JPWO2015125861A1 - Thermal recording material - Google Patents
Thermal recording material Download PDFInfo
- Publication number
- JPWO2015125861A1 JPWO2015125861A1 JP2016504157A JP2016504157A JPWO2015125861A1 JP WO2015125861 A1 JPWO2015125861 A1 JP WO2015125861A1 JP 2016504157 A JP2016504157 A JP 2016504157A JP 2016504157 A JP2016504157 A JP 2016504157A JP WO2015125861 A1 JPWO2015125861 A1 JP WO2015125861A1
- Authority
- JP
- Japan
- Prior art keywords
- bis
- heat
- recording material
- sensitive recording
- sulfone
- 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
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
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- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical class C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
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- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FEEPBTVZSYQUDP-UHFFFAOYSA-N heptatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O FEEPBTVZSYQUDP-UHFFFAOYSA-N 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- HFRLHSQAZLWVEE-HZJYTTRNSA-N linoleylanilide Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)NC1=CC=CC=C1 HFRLHSQAZLWVEE-HZJYTTRNSA-N 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
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- DLKDXCZRLIQWMN-UHFFFAOYSA-N n,n-diethyl-7-fluorooctan-3-amine Chemical compound CCN(CC)C(CC)CCCC(C)F DLKDXCZRLIQWMN-UHFFFAOYSA-N 0.000 description 1
- HNUFCQUTJXHEPI-UHFFFAOYSA-N n-methyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NC HNUFCQUTJXHEPI-UHFFFAOYSA-N 0.000 description 1
- ZOLJFBQEKSZVCB-UHFFFAOYSA-N n-phenyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NC1=CC=CC=C1 ZOLJFBQEKSZVCB-UHFFFAOYSA-N 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 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
- 125000001181 organosilyl group Chemical group [SiH3]* 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- WMIWKXQBBHIBDO-UHFFFAOYSA-N phenyl 1-hydroxy-2h-naphthalene-1-carboxylate Chemical compound C1C=CC2=CC=CC=C2C1(O)C(=O)OC1=CC=CC=C1 WMIWKXQBBHIBDO-UHFFFAOYSA-N 0.000 description 1
- BBTGZLICINVWQG-UHFFFAOYSA-N phenyl 2,4,6-trimethylbenzenesulfonate Chemical compound CC1=CC(C)=CC(C)=C1S(=O)(=O)OC1=CC=CC=C1 BBTGZLICINVWQG-UHFFFAOYSA-N 0.000 description 1
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- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000004897 thiazines Chemical class 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
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/337—Additives; Binders
- B41M5/3375—Non-macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
- B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
- B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/04—Direct thermal recording [DTR]
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
支持体上に設けた感熱記録層は通常無色ないし淡色の発色性化合物、該発色性化合物を熱時発色させうる顕色性化合物及び増感剤を主要成分とする感熱記録材料を含む。本発明においては、α型の結晶を有するビス（３−アリル−４−ヒドロキシフェニル）スルホンとビス（ｐ−アリルオキシフェニル）スルホンとの重量比が７：３〜６：４の割合で含まれる感熱記録材料とする。The heat-sensitive recording layer provided on the support usually contains a colorless or light-coloring color developing compound, a color developing compound capable of developing the color developing compound when heated, and a heat sensitive recording material mainly composed of a sensitizer. In the present invention, the weight ratio of bis (3-allyl-4-hydroxyphenyl) sulfone having α-type crystals to bis (p-allyloxyphenyl) sulfone is included in a ratio of 7: 3 to 6: 4. A heat-sensitive recording material is used.
Description
本発明は感熱記録材料に関する。更に詳しくは、発色記録した後の発色画像の保存安定性に優れた感熱記録材料に関する。 The present invention relates to a heat-sensitive recording material. More specifically, the present invention relates to a heat-sensitive recording material having excellent storage stability of a color image after color recording.
感熱記録材料は、一般に発色性化合物とフェノール性物質等の顕色性化合物とをそれぞれ別個に微粒子状に分散化後、両者を混合し、これに結合剤、増感剤、充填剤、滑剤等の添加剤を添加して塗液とし、紙、フィルム、合成紙等に塗布したものであり、加熱により発色性化合物と顕色性化合物の一方又は両者が溶融、接触して起こる化学反応により発色記録を得る。このような感熱記録材料の発色のためには、サーマルヘッドを内蔵したサーマルプリンター等が用いられる。この感熱記録法は他の記録法に比較して、（１）記録時に騒音がでない、（２）現像、定着等の必要がない、（３）メンテナンスフリーである、（４）機械が比較的安価である等の特徴により、ファクシミリ分野、コンピューターのアウトプット、電卓等で利用されるプリンターの分野、医療計測用のレコーダー分野、自動券売機分野、感熱記録型ラベル分野等に広く用いられている。 In general, a heat-sensitive recording material is obtained by dispersing a coloring compound and a developing compound such as a phenolic substance separately into fine particles, and then mixing both of them together with a binder, a sensitizer, a filler, a lubricant, etc. Additive additive is used as a coating liquid, and is applied to paper, film, synthetic paper, etc., and color is developed by chemical reaction that occurs when one or both of the color developing compound and the color developing compound are melted and contacted by heating. Get a record. For the color development of such a heat-sensitive recording material, a thermal printer or the like with a built-in thermal head is used. Compared to other recording methods, this thermal recording method is (1) no noise during recording, (2) no need for development, fixing, etc. (3) maintenance-free, (4) machine relatively It is widely used in the fields of facsimile, computer output, printers used in calculators, medical measurement recorders, automatic ticket vending machines, thermal recording labels, etc. .
