JPS62167086A - Thermal recording paper - Google Patents
Thermal recording paperInfo
- Publication number
- JPS62167086A JPS62167086A JP61008719A JP871986A JPS62167086A JP S62167086 A JPS62167086 A JP S62167086A JP 61008719 A JP61008719 A JP 61008719A JP 871986 A JP871986 A JP 871986A JP S62167086 A JPS62167086 A JP S62167086A
- Authority
- JP
- Japan
- Prior art keywords
- recording paper
- thermal recording
- methyl
- crystal
- ethylhexylaminofluorane
- 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
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000010586 diagram Methods 0.000 claims description 5
- 150000002440 hydroxy compounds Chemical class 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 14
- 230000009466 transformation Effects 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000000844 transformation Methods 0.000 abstract 2
- 238000001556 precipitation Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 description 14
- 238000012986 modification Methods 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- -1 phthalide compound Chemical class 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 239000000975 dye Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 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 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 2
- ZSBDGXGICLIJGD-UHFFFAOYSA-N 4-phenoxyphenol Chemical compound C1=CC(O)=CC=C1OC1=CC=CC=C1 ZSBDGXGICLIJGD-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WOROHGKCJHVOTH-UHFFFAOYSA-N N-ethyl-N-fluorohexan-1-amine Chemical compound C(CCCCC)N(CC)F WOROHGKCJHVOTH-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- WNZQDUSMALZDQF-UHFFFAOYSA-N isobenzofuranone Natural products C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JQCVPZXMGXKNOD-UHFFFAOYSA-N 1,2-dibenzylbenzene Chemical compound C=1C=CC=C(CC=2C=CC=CC=2)C=1CC1=CC=CC=C1 JQCVPZXMGXKNOD-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- DYULYMCXVSRUPB-UHFFFAOYSA-N 1,4-bis(phenylmethoxy)benzene Chemical compound C=1C=CC=CC=1COC(C=C1)=CC=C1OCC1=CC=CC=C1 DYULYMCXVSRUPB-UHFFFAOYSA-N 0.000 description 1
- AGPLQTQFIZBOLI-UHFFFAOYSA-N 1-benzyl-4-phenylbenzene Chemical group C=1C=C(C=2C=CC=CC=2)C=CC=1CC1=CC=CC=C1 AGPLQTQFIZBOLI-UHFFFAOYSA-N 0.000 description 1
- JWSWULLEVAMIJK-UHFFFAOYSA-N 1-phenylmethoxynaphthalene Chemical compound C=1C=CC2=CC=CC=C2C=1OCC1=CC=CC=C1 JWSWULLEVAMIJK-UHFFFAOYSA-N 0.000 description 1
- JTMODJXOTWYBOZ-UHFFFAOYSA-N 2-methyl-n-phenylaniline Chemical compound CC1=CC=CC=C1NC1=CC=CC=C1 JTMODJXOTWYBOZ-UHFFFAOYSA-N 0.000 description 1
- CYMPUOGZUXAIMY-UHFFFAOYSA-N 4-methoxy-2-methyl-n-phenylaniline Chemical compound CC1=CC(OC)=CC=C1NC1=CC=CC=C1 CYMPUOGZUXAIMY-UHFFFAOYSA-N 0.000 description 1
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- MOZDKDIOPSPTBH-UHFFFAOYSA-N Benzyl parahydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OCC1=CC=CC=C1 MOZDKDIOPSPTBH-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- XAUGWFWQVYXATQ-UHFFFAOYSA-N n-phenylbenzenesulfonamide Chemical compound C=1C=CC=CC=1S(=O)(=O)NC1=CC=CC=C1 XAUGWFWQVYXATQ-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-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
- 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
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000001993 wax Substances 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/323—Organic colour formers, e.g. leuco dyes
- B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
- B41M5/3275—Fluoran compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
【発明の詳細な説明】
「産業上の利用分野」
本発明はロイコ染料と顕色剤から成る感熱記録紙に関す
るものである。さらに詳しくはロイコ染料として２−ア
ニリノ−５−メチル−６−Ｎ−エチルヘキシルアミノフ
ルオランを使用した黒発色感熱記録紙に関するものであ
る。ロイコ染料方式の感熱記録紙は普通紙様の外観を有
し、−次発色で定着の必要が無い、無騒音で高速記録が
可能、安価でメンテナスフリー等の理由によシ、ファク
シミリ、各種プリンター、レコーダー用記録紙、ＰＯＳ
（Ｐｏｉｎｔ ｏｆ ５ａｌｅｓ）ラベル、乗車券に使
われ急速に需要が拡大している。DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a thermal recording paper comprising a leuco dye and a color developer. More specifically, the present invention relates to a black coloring thermosensitive recording paper using 2-anilino-5-methyl-6-N-ethylhexylaminofluoran as a leuco dye. Thermal recording paper using the leuco dye method has the appearance of plain paper, and is suitable for printing, facsimile, and various printers because it is color-forming and does not require fixing, can perform noiseless and high-speed recording, is inexpensive, and maintenance-free. , recorder paper, POS
(Point of 5ales) Used in labels and tickets, demand is rapidly increasing.
