferably within the range of 3 to 10 g/rrf.
支持体としては、紙、合成繊維紙、透明又は不透明のプ
ラスチックフィルムなどが用いられる。As the support, paper, synthetic fiber paper, transparent or opaque plastic film, etc. are used.
尚、支持体と感熱記録層との間に下塗り層を設けること
も可能であり、支持体の裏面に保護層を設けたり、さら
には粘着加工を施すなど感熱記録体製造分野における各
種の公知技術が付加し得るものである。It is also possible to provide an undercoat layer between the support and the heat-sensitive recording layer, and various known techniques in the field of heat-sensitive recording material manufacturing may be used, such as providing a protective layer on the back side of the support or applying adhesive processing. can be added.
「実施例」
以下に実施例を示し、本発明をより具体的に説明するが
、勿論これらに限定されるものではない。"Example" The present invention will be described in more detail with reference to Examples below, but the present invention is of course not limited to these.
また、特に断らない限り例中の部および%はそれぞれ重
量部および重量%を示す。Further, unless otherwise specified, parts and % in the examples indicate parts by weight and % by weight, respectively.
実施例1
〔下塗り履用塗液の調製〕
吸油量160cc/100gの無定形シリカ(商品名:
ミズ力シールP−527.水沢化学社製)100部
スチレン−ブタジェン共重合体ラテックス(Tg点コニ
−35C) (固形分換算) 15部ヒドロキ
シプロピル化澱粉(固形分換算)5部
分散剤(固形分換算)0.5部
この組成物を均一に混合し、固形分濃度30%の下塗り
履用塗液を得た。Example 1 [Preparation of undercoat coating liquid] Amorphous silica (trade name:
Mizuriki Seal P-527. (manufactured by Mizusawa Chemical Co., Ltd.) 100 parts Styrene-butadiene copolymer latex (Tg point Kony-35C) (in terms of solid content) 15 parts Hydroxypropylated starch (in terms of solid content) 5 parts Dispersant (in terms of solid content) 0.5 parts The composition was mixed uniformly to obtain an undercoat shoe coating liquid with a solid content concentration of 30%.
45g/r+fの上質紙に上記下塗り履用塗液を、乾燥
後の塗布量が15 g/rrrとなるようにバーコータ
ーで塗布乾燥し、下塗り塗布紙を得た。The above-mentioned undercoat coating solution was applied to a 45 g/r+f high-quality paper using a bar coater so that the coated amount after drying was 15 g/rrr and dried to obtain an undercoat coated paper.
へ放且製
3−ジブチルアミノ−6−メチル−7−フェニルアミノ
フルオラン 10部ベンジル−4−メチル
チオフェニルエーテル20部
メチルセルロース5%水溶液 15部水
80部この組成
物をサンドミルで平均粒子径が1μmになるまで粉砕し
た。3-Dibutylamino-6-methyl-7-phenylaminofluorane 10 parts Benzyl-4-methylthiophenyl ether 20 parts Methyl cellulose 5% aqueous solution 15 parts water
80 parts of this composition was ground in a sand mill until the average particle size was 1 μm.
旦撒星製
4−ヒドロキシ−4′−イソプロポキシジフェニルスル
ホン 30部メチルセルロース5%
水溶液 30部水
70部この組成物をサンドミルで平均
粒子径が2μmになるまで粉砕した。4-Hydroxy-4'-isopropoxydiphenylsulfone 30 parts Methyl cellulose 5%
Aqueous solution 30 parts water
70 parts of this composition was ground in a sand mill until the average particle size was 2 μm.
A液125部、B液130部、無定形シリカ(吸油量1
80cc/100g)30部、20%酸化澱粉水溶液1
50部、水55部を撹拌・混合して記録層用塗液を調製
した。125 parts of liquid A, 130 parts of liquid B, amorphous silica (oil absorption 1
80cc/100g) 30 parts, 20% oxidized starch aqueous solution 1
A recording layer coating liquid was prepared by stirring and mixing 50 parts and 55 parts of water.