近年、感熱記録材料の使用用途が拡大すると共に、より生産性を向上させるため高速記録に対する要求が一段と高くなり、高速記録に十分対応しうる感熱記録材料の開発が強く望まれている。しかし、一般に感熱記録材料の感度を高めて熱応答性を良くすると、製造時、使用時あるいは保管時に発色画像の保存安定性が低下するという欠点があらわれやすくなる。そこで、以前より感熱記録材料の発色部（印字部）についての安定性の向上が望まれている。
このような発色画像の保存安定性等の良好な感熱記録材料を開発する試みは種々行われており、例えば文献１〜３等には、２，４’−ジヒドロキシジフェニルスルホンを顕色性化合物として使用して、画像の保存安定性等を向上できるとする感熱記録材料が記載されている。しかし、これらの感熱記録材料では、発色性や耐可塑剤性（保存安定性）は未だ不十分であった。In recent years, the use of thermal recording materials has been expanded, and the demand for high-speed recording has been further increased in order to further improve productivity, and development of a thermal recording material that can sufficiently cope with high-speed recording is strongly desired. However, generally, when the sensitivity of the heat-sensitive recording material is increased to improve the thermal response, there is a tendency that the storage stability of the color image is lowered during production, use or storage. Therefore, it has been desired to improve the stability of the coloring portion (printing portion) of the thermosensitive recording material.
Various attempts have been made to develop such heat-sensitive recording materials such as storage stability of color images. For example, in References 1 to 3 and the like, 2,4′-dihydroxydiphenylsulfone is used as a color developing compound. A heat-sensitive recording material is described that can be used to improve the storage stability of an image. However, these heat-sensitive recording materials still have insufficient color developability and plasticizer resistance (storage stability).
本発明の目的は、前記の従来技術の欠点を解決し、発色性に優れ、且つ発色画像の保存安定性、特に耐可塑剤性に優れる、感熱記録材料を提供することにある。 An object of the present invention is to solve the above-mentioned drawbacks of the prior art, and to provide a heat-sensitive recording material having excellent color developability and excellent storage stability of a color image, particularly plasticizer resistance.
本発明者は、前記目的を達成すべく種々の検討を重ねた結果、本発明を完成させたものである。 The present inventor has completed the present invention as a result of various studies to achieve the above object.
即ち本発明は、以下の感熱記録材料に関する。
（１）発色性化合物と、α型の結晶を有するビス（３−アリル−４−ヒドロキシフェニル）スルホンとビス（ｐ−アリルオキシフェニル）スルホンとを含み、α型の結晶を有するビス（３−アリル−４−ヒドロキシフェニル）スルホンとビス（ｐ−アリルオキシフェニル）スルホンとの重量比が７：３〜６：４である感熱記録材料、
（２）前記発色性化合物が３−ジブチルアミノ−６−メチル−７−アニリノフルオランである（１）に記載の感熱記録材料、及び
（３）（１）または（２）に記載の感熱記録材料を含む感熱記録層。That is, the present invention relates to the following heat-sensitive recording material.
(1) Bis (3-allyl-4-hydroxyphenyl) sulfone having α-type crystals and bis (3-allyloxyphenyl) sulfone having α-type crystals and having α-type crystals A thermosensitive recording material in which the weight ratio of allyl-4-hydroxyphenyl) sulfone to bis (p-allyloxyphenyl) sulfone is 7: 3 to 6: 4;
(2) The thermosensitive recording material according to (1), wherein the color forming compound is 3-dibutylamino-6-methyl-7-anilinofluorane, and (3) the thermosensitive material according to (1) or (2). A heat-sensitive recording layer containing a recording material.
本発明により、発色性及び発色画像の保存安定性、特に耐可塑剤性に優れた感熱記録材料を提供する事が出来る。 According to the present invention, it is possible to provide a heat-sensitive recording material excellent in color developability and storage stability of a color image, in particular, plasticizer resistance.