「従来技術」と「本発明が解決しようとする問題点」こ
のような感熱記録紙に用いられるロイコ染料は発色感度
、発色濃度、画像及び地肌の耐光性、保存性等に優れて
いることが必要である。本発明者らは先に特公昭５６−
５２７５９号公報に示した通り、２−アニＩＪ ／ −
３−メチル−６−Ｎ−エチルヘキシルアミノフルオラン
が発色感度等の諸性質に優れている事を明らかにしたが
、通常の晶析法で得られる融点１４９〜１５１″Ｃの結
晶を使用して感熱記録紙を製造すると得られた感熱記録
紙の地肌耐光性が不良（日光照射によシ地肌が黄変する
）である事が判明した。本発明はこの点を改善すべく鋭
意検討した結果到達したものである。``Prior art'' and ``Problems to be solved by the present invention'' The leuco dyes used in such thermal recording paper are known to have excellent coloring sensitivity, coloring density, light fastness of images and backgrounds, and storage stability. is necessary. The present inventors previously proposed the
As shown in Publication No. 52759, 2-AniIJ/-
It was revealed that 3-methyl-6-N-ethylhexylaminofluorane has excellent properties such as color development sensitivity, but it was found that 3-methyl-6-N-ethylhexylaminofluorane is excellent in various properties such as color development sensitivity. When producing thermal recording paper, it was found that the surface light resistance of the resulting thermal recording paper was poor (the surface yellowed when exposed to sunlight).The present invention was developed as a result of intensive studies to improve this point. It has been reached.
「問題点を解決する為の手段」と「作用」２−アニ１７
／ −３−メチル−６−Ｎ−エチルヘキシルアミノフ
ルオランの晶析法について種々検討した結果、本化合物
には２つの結晶変態があシ、これらの結晶変態の違いに
よって地肌耐光性が異る事が判った。“Means for solving problems” and “effects” 2-Ani 17
/ As a result of various studies on the crystallization method of -3-methyl-6-N-ethylhexylaminofluorane, we found that this compound has two crystal modifications, and that the surface light resistance differs depending on the difference in these crystal modifications. It turns out.
すなわち、通常の晶析法で得られる融点１４９〜１５１
″Ｃの結晶（α型変態と称する）は感熱記録紙の地肌耐
光性が不良で、溶媒量を減らし高温で晶析した融点１５
５〜１５７″Ｃの結晶（β型変態と称する）は地肌耐光
性が良好である。なお、類似化合物である２−アニリノ
−３−メチル−６−Ｎ−エチル−１Ｓ○−ペンチルアミ
ノフルオランにも融点１６５〜１６７℃と１７０〜１７
２℃の２つの結晶変態があるが、この化合物の場合には
、通常の晶析法で得られる低融点の方が地肌耐光性が良
い。That is, a melting point of 149 to 151 obtained by a normal crystallization method.
"C crystals (referred to as α-type modification) have poor light resistance on the surface of heat-sensitive recording paper, and crystals with a melting point of 15 are obtained by reducing the amount of solvent and crystallizing at a high temperature.
Crystals of 5 to 157″C (referred to as β-type modification) have good surface light resistance.In addition, the similar compound 2-anilino-3-methyl-6-N-ethyl-1S○-pentylaminofluorane Also melting point 165-167℃ and 170-17℃
There are two crystal modifications at 2°C, but in the case of this compound, the one with a lower melting point obtained by a normal crystallization method has better surface light resistance.
本発明に使用する２−アニリノ−３−メチル−６−Ｎ−
エチルヘキシルアミノフルオランは公知の次の方法によ
シ製造する事が出来る。2-anilino-3-methyl-6-N- used in the present invention
Ethylhexylaminofluorane can be produced by the following known method.