得られた記録層用塗液を、前記下塗り塗布紙上に乾燥後
の塗布量が5g/mとなるようにマイヤ−バーで塗布・
乾燥して感熱記録紙を得た。The obtained recording layer coating liquid was applied onto the undercoat coated paper using a Mayer bar so that the coating amount after drying was 5 g/m.
A thermosensitive recording paper was obtained by drying.
下記組成物を下記の固形分比率で配合し塗料濃度7%の
オーバーコート履用塗液を調製した。An overcoat shoe coating liquid having a paint concentration of 7% was prepared by blending the following composition at the solid content ratio shown below.
超微細軽質炭酸カルシウム(商品名:PX、白石カルシ
ウム社製、−次粒子の平均粒子径0.1μm)
35部重質炭酸カルシウム(商品名
:ソフトン1500、備北粉化工業社製、−次粒子の平
均粒子径1.5μm) lo部
部外性ポリビニルアルコール商品名:ゴーセハイマーZ
−200,日本合成化学社製)30部
ステアリン酸亜鉛エマルジョン(商品名:ハイドリンZ
−7.中京油脂社製) 5部分散剤(商品名ニ
アロンA−9.東亜合成化学社製)0.3部
〔オーバーコート層の形成〕
先に形成した感熱記録層上に上記オーバーコート履用塗
液を乾燥塗布量が2.0g/ボになる様にマイヤーバー
で塗布・乾燥し、スーパーカレンダーで平滑化して感熱
記録紙を得た。Ultrafine light calcium carbonate (trade name: PX, manufactured by Shiraishi Calcium Co., Ltd., average particle size of secondary particles 0.1 μm)
35 parts heavy calcium carbonate (trade name: Softon 1500, manufactured by Bihoku Funka Kogyo Co., Ltd., average particle size of secondary particles 1.5 μm) lo part exogenous polyvinyl alcohol trade name: Goseheimer Z
-200, manufactured by Nippon Gosei Kagaku Co., Ltd.) 30 parts zinc stearate emulsion (product name: Hydrin Z)
-7. (manufactured by Chukyo Yushi Co., Ltd.) 0.3 parts of 5-part dispersant (trade name: Nearon A-9. Manufactured by Toagosei Kagaku Co., Ltd.) [Formation of overcoat layer] The above-mentioned overcoat coating liquid was applied on the previously formed heat-sensitive recording layer. It was coated and dried with a Mayer bar so that the dry coating amount was 2.0 g/bore, and smoothed with a super calendar to obtain a heat-sensitive recording paper.
実施例2
実施例1のオーバーコート履用塗液の調製において、超
微細軽質炭酸カルシウムの代わりに超微細酸化亜鉛(商
品名:FINEX−25,堺化学社製、−次粒子の平均
粒子径0.06μm)を用いた以外は実施例1と同様に
して感熱記録紙を得た。Example 2 In the preparation of the overcoat shoe coating liquid of Example 1, ultrafine zinc oxide (trade name: FINEX-25, manufactured by Sakai Kagaku Co., Ltd., average particle diameter of 0) was used instead of ultrafine light calcium carbonate. A thermosensitive recording paper was obtained in the same manner as in Example 1, except that .06 μm) was used.
実施例3
実施例1のオーバーコート履用塗液の調製において、超
微細軽質炭酸カルシウムの代わりに超微細酸化珪素(商
品名:レオロシール102.徳山ソーダ社製、−次粒子
の平均粒子径0.015μm)を用いた以外は全て実施
例1と同様にして感熱記録紙を得た。Example 3 In the preparation of the overcoat shoe coating liquid of Example 1, ultrafine silicon oxide (trade name: Rheolo Seal 102, manufactured by Tokuyama Soda Co., Ltd., average particle diameter of 0.000000 particles) was used instead of ultrafine light calcium carbonate. A thermosensitive recording paper was obtained in the same manner as in Example 1 except that 015 μm) was used.