本発明を詳細に説明する。本発明の感熱記録材料は、主成分として、発色性化合物と、α型の結晶を有するビス（３−アリル−４−ヒドロキシフェニル）スルホン及びビス（ｐ−アリルオキシフェニル）スルホンとの混合物を含み、必要に応じて、他の顕色性化合物、及び増感剤、結合剤、充填剤、その他の添加物の１種又は２種以上を含んでもよい。 The present invention will be described in detail. The heat-sensitive recording material of the present invention contains, as a main component, a mixture of a color-forming compound and bis (3-allyl-4-hydroxyphenyl) sulfone and bis (p-allyloxyphenyl) sulfone having α-type crystals. If necessary, other color developing compounds and one or more of sensitizers, binders, fillers, and other additives may be included.
本発明に用いられるα型の結晶を有するビス（３−アリル−４−ヒドロキシフェニル）スルホンは、特開平１１−２９５４９号に基づき合成できる。また、ビス（ｐ−アリルオキシフェニル）スルホンは特開昭６１−０８９０９０号に基づき合成できる。 Bis (3-allyl-4-hydroxyphenyl) sulfone having α-type crystals used in the present invention can be synthesized based on JP-A-11-29549. Bis (p-allyloxyphenyl) sulfone can be synthesized based on JP-A 61-089090.
本発明における感熱記録材料中に含まれる主な各成分の含有率であるが、発色性化合物は通常１〜５０重量％、好ましくは５〜３０重量％である。α型の結晶を有するビス（３−アリル−４−ヒドロキシフェニル）スルホン及びビス（ｐ−アリルオキシフェニル）スルホンの総量は通常１〜７０重量％、好ましくは１０〜５０重量％である。増感剤の含有率は通常１〜８０重量％であり、結合剤の含有率は通常１〜９０重量％であり、充填剤の含有率は通常０〜８０重量％である。更に、α型の結晶を有するビス（３−アリル−４−ヒドロキシフェニル）スルホン及びビス（ｐ−アリルオキシフェニル）スルホンの総量は、発色性化合物に対して、重量比で、通常０．５〜２０倍であり、より好ましくは１〜５倍である。
また、α型の結晶を有するビス（３−アリル−４−ヒドロキシフェニル）スルホンとビス（ｐ−アリルオキシフェニル）スルホンとの重量比は７：３〜６：４である。その他、滑剤、界面活性剤、消泡剤、紫外線吸収剤等は各々任意の割合で通常０〜３０重量％の範囲で含ませることができる。本発明の感熱記録材料は、これらの成分以外にも、他の顕色性化合物、又は増感剤、その他の添加物を含むことができる。The content of each main component contained in the heat-sensitive recording material in the present invention is usually 1 to 50% by weight, preferably 5 to 30% by weight of the color forming compound. The total amount of bis (3-allyl-4-hydroxyphenyl) sulfone and bis (p-allyloxyphenyl) sulfone having α-type crystals is usually 1 to 70% by weight, preferably 10 to 50% by weight. The content of the sensitizer is usually 1 to 80% by weight, the content of the binder is usually 1 to 90% by weight, and the content of the filler is usually 0 to 80% by weight. Furthermore, the total amount of bis (3-allyl-4-hydroxyphenyl) sulfone and bis (p-allyloxyphenyl) sulfone having α-type crystals is usually 0.5 to 0.5 by weight with respect to the chromogenic compound. It is 20 times, more preferably 1 to 5 times.
The weight ratio of bis (3-allyl-4-hydroxyphenyl) sulfone having α-type crystals to bis (p-allyloxyphenyl) sulfone is 7: 3 to 6: 4. In addition, lubricants, surfactants, antifoaming agents, ultraviolet absorbers, and the like can be included in an arbitrary ratio, usually in the range of 0 to 30% by weight. In addition to these components, the heat-sensitive recording material of the present invention can contain other color developing compounds, sensitizers, and other additives.
本発明に用いられる発色性化合物は、一般に感圧記録紙や感熱記録紙に用いられるものであればよく、例えばフルオラン系化合物、トリアリールメタン系化合物、スピロ系化合物、ジフェニルメタン系化合物、チアジン系化合物、ラクタム系化合物、フルオレン系化合物等が挙げられ、フルオラン系化合物が好ましい。 The color-forming compound used in the present invention may be any compound that is generally used for pressure-sensitive recording paper and heat-sensitive recording paper. For example, a fluorane compound, a triarylmethane compound, a spiro compound, a diphenylmethane compound, and a thiazine compound. , Lactam compounds, fluorene compounds and the like, and fluoran compounds are preferred.