２−（２−ヒドロキシ−４−Ｎ−エチルへキシルアミノ
）ベンゾイル安息香酸（Ｉ）１モルと４−アルコキシ−
２−メチルジフェニルアミン（１）１モルとを濃硫酸等
の脱水縮合剤の存在下反応させてフタリド化合物（１）
を合成する。これをアルカリの存在下閉環する事により
無色の２−アニリノ−５−メチル−６−Ｎ−エチルヘキ
シルアミノフルオランが得られる。1 mol of 2-(2-hydroxy-4-N-ethylhexylamino)benzoylbenzoic acid (I) and 4-alkoxy-
A phthalide compound (1) is obtained by reacting 1 mole of 2-methyldiphenylamine (1) in the presence of a dehydration condensation agent such as concentrated sulfuric acid.
Synthesize. By ring-closing this in the presence of an alkali, colorless 2-anilino-5-methyl-6-N-ethylhexylaminofluorane is obtained.
次に合成例を挙げβ型変態及びα型変態の製造法を具体
的に説明する。Next, the production method of the β-type modification and the α-type modification will be specifically explained using synthesis examples.
合成例 １．−β型変態の製造−
９８％硫酸５ｏｙｒｌ中に２−（２−ヒトｃｔキシー４
−Ｎ−エチルへキシルアミノ）ベンゾイル安息香酸１８
．５ ｇと４−メトキシ−２−メチルジフェニルアミン
１２．８９を溶解し１０〜２０℃で４８時間反応した。Synthesis example 1. -Production of β-type metamorphosis- 2-(2-human ct xy4
-N-ethylhexylamino)benzoylbenzoic acid 18
．． 5 g and 12.89 g of 4-methoxy-2-methyldiphenylamine were dissolved and reacted at 10 to 20°C for 48 hours.
反応物を５００ｇの氷水中に注加し、析出したフタリド
化合物をｐ果した。得られたケーキにトルエン１００π
ｌと２０％水酸化ナトリウム水溶液７０罰を加えた後８
５でで３０分間かきまぜて閉環反応（脱メタノール）を
完了させた。The reaction product was poured into 500 g of ice water to remove the precipitated phthalide compound. Toluene 100π to the obtained cake
l and 20% sodium hydroxide aqueous solution 70 times after adding 8
5 for 30 minutes to complete the ring-closing reaction (de-methanol).
次いでトルエン層を分取しカーボンを加えて熱沖過後８
０″Ｃでトルエンを殆んど留去し同温度で結晶を析出さ
せた。濾過後乾燥してはｙ無色の２−アニリツー５−メ
チル−６−Ｎ−エチルヘキシルアミノフルオラン２２．
５’ｉを得た。ｍ、ｐ １５５〜１５７で これはβ型
変態であシ第１図の様なＸ線回析図を示す。Next, the toluene layer was separated, carbon was added, and after heating,
Most of the toluene was distilled off at 0''C, and crystals were precipitated at the same temperature.After filtration and drying, colorless 2-anili2-5-methyl-6-N-ethylhexylaminofluorane 22.
5'i was obtained. m, p 155-157 This indicates β-type modification and shows an X-ray diffraction diagram as shown in FIG.
合成例 ２．−α型変態の製造−
合成例１と同様に反応・閉環、カーボン濾過を行いトル
エン溶液を得た。この液を濃縮する事なく通常の方法で
冷却し結晶を得た。この結晶はｍ−ｐ１４９〜１５１℃
のα型変態であり、第２図の様なＸ線回析図を示す。Synthesis example 2. -Production of α-type modification- Reaction, ring closure, and carbon filtration were performed in the same manner as in Synthesis Example 1 to obtain a toluene solution. This liquid was cooled in a conventional manner without concentrating to obtain crystals. This crystal is m-p149~151℃
It is an α-type modification of , and shows an X-ray diffraction diagram as shown in FIG.
この様にして得たフルオラン化合物を使用して感熱記録
紙を製造するに轟っては公知の方法を採用する事が出来
る。例えば特公昭４５−１４０３９号公報に記載の方法
である。顕色剤、バインダー、増感剤等も公知のものを
使用する事が出来る。例えば次の様なものが挙げられる
。A known method can be used to produce heat-sensitive recording paper using the fluoran compound thus obtained. For example, there is a method described in Japanese Patent Publication No. 45-14039. Known color developers, binders, sensitizers, etc. can also be used. Examples include the following:
顕色剤；
４− ｔ＋３ｒｔ −７”チルフェノール、４−フェニ
ルフエノール、４−ヒドロキシジフェニルエーテル、α
−す７トール、β−ナットール、４−ヒドロキシ安息香
酸メチルエステル、４−ヒドロキシ安息香酸ベンジルエ
ステル、ビスフェノールＡ、４．４１−ジヒドロキシジ
フェニルスルホン、４−ヒドロキシ−４ｆ−メチルジフ
ェニルスルホン等ノ８０℃〜１８０℃ノ融点を有するヒ
ドロキシ化合物。Color developer; 4-t+3rt-7” thylphenol, 4-phenylphenol, 4-hydroxydiphenyl ether, α
-Su7tol, β-nuttol, 4-hydroxybenzoic acid methyl ester, 4-hydroxybenzoic acid benzyl ester, bisphenol A, 4,41-dihydroxydiphenylsulfone, 4-hydroxy-4f-methyldiphenylsulfone, etc. from 80°C to A hydroxy compound with a melting point of 180°C.