実施例4
実施例1のオーバーコート履用塗液の調製において、重
質炭酸カルシウム(商品名:ソフトン1500)の代わ
りに超微細軽質炭酸カルシウム(商品名:PX)を使用
した以外は全て実施例1と同様にして感熱記録紙を得た
。Example 4 All examples were the same as in Example 1 except that ultrafine light calcium carbonate (trade name: PX) was used instead of heavy calcium carbonate (trade name: Softon 1500) in the preparation of the overcoat shoe coating liquid. A thermosensitive recording paper was obtained in the same manner as in 1.
実施例5
旦丘皿製
3−ジブチルアミノ−6−メチル−7−フェニルアミノ
フルオラン 10部1−(2−メチルフ
ェノキシ)−2−(4−メトキシフェノキシ)エタン
20部メチルセルロース5%水溶液 15
部水 8
0部この組成物をサンドミルで平均粒子径が1μmにな
るまで粉砕した。Example 5 3-dibutylamino-6-methyl-7-phenylaminofluorane manufactured by Dankyu Sara 10 parts 1-(2-methylphenoxy)-2-(4-methoxyphenoxy)ethane
20 parts methylcellulose 5% aqueous solution 15
Department water 8
0 parts This composition was ground in a sand mill until the average particle size was 1 μm.
■丘R製
4−ヒドロキシ−4′−イソプロポキシジフェニルスル
ホン 30部4−(3−p−トリル
スルホニルプロピルオキシ)サリチル酸の亜鉛塩
25部メチルセルロース5%水溶液 30部
水 70
部この組成物をサンドミルで平均粒子径が2μmになる
まで粉砕した。■4-Hydroxy-4'-isopropoxydiphenylsulfone manufactured by Oka R 30 parts Zinc salt of 4-(3-p-tolylsulfonylpropyloxy)salicylic acid
25 parts 5% methylcellulose aqueous solution 30 parts water 70
This composition was ground in a sand mill until the average particle size was 2 μm.
実施例3におけるA液125部、B液130部をそれぞ
れC液125部、D液155部に代えた以外は全て実施
例3と同様にして感熱記録紙を得た。A thermosensitive recording paper was obtained in the same manner as in Example 3 except that 125 parts of Liquid A and 130 parts of Liquid B in Example 3 were replaced with 125 parts of Liquid C and 155 parts of Liquid D, respectively.
比較例1
実施例1のオーバーコート履用塗液の調製において、超
微細軽質炭酸カルシウムの代わりに軽質炭酸カルシウム
(商品名:PZ、白石カルシウム社製、−次粒子の平均
粒子径0.25μm)を用いた以外は全て実施例工と同
様にして感熱記録紙を得た。Comparative Example 1 In the preparation of the overcoat shoe coating liquid of Example 1, light calcium carbonate (trade name: PZ, manufactured by Shiraishi Calcium Co., Ltd., average particle size of secondary particles 0.25 μm) was used instead of ultrafine light calcium carbonate. A thermosensitive recording paper was obtained in the same manner as in the example except that .
比較例2
実施例Iのオーバーコート履用塗液の調製において、超
微細軽質炭酸カルシウムの代わりに酸化亜鉛、亜鉛華1
号(堺化学社製、−次粒子の平均粒子径0.6μm)を
使用した以外は実施例1と同様にして感熱記録紙を得た
。Comparative Example 2 In the preparation of the overcoat shoe coating liquid of Example I, zinc oxide and zinc white 1 were used instead of ultrafine light calcium carbonate.
A thermosensitive recording paper was obtained in the same manner as in Example 1, except that No. (manufactured by Sakai Chemical Co., Ltd., average particle size of secondary particles 0.6 μm) was used.