フルオラン系化合物の具体例としては、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−ジブチルアミノ−６−メチル−７−アニリノフルオラン、３−（Ｎ−メチル−Ｎ−シクロヘキシルアミノ）−６−メチル−７−アニリノフルオラン、３−（Ｎ−エチル−Ｎ−イソペンチルアミノ）−６−メチル−７−アニリノフルオラン、３−（Ｎ−エチル−Ｎ−イソブチルアミノ）−６−メチル−７−アニリノフルオラン、３−［Ｎ−エチル−Ｎ−（３−エトキシプロピル）アミノ］−６−メチル−７−アニリノフルオラン、３−（Ｎ−エチル−Ｎ−ヘキシルアミノ）−６−メチル−７−アニリノフルオラン、３−ジペンチルアミノ−６−メチル−７−アニリノフルオラン、３−（Ｎ−メチル−Ｎ−プロピルアミノ）−６−メチル−７−アニリノフルオラン、３−（Ｎ−エチル−Ｎ−テトラヒドロフリルアミノ）−６−メチル−７−アニリノフルオラン、３−ジエチルアミノ−６−メチル−７−（ｐ−クロロアニリノ）フルオラン、３−ジエチルアミノ−６−メチル−７−（ｐ−フルオロアニリノ）フルオラン、３−［Ｎ−エチル−Ｎ−（ｐ−トリル）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−メチル−７−（ｐ−トルイジノ）フルオラン、３−ジエチルアミノ−７−（ｏ−クロロアニリノ）フルオラン、３−ジブチルアミノ−７−（ｏ−クロロアニリノ）フルオラン、３−ジエチルアミノ−７−（ｏ−フルオロアニリノ）フルオラン、３−ジブチルアミノ−７−（ｏ−フルオロアニリノ）フルオラン、３−ジエチルアミノ−７−（３，４−ジクロロアニリノ）フルオラン、３−ピロリジノ−６−メチル−７−アニリノフルオラン、３−ジエチルアミノ−６−クロロ−７−エトキシエチルアミノフルオラン、３−ジエチルアミノ−６−クロロ−７−アニリノフルオラン、３−ジエチルアミノ−７−クロロフルオラン、３−ジエチルアミノ−７−メチルフルオラン、３−ジエチルアミノ−７−オクチルフルオラン、３−［Ｎ−エチル−Ｎ−（ｐ−トリル）アミノ］−６−メチル−７−フェネチルフルオラン等が挙げられ、３−ジブチルアミノ−６−メチル−７−アニリノフルオランが好ましい。 Specific examples of the fluorane compound include 3-diethylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3- (N-methyl-N- Cyclohexylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isopentylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isobutyl) Amino) -6-methyl-7-anilinofluorane, 3- [N-ethyl-N- (3-ethoxypropyl) amino] -6-methyl-7-anilinofluorane, 3- (N-ethyl- N-hexylamino) -6-methyl-7-anilinofluorane, 3-dipentylamino-6-methyl-7-anilinofluorane, 3- (N-methyl-N-propylamino) -6-me Ru-7-anilinofluorane, 3- (N-ethyl-N-tetrahydrofurylamino) -6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7- (p-chloroanilino) fluorane 3-diethylamino-6-methyl-7- (p-fluoroanilino) fluorane, 3- [N-ethyl-N- (p-tolyl) amino] -6-methyl-7-anilinofluorane, 3- Diethylamino-6-methyl-7- (p-toluidino) fluorane, 3-diethylamino-7- (o-chloroanilino) fluorane, 3-dibutylamino-7- (o-chloroanilino) fluorane, 3-diethylamino-7- (o -Fluoroanilino) fluorane, 3-dibutylamino-7- (o-fluoroanilino) fluorane, 3-diethylamino-7- 3,4-dichloroanilino) fluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-diethylamino-6-chloro-7-ethoxyethylaminofluorane, 3-diethylamino-6-chloro-7 -Anilinofluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-7-methylfluorane, 3-diethylamino-7-octylfluorane, 3- [N-ethyl-N- (p-tolyl) Amino] -6-methyl-7-phenethylfluorane and the like, and 3-dibutylamino-6-methyl-7-anilinofluorane is preferred.
トリアリールメタン系化合物の具体例としては、例えば３，３−ビス（ｐ−ジメチルアミノフェニル）−６−ジメチルアミノフタリド（別名：クリスタルバイオレットラクトン又はＣＶＬ）、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−ジメチルアミノインドール−３−イル）フタリド、３−（ｐ−ジメチルアミノフェニル）−３−（２−メチルインドール−３−イル）フタリド、３−（ｐ−ジメチルアミノフェニル）−３−（２−フェニルインドール−３−イル）フタリド、３，３−ビス（１，２−ジメチルインドール−３−イル）−５−ジメチルアミノフタリド、３，３−ビス（１，２−ジメチルインドール−３−イル）−６−ジメチルアミノフタリド、３，３−ビス（９−エチルカルバゾール−３−イル）−５−ジメチルアミノフタリド、３，３−（２−フェニルインドール−３−イル）−５−ジメチルアミノフタリド、３−ｐ−ジメチルアミノフェニル−３−（１−メチルピロール−２−イル）−６−ジメチルアミノフタリド等が挙げられる。 Specific examples of triarylmethane compounds include, for example, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (also known as crystal violet lactone or CVL), 3,3-bis (p-dimethyl). Aminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethylaminoindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindole- 3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-phenylindol-3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5 Dimethylaminophthalide, 3,3-bis (1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3,3-bis 9-ethylcarbazol-3-yl) -5-dimethylaminophthalide, 3,3- (2-phenylindol-3-yl) -5-dimethylaminophthalide, 3-p-dimethylaminophenyl-3- ( 1-methylpyrrol-2-yl) -6-dimethylaminophthalide and the like.