バインダー逼
ポリビニルアルコール、メチルセルローズ、ヒドロキシ
エチルセルローズ、カルポキシメチルセレイン酸共重合
物等の水溶性高分子物質。Binder: Water-soluble polymer substances such as polyvinyl alcohol, methyl cellulose, hydroxyethyl cellulose, and carpoxymethyl selenium copolymer.
増感剤；
尿素、無水フタル酸、アセトアニリド、ノくラフインろ
う、カルナウバろう、高級脂肪酸、高級脂肪酸エステル
、高級脂肪酸アミド、サリチル酸、フタル酸エステル、
テレフタル酸エステル、ナフトールベンジルエーテル、
１．４ジアルコキシナフタレン、ｍ−ターフェニル、Ｐ
−ベンジルビフェニル、ジベンジルベンゼン、１−ヒド
ロキシ−２−ナフトエ酸フェニル、４．４′−ジアルコ
キシジフェニルスルホン、ペンツアミド、ジフェニルア
ミン、ベンゼンスルホンアミド、ベンゼンスルホンアニ
リド、カルバゾール、ハイドロキノンジベンジルエーテ
ル、Ｐ−ベンジルオキシ安息香酸ベンジル等の融点７０
℃〜１５０℃の熱可融性物質。Sensitizer; urea, phthalic anhydride, acetanilide, nokurafuin wax, carnauba wax, higher fatty acid, higher fatty acid ester, higher fatty acid amide, salicylic acid, phthalic acid ester,
Terephthalic acid ester, naphthol benzyl ether,
1.4 dialkoxynaphthalene, m-terphenyl, P
-benzylbiphenyl, dibenzylbenzene, phenyl 1-hydroxy-2-naphthoate, 4,4'-dialkoxydiphenylsulfone, penzamide, diphenylamine, benzenesulfonamide, benzenesulfonanilide, carbazole, hydroquinone dibenzyl ether, P-benzyl Melting point of benzyl oxybenzoate etc. 70
Thermofusible material from °C to 150 °C.
「実施例等」
次に実施例、参考例、比較試験によシ本発明を具体的に
説明するが実施例はこれらに限定されるものではない。"Examples, etc." Next, the present invention will be specifically explained using Examples, Reference Examples, and Comparative Tests, but the Examples are not limited to these.
（実施例、参考例中の部は重量部を示す）
実施例τβ型変態を使用しての感熱記録紙の製造例−１
発色剤（ロイコ染料）分散液の調整
１０％ポリビニルアルコール水溶ｉ １００部
水 ８５部
上記上記物をペイントシェーカー（■東洋精機製）で発
色剤の平均粒子径が２ミクロンになるまで粉砕した。(Parts in Examples and Reference Examples indicate parts by weight) Example Production Example-1 of thermal recording paper using τβ type transformation
Preparation of dispersion of color former (leuco dye) 10% polyvinyl alcohol dissolved in water 100 parts Water 85 parts The above-mentioned product was pulverized using a paint shaker (■ Toyo Seiki Co., Ltd.) until the average particle size of the color former was 2 microns.
１１ 顕色剤、増感剤分散液（Ｂ液）の調整ビスフェノ
ールＡ １５部ステアリン酸亜鉛
１０部ステアリン酸アミド
２０部ｌＯ％ポリビニルアルコール水溶液
１５０部上記混合物をペイントシェーカーで平均粒
子径が３ミクロンになるまで粉砕した。11 Preparation of developer and sensitizer dispersion (solution B) Bisphenol A 15 parts Zinc stearate
10 parts stearic acid amide
20 parts lO% polyvinyl alcohol aqueous solution
150 parts of the above mixture was ground in a paint shaker until the average particle size was 3 microns.