比較例3
実施例1のオーバーコート履用塗液の調製において、超
微細軽質炭酸カルシウムの代わりに酸化珪素(商品名:
5P−11,徳山ソーダ社製、一次粒子の平均子粒径0
.30μm)を使用した以外は実施例1と同様にして感
熱記録紙を得た。Comparative Example 3 In the preparation of the overcoat shoe coating liquid of Example 1, silicon oxide (trade name:
5P-11, manufactured by Tokuyama Soda Co., Ltd., average particle size of primary particles 0
.. A thermosensitive recording paper was obtained in the same manner as in Example 1, except that 30 μm) was used.
比較例4
実施例1のオーバーコート要用塗液の調製において、超
微細軽質炭酸カルシウムの代わりに軽質炭酸カルシウム
(商品名:アルバグロス、ファイザー社製、−次粒子の
平均粒径0.6μm)を使用した以外は実施例1と同様
にして感熱記録紙を得た。Comparative Example 4 In the preparation of the coating solution for overcoating in Example 1, light calcium carbonate (trade name: Albagros, manufactured by Pfizer Inc., average particle size of secondary particles 0.6 μm) was used instead of ultrafine light calcium carbonate. A thermosensitive recording paper was obtained in the same manner as in Example 1 except that .
比較例5
実施例1のオーバーコート要用塗液の調製において、超
微細軽質炭酸カルシウムの代わりに重質炭酸カルシウム
(商品名:BF−100,備北粉化工業社製、−次粒子
の平均粒子径3.6μm)を使用した以外は実施例1と
同様にして感熱記録紙を得た。Comparative Example 5 In the preparation of the coating solution for overcoating in Example 1, heavy calcium carbonate (trade name: BF-100, manufactured by Bihoku Funka Kogyo Co., Ltd., average particle size of -2) was used instead of ultrafine light calcium carbonate. A thermosensitive recording paper was obtained in the same manner as in Example 1 except that a paper sheet (diameter: 3.6 μm) was used.
比較例6
比較例1のオーバーコート要用塗液の調製において、重
質炭酸カルシウム(商品名:ソフトン1500)の代わ
りに軽質炭酸カルシウム(商品名:PZ)を使用した以
外は比較例1と同様にして感熱記録紙を得た。Comparative Example 6 Same as Comparative Example 1 except that light calcium carbonate (trade name: PZ) was used instead of heavy calcium carbonate (trade name: Softon 1500) in the preparation of the coating solution that required overcoat in Comparative Example 1. A thermosensitive recording paper was obtained.
かくして得られた10種類の感熱記録紙を京セラ感熱シ
ュミレークー(電圧 16■、パルスサイクル 5m5
ec)を使用して、印字パルス時間0.35m5ecと
0.45m5ecで記録し、各々の発色濃度をマクベス
濃度計(RD−100R型、アンバーフィルター使用)
で測定し、結果を表に記載した。また、各記録像の白化
現象の程度を目視で評価し、白化現象の認められるもの
を×、白化現象が認められないものを○とし、その結果
を表に付記した。The 10 types of thermal recording papers obtained in this way were heated using a Kyocera thermal simulator (voltage: 16cm, pulse cycle: 5m5).
ec) was used to record printing pulse times of 0.35 m5 ec and 0.45 m5 ec, and each color density was measured using a Macbeth densitometer (RD-100R model, using an amber filter).
The results are listed in the table. In addition, the degree of whitening of each recorded image was visually evaluated, and those where whitening was observed were marked as x, and those where no whitening was observed were marked as ○, and the results were added to the table.
尚、発色濃度が低いのは、白化現象のためである。Note that the color density is low because of the whitening phenomenon.
次に、非印字部分に印鑑を押し、1分後にその朱肉部分
を指でこすって染着性を評価した。この場合、評価の基
準として上質紙(参考例1)を用い、これと同等の染着
性を有するものを○とし、染着性が悪いものを×、極め
て良いものを@とした。Next, a seal was placed on the non-printed area, and after 1 minute, the vermilion area was rubbed with a finger to evaluate the dyeability. In this case, high-quality paper (Reference Example 1) was used as the evaluation standard, and those with the same dyeability were marked as ○, those with poor dyeability were marked as ×, and those with very good dyeability were marked as @.