スピロ系化合物の具体例としては、例えば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、３，３’−ジクロロ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−プロピルスピロベンゾピラン、３−メチルナフト−（３−メトキシベンゾ）スピロピラン、１，３，３−トリメチル−６−ニトロ−８’−メトキシスピロ（インドリン−２，２’−ベンゾピラン）等が挙げられる。ジフェニルメタン系化合物の具体例としては、例えばＮ−ハロフェニル−ロイコオーラミン、４，４−ビス−ジメチルアミノフェニルベンズヒドリルベンジルエーテル、Ｎ−２，４，５−トリクロロフェニルロイコオーラミン等が挙げられる。チアジン系化合物の具体例としては、例えば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が挙げられる。ラクタム系化合物の具体例としては、例えばローダミンＢアニリノラクタム、ローダミンＢ−ｐ−クロロアニリノラクタム等が挙げられる。フルオレン系化合物の具体例としては、例えば３，６−ビス（ジメチルアミノ）フルオレンスピロ（９，３’）−６’−ジメチルアミノフタリド、３，６−ビス（ジメチルアミノ）フルオレンスピロ（９，３’）−６’−ピロリジノフタリド、３−ジメチルアミノ−６−ジエチルアミノフルオレンスピロ（９，３’）−６’−ピロリジノフタリド等が挙げられる。これらの発色性化合物は単独もしくは混合して用いられる。 Specific examples of the spiro compound include, for example, 3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran, 3,3′-dichlorospirodinaphthopyran, 3-benzylspirodinaphthopyran, 3-propylspirobenzo. Examples include pyran, 3-methylnaphtho- (3-methoxybenzo) spiropyran, 1,3,3-trimethyl-6-nitro-8′-methoxyspiro (indoline-2,2′-benzopyran) and the like. Specific examples of the diphenylmethane compound include N-halophenyl-leucooramine, 4,4-bis-dimethylaminophenylbenzhydrylbenzyl ether, N-2,4,5-trichlorophenylleucooramine, and the like. . Specific examples of thiazine compounds include benzoyl leucomethylene blue and p-nitrobenzoyl leucomethylene blue. Specific examples of the lactam compound include rhodamine B anilinolactam and rhodamine Bp-chloroanilinolactam. Specific examples of the fluorene compound include, for example, 3,6-bis (dimethylamino) fluorene spiro (9,3 ′)-6′-dimethylaminophthalide, 3,6-bis (dimethylamino) fluorene spiro (9, 3 ′)-6′-pyrrolidinophthalide, 3-dimethylamino-6-diethylaminofluorene spiro (9,3 ′)-6′-pyrrolidinophthalide, and the like. These color forming compounds are used alone or in combination.
本発明において併用可能な顕色性化合物としては、特に制限されないが、一般に感圧記録紙や感熱記録紙に用いられているものであればよく、例えばα−ナフトール、β−ナフトール、ｐ−オクチルフェノール、４−ｔ−オクチルフェノール、ｐ−ｔ−ブチルフェノール、ｐ−フェニルフェノール、１，１−ビス（ｐ−ヒドロキシフェニル）プロパン、２，２−ビス（ｐ−ヒドロキシフェニル）プロパン（別名：ビスフェノールＡ又はＢＰＡ）、２，２−ビス（ｐ−ヒドロキシフェニル）ブタン、１，１−ビス（ｐ−ヒドロキシフェニル）シクロヘキサン、４，４’−チオビスフェノール、４，４’−シクロ−ヘキシリデンジフェノール、２，２’−ビス（２，５−ジブロム−４−ヒドロキシフェニル）プロパン、４，４’−イソプロピリデンビス（２−ｔ−ブチルフェノール）、２，２’−メチレンビス（４−クロロフェノール）、４，４’−ジヒドロキシジフェニルスルホン、４−ヒドロキシ−４’−メト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’−エトキシジフェニルスルホン、４−ヒドロキシ−４’−ブトキシジフェニルスルホン、４−ヒドロキシ−４’−ベンジルオキシジフェニルスルホン、ビス（４−ヒドロキシフェニル）酢酸メチル、ビス（４−ヒドロキシフェニル）酢酸ブチル、ビス（４−ヒドロキシフェニル）酢酸ベンジル、２，４−ジヒドロキシ−２’−メトキシベンズアニリド等のフェノール性化合物、ｐ−ヒドロキシ安息香酸ベンジル、ｐ−ヒドロキシ安息香酸エチル、４−ヒドロキシフタル酸ジベンジル、４−ヒドロキシフタル酸ジメチル、５−ヒドロキシイソフタル酸エチル、３，５−ジ−ｔ−ブチルサリチル酸、３，５−ジ−α−メチルベンジルサリチル酸等の芳香族カルボン酸誘導体、芳香族カルボン酸又はその多価金属塩等が挙げられる。 The color developing compound that can be used in combination in the present invention is not particularly limited, and may be any compound that is generally used for pressure-sensitive recording paper and heat-sensitive recording paper. For example, α-naphthol, β-naphthol, p-octylphenol. 