１１１感熱塗液の調整及び塗工
Ａ液１０部、Ｂ液６．５部を混合攪拌して感熱塗液を得
た。この塗液をワイヤーバーで固形分重量が５９／ｍ”
となる様上質紙に均一に塗布後乾燥して感熱記録紙（イ
）を得た。Preparation and Coating of 111 Heat-Sensitive Coating Liquid 10 parts of liquid A and 6.5 parts of liquid B were mixed and stirred to obtain a heat-sensitive coating liquid. This coating liquid was coated with a wire bar until the solid content was 59/m”.
The mixture was coated uniformly on high quality paper and dried to obtain heat-sensitive recording paper (A).
参考例 −α型変態を使用しての感熱記録紙の製造例−
発色剤として２−アニリノ−３−メチル−Ｎ−エチルヘ
キシルアミノフルオランのβ型変態の代シにα型変態を
使用した以外は実施例と同様に操作して感熱記録紙（ロ
）を得た０
比較試験
本発明のβ型変態を使用した感熱記録紙（イ）とα型変
態を使用した感熱記録紙（ロ）の地肌射光ａｔフェード
テスターで試験した（照射時間 ２時間）。Reference example −Example of manufacturing thermal recording paper using α-type transformation−
Thermal recording paper (B) was obtained in the same manner as in Example except that α-type modification was used instead of β-type modification of 2-anilino-3-methyl-N-ethylhexylaminofluorane as a coloring agent. 0 Comparative Test Thermal recording paper (a) using β-type transformation of the present invention and thermal recording paper (b) using α-type transformation were tested using a background light AT fade tester (irradiation time: 2 hours).
結果は次の通シであった。The results were as follows.
「発明の効果」
本発明の感熱記録紙は２−アニリノ−３−メチル−６−
Ｎ−エチルヘキシルアミノフルオランの従来知られてい
なかった地肌耐光性の良い結晶変態を使用したものであ
シ産業上利用価値の高いものである。"Effects of the Invention" The thermal recording paper of the present invention has 2-anilino-3-methyl-6-
It uses a previously unknown crystal modification of N-ethylhexylaminofluorane with good surface light resistance, and is of high value for industrial use.
第１図は２−アニリノ−３−メチル−６−Ｎ−エチルヘ
キシルアミノフルオランのβ型変態のまた、第２図は同
α型変態のＸ線回析図である。
図において横軸は回析角（２θ）を表わし、縦軸は回折
強度を表わす０FIG. 1 is an X-ray diffraction diagram of the β-type modification of 2-anilino-3-methyl-6-N-ethylhexylaminofluorane, and FIG. 2 is an X-ray diffraction diagram of the α-type modification. In the figure, the horizontal axis represents the diffraction angle (2θ), and the vertical axis represents the diffraction intensity.
Claims (1)
熱時発色させるヒドロキシ化合物から成る感熱層を設け
た感熱記録紙において、ロイコ染料としてＣ＿１＿２−
Ｋα線によるＸ線回析法における回析角（２θ）１１．
８°、１２．４°、１６．１°、２１．６°、２１．８
°に強いピークを示すＸ線回析図により特徴づけられる
融点１５５℃〜１５７℃の２−アニリノ−３−メチル−
６−Ｎ−エチルヘキシルアミノフルオランを使用した事
を特徴とする感熱記録紙。(1) In a thermal recording paper provided with a heat-sensitive layer consisting of a normally colorless or light-colored leuco dye and a hydroxy compound that causes the leuco dye to develop color when heated, the leuco dye is C_1_2-
Diffraction angle (2θ) in X-ray diffraction method using Kα rays11.
8°, 12.4°, 16.1°, 21.6°, 21.8
2-anilino-3-methyl- with a melting point of 155°C to 157°C, characterized by an X-ray diffraction diagram showing a strong peak at
A thermal recording paper characterized by using 6-N-ethylhexylaminofluorane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61008719A JPS62167086A (en) | 1986-01-17 | 1986-01-17 | Thermal recording paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61008719A JPS62167086A (en) | 1986-01-17 | 1986-01-17 | Thermal recording paper |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62167086A true JPS62167086A (en) | 1987-07-23 |
Family
ID=11700751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61008719A Pending JPS62167086A (en) | 1986-01-17 | 1986-01-17 | Thermal recording paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62167086A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5283222A (en) * | 1990-06-19 | 1994-02-01 | Mitsui Toatsu Chemicals, Inc. | Recording material comprising novel crystalline fluoran and process for prepartion of the said crystalline fluoran |
-
1986
- 1986-01-17 JP JP61008719A patent/JPS62167086A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5283222A (en) * | 1990-06-19 | 1994-02-01 | Mitsui Toatsu Chemicals, Inc. | Recording material comprising novel crystalline fluoran and process for prepartion of the said crystalline fluoran |
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