また、鉛筆(HB)で非印字部分に筆記してその書き易
さを評価した。これも上質紙を評価の基準としこれと同
等のものを○、筆記性の悪いものを×、極めて良いもの
を◎とした。In addition, the ease of writing was evaluated by writing on the non-printing area with a pencil (HB). In this case, high-quality paper was also used as the evaluation standard, and those equivalent to this paper were rated as ○, those with poor writing properties were rated as ×, and those with extremely good writing properties were rated as ◎.
また、ボールペンについても同様に評価した。Further, ballpoint pens were also evaluated in the same manner.
次に、軽く爪で引っ掻き(スクラッチ)その発色程度を
非オーバーコート感熱紙(参考例2)と比較し、その結
果を表に付記した。実用上スクラッチが良好なものをO
とし、非オーバーコート感熱紙を×とした。Next, the paper was lightly scratched with a fingernail and the degree of color development was compared with that of non-overcoated thermal paper (Reference Example 2), and the results are added to the table. O that has good scratch resistance in practical use
The non-overcoated thermal paper was rated as ×.
さらに、感熱ファクシミリ (NEFAX−27)で印
字し、スティッキングのレベルを評価した。Furthermore, printing was performed using a thermal facsimile (NEFAX-27) to evaluate the level of sticking.
スティッキングが良好なものを○とし、ややスティッキ
ングが認められるものをΔとした。Good sticking was evaluated as ○, and cases with slight sticking were evaluated as Δ.
「効果」
表から明らかな様に、本発明で得られた感熱記録体は、
白化現象及それに伴う画像濃度の低下がなく、朱肉の染
着性が極めて良好で筆記性も良く、しかもスティッキン
グの改良された極めて普通紙に近い特性を有する優れた
感熱記録体であった。"Effects" As is clear from the table, the heat-sensitive recording material obtained by the present invention has
It was an excellent heat-sensitive recording material with no whitening phenomenon or accompanying decrease in image density, very good ink dye adhesion, good writability, improved sticking, and properties very close to those of plain paper.
Claims (3)
接触して呈色しうる呈色剤を含有する感熱記録層上にオ
ーバーコート層を設けた感熱記録体において、該オーバ
ーコート層中に一次粒子の平均粒子径が0.2μm以下
の顔料を含有せしめたことを特徴とする感熱記録体。(1) In a heat-sensitive recording material in which an overcoat layer is provided on a heat-sensitive recording layer containing a colorless or light-colored basic dye and a coloring agent that can change color when it comes into contact with the basic dye, the overcoat layer contains a colorless or light-colored basic dye. 1. A heat-sensitive recording material comprising a pigment having an average primary particle diameter of 0.2 μm or less.
併用した請求項(1)記載の感熱記録体。(2) The heat-sensitive recording material according to claim (1), further comprising a pigment whose primary particles have an average particle diameter of 1.0 μm or more.
2−(4−メトキシフェノキシ)エタンを含有せしめた
請求項(1)〜(2)記載の感熱記録体。(3) 1-(2-methylphenoxy)- in the heat-sensitive recording layer
The heat-sensitive recording material according to claims (1) and (2), which contains 2-(4-methoxyphenoxy)ethane.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1334273A JPH03193387A (en) | 1989-12-22 | 1989-12-22 | Thermal recording body |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1334273A JPH03193387A (en) | 1989-12-22 | 1989-12-22 | Thermal recording body |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH03193387A true JPH03193387A (en) | 1991-08-23 |
Family
ID=18275495
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1334273A Pending JPH03193387A (en) | 1989-12-22 | 1989-12-22 | Thermal recording body |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH03193387A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6339041B1 (en) | 1998-10-19 | 2002-01-15 | Fuji Photo Film Co., Ltd. | Heat-sensitive recording material |
-
1989
- 1989-12-22 JP JP1334273A patent/JPH03193387A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6339041B1 (en) | 1998-10-19 | 2002-01-15 | Fuji Photo Film Co., Ltd. | Heat-sensitive recording material |
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