4-tert-octylphenol, pt-butylphenol, p-phenylphenol, 1,1-bis (p-hydroxyphenyl) propane, 2,2-bis (p-hydroxyphenyl) propane (also known as bisphenol A or BPA) ), 2,2-bis (p-hydroxyphenyl) butane, 1,1-bis (p-hydroxyphenyl) cyclohexane, 4,4′-thiobisphenol, 4,4′-cyclo-hexylidene diphenol, 2, 2'-bis (2,5-dibromo-4-hydroxyphenyl) propane, 4,4'-isopropylidene Bis (2-t-butylphenol), 2,2′-methylenebis (4-chlorophenol), 4,4′-dihydroxydiphenylsulfone, 4-hydroxy-4′-methoxydiphenylsulfone, 2,4′-dihydroxydiphenylsulfone 4-hydroxy-4′-isopropoxydiphenylsulfone, 4-hydroxy-4′-ethoxydiphenylsulfone, 4-hydroxy-4′-butoxydiphenylsulfone, 4-hydroxy-4′-benzyloxydiphenylsulfone, bis (4 Phenolic compounds such as -hydroxyphenyl) methyl acetate, bis (4-hydroxyphenyl) butyl acetate, bis (4-hydroxyphenyl) acetate benzyl, 2,4-dihydroxy-2'-methoxybenzanilide, p-hydroxybenzoic acid Benzyl, p- Such as ethyl droxybenzoate, dibenzyl 4-hydroxyphthalate, dimethyl 4-hydroxyphthalate, ethyl 5-hydroxyisophthalate, 3,5-di-t-butylsalicylic acid, 3,5-di-α-methylbenzylsalicylic acid, etc. An aromatic carboxylic acid derivative, an aromatic carboxylic acid or a polyvalent metal salt thereof can be used.
本発明に用いられる増感剤（熱可融性化合物）の具体例としては、例えば動植物性ワックス、合成ワックスなどのワックス類、高級脂肪酸、高級脂肪酸アミド、高級脂肪酸アニリド、ナフタレン誘導体、芳香族エーテル、芳香族カルボン酸誘導体、芳香族スルホン酸エステル誘導体、炭酸又はシュウ酸ジエステル誘導体、ビフェニル誘導体、ターフェニル誘導体、スルホン誘導体等が挙げられ、中でも常温では固体で、融点が６０℃以上のものが好ましく使用される。 Specific examples of the sensitizer (thermofusible compound) used in the present invention include, for example, waxes such as animal and vegetable waxes and synthetic waxes, higher fatty acids, higher fatty acid amides, higher fatty acid anilides, naphthalene derivatives, aromatic ethers. , Aromatic carboxylic acid derivatives, aromatic sulfonic acid ester derivatives, carbonic acid or oxalic acid diester derivatives, biphenyl derivatives, terphenyl derivatives, sulfone derivatives, etc. Among them, those which are solid at room temperature and have a melting point of 60 ° C. or higher are preferable. used.
ワックス類の具体例としては、例えば木ろう、カルナウバろう、シェラック、パラフィン、モンタンろう、酸化パラフィン、ポリエチレンワックス、酸化ポリエチレン等が挙げられる。高級脂肪酸としては、例えばステアリン酸、ベヘン酸等が挙げられる。高級脂肪酸アミドとしては、例えばステアリン酸アミド、オレイン酸アミド、Ｎ−メチルステアリン酸アミド、エルカ酸アミド、メチロールベヘン酸アミド、メチレンビスステアリン酸アミド、エチレンビスステアリン酸アミド等が挙げられる。高級脂肪酸アニリドとしては、例えばステアリン酸アニリド、リノール酸アニリド等が挙げられる。ナフタレン誘導体としては、例えば１−ベンジルオキシナフタレン、２−ベンジルオキシナフタレン、１−ヒドロキシナフトエ酸フェニルエステル等が挙げられる。芳香族エーテルとしては、例えば１，２−ジフェノキシエタン、１，４−ジフェノキシブタン、１，２−ビス（３−メチルフェノキシ）エタン、１，２−ビス（４−メトキシフェノキシ）エタン、１，２−ビス（３，４−ジメチルフェニル）エタン、１−フェノキシ−２−（４−クロロフェノキシ）エタン、１−フェノキシ−２−（４−メトキシフェノキシ）エタン、１，２−ジフェノキシメチルベンゼン等が挙げられる。芳香族カルボン酸誘導体としては、例えばｐ−ヒドロキシ安息香酸ベンジルエステル、ｐ−ベンジルオキシ安息香酸ベンジルエステル、テレフタル酸ジベンジルエステル等が挙げられる。芳香族スルホン酸エステル誘導体としては、例えばｐ−トルエンスルホン酸フェニルエステル、フェニルメシチレンスルホナート、４−メチルフェニルメシチレンスルホナート等が挙げられる。炭酸又はシュウ酸ジエステル誘導体としては、例えば炭酸ジフェニル、シュウ酸ジベンジルエステル、シュウ酸ジ（４−クロロベンジル）エステル、シュウ酸ジ（４−メチルベンジル）エステル類が挙げられる。ビフェニル誘導体としては、例えばｐ−ベンジルビフェニル、ｐ−アリルオキシビフェニル等が挙げられる。ターフェニル誘導体としては、例えばｍ−ターフェニル等；スルホン誘導体としては、例えばジフェニルスルホン等が挙げられる。 Specific examples of waxes include, for example, wood wax, carnauba wax, shellac, paraffin, montan wax, oxidized paraffin, polyethylene wax, oxidized polyethylene and the like. Examples of higher fatty acids include stearic acid and behenic acid. Examples of the higher fatty acid amide include stearic acid amide, oleic acid amide, N-methyl stearic acid amide, erucic acid amide, methylol behenic acid amide, methylene bis stearic acid amide, and ethylene bis stearic acid amide. Examples of the higher fatty acid anilide include stearic acid anilide and linoleic acid anilide. Examples of naphthalene derivatives include 1-benzyloxynaphthalene, 2-benzyloxynaphthalene, 1-hydroxynaphthoic acid phenyl ester and the like. Examples of the aromatic ether include 1,2-diphenoxyethane, 1,4-diphenoxybutane, 1,2-bis (3-methylphenoxy) ethane, 1,2-bis (4-methoxyphenoxy) ethane, 1 , 2-bis (3,4-dimethylphenyl) ethane, 1-phenoxy-2- (4-chlorophenoxy) ethane, 1-phenoxy-2- (4-methoxyphenoxy) ethane, 1,2-diphenoxymethylbenzene Etc. Examples of the aromatic carboxylic acid derivative include p-hydroxybenzoic acid benzyl ester, p-benzyloxybenzoic acid benzyl ester, and terephthalic acid dibenzyl ester. Examples of the aromatic sulfonic acid ester derivative include p-toluenesulfonic acid phenyl ester, phenyl mesitylene sulfonate, 4-methylphenyl mesitylene sulfonate, and the like. Examples of the carbonic acid or oxalic acid diester derivative include diphenyl carbonate, oxalic acid dibenzyl ester, oxalic acid di (4-chlorobenzyl) ester, and oxalic acid di (4-methylbenzyl) ester. Examples of the biphenyl derivative include p-benzylbiphenyl and p-allyloxybiphenyl. Examples of the terphenyl derivative include m-terphenyl and the like, and examples of the sulfone derivative include diphenylsulfone and the like.
本発明に用いられる結合剤の具体例としては、例えばメチルセルロース、メトキシセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース、ナトリウムカルボキシメチルセルロース、セルロース、ポリビニルアルコール（ＰＶＡ）、カルボキシル基変性ポリビニルアルコール、スルホン酸基変性ポリビニルアルコール、シリル基変性ポリビニルアルコール、ポリビニルピロリドン、ポリアクリルアミド、ポリアクリル酸、デンプン及びその誘導体、カゼイン、ゼラチン、水溶性イソプレンゴム、スチレン／無水マレイン酸共重合体のアルカリ塩、イソ（又はジイソ）ブチレン／無水マレイン酸共重合体のアルカリ塩等の水溶性の結合剤；並びに（メタ）アクリル酸エステル共重合体、スチレン／（メタ）アクリル酸エステル共重合体、ポリウレタン、ポリエステル系ポリウレタン、ポリエーテル系ポリウレタン、ポリ酢酸ビニル、エチレン／酢酸ビニル共重合体、ポリ塩化ビニル、塩化ビニル／酢酸ビニル共重合体、ポリ塩化ビニリデン、ポリスチレン、スチレン／ブタジエン（ＳＢ）共重合体、カルボキシル化スチレン／ブタジエン（ＳＢ）共重合体、スチレン／ブタジエン／アクリル酸系共重合体、アクリロニトリル／ブタジエン（ＮＢ）共重合体、カルボキシル化アクリロニトリル／ブタジエン（ＮＢ）共重合体、コロイダルシリカと（メタ）アクリル樹脂の複合体粒子等の疎水性高分子エマルジョン等が挙げられる。 Specific examples of the binder used in the present invention include, for example, methyl cellulose, methoxy cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, cellulose, polyvinyl alcohol (PVA), carboxyl group-modified polyvinyl alcohol, sulfonic acid group-modified polyvinyl alcohol, Silyl group-modified polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polyacrylic acid, starch and derivatives thereof, casein, gelatin, water-soluble isoprene rubber, alkali salt of styrene / maleic anhydride copolymer, iso (or diiso) butylene / anhydrous Water-soluble binder such as alkali salt of maleic acid copolymer; and (meth) acrylic acid ester copolymer, styrene / (meth) acrylic acid ester Polymer, polyurethane, polyester polyurethane, polyether polyurethane, polyvinyl acetate, ethylene / vinyl acetate copolymer, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, polyvinylidene chloride, polystyrene, styrene / butadiene (SB) ) Copolymer, carboxylated styrene / butadiene (SB) copolymer, styrene / butadiene / acrylic acid copolymer, acrylonitrile / butadiene (NB) copolymer, carboxylated acrylonitrile / butadiene (NB) copolymer, Examples include hydrophobic polymer emulsions such as composite particles of colloidal silica and (meth) acrylic resin.
本発明に用いられる充填剤の具体例としては、例えば炭酸カルシウム、炭酸マグネシウム、酸化マグネシウム、シリカ、ホワイトカーボン、タルク、クレー、アルミナ、水酸化マグネシウム、水酸化アルミニウム、酸化アルミニウム、硫酸バリウム、ポリスチレン樹脂、尿素−ホルマリン樹脂等が挙げられる。 Specific examples of the filler used in the present invention include, for example, calcium carbonate, magnesium carbonate, magnesium oxide, silica, white carbon, talc, clay, alumina, magnesium hydroxide, aluminum hydroxide, aluminum oxide, barium sulfate, polystyrene resin. And urea-formalin resin.
更に本発明においては上記以外の種々の添加剤を使用することができ、例えばサーマルヘッド磨耗防止、スティッキング防止等の目的でのステアリン酸亜鉛、ステアリン酸カルシウム等の高級脂肪酸金属塩を使用することができる。また、酸化防止あるいは老化防止効果を付与する為にフェノール誘導体、ベンゾフェノン系化合物、ベンゾトリアゾール系化合物等の紫外線吸収剤を使用することができる。また、各種の界面活性剤、消泡剤を使用してもよい。 Further, in the present invention, various additives other than those described above can be used. For example, higher fatty acid metal salts such as zinc stearate and calcium stearate for the purpose of preventing thermal head wear and sticking can be used. . In addition, in order to impart an antioxidant or anti-aging effect, an ultraviolet absorber such as a phenol derivative, a benzophenone compound, or a benzotriazole compound can be used. Various surfactants and antifoaming agents may be used.
次に、本発明の感熱記録材料の調製方法を説明する。例えば、発色性化合物、α型の結晶を有するビス（３−アリル−４−ヒドロキシフェニル）スルホン及びビス（ｐ−アリルオキシフェニル）スルホンを、それぞれ別々に結合剤あるいは必要に応じてその他の添加剤等と共にボールミル、アトライター、サンドミル等の分散機にて粉砕、分散化した後、各分散液を混合して（通常、粉砕や分散を湿式で行うときは水を媒体として用いる）、本発明の感熱記録材料を得ることができる。本発明の感熱記録材料からなる塗布液は、紙（普通紙、上質紙、コート紙等が使用出来る）、プラスチックシート、合成紙等の支持体上に通常乾燥重量で１〜２０ｇ／ｍ２になるようにバーコーター、ブレードコーター等により塗布、乾燥することで、本発明の感熱記録材料を含む感熱記録層を作製することができる。
また、必要に応じて感熱記録層と支持体の間に中間層を設けたり、感熱記録層上にオーバーコート層（保護層）を設けても良い。中間層、オーバーコート層（保護層）は、例えば前記の結合剤あるいは必要に応じてその他の添加物と共に、感熱記録材料の調製におけるのと同様に必要に応じて粉砕、分散して中間層用塗布液又はオーバーコート層（保護層）用塗布液とした後、乾燥時の重量で通常０．１〜１０ｇ／ｍ２程度となるように塗布し、乾燥することにより設けられる。Next, a method for preparing the heat-sensitive recording material of the present invention will be described. For example, a chromogenic compound, bis (3-allyl-4-hydroxyphenyl) sulfone having α-type crystals, and bis (p-allyloxyphenyl) sulfone, each separately as a binder or other additives as required Etc. together with a ball mill, an attritor, a sand mill, etc. A heat-sensitive recording material can be obtained. The coating liquid comprising the heat-sensitive recording material of the present invention is usually 1 to 20 g / m 2 in dry weight on a support such as paper (plain paper, high-quality paper, coated paper, etc.), plastic sheet, synthetic paper or the like. By applying and drying with a bar coater, a blade coater or the like, a heat-sensitive recording layer containing the heat-sensitive recording material of the present invention can be produced.
If necessary, an intermediate layer may be provided between the heat-sensitive recording layer and the support, or an overcoat layer (protective layer) may be provided on the heat-sensitive recording layer. For the intermediate layer, the intermediate layer and overcoat layer (protective layer) are pulverized and dispersed as necessary, for example, in the same manner as in the preparation of the heat-sensitive recording material, together with the binder or other additives as required. After the coating solution or the coating solution for the overcoat layer (protective layer) is formed, the coating solution is applied by drying so that the weight is usually about 0.1 to 10 g / m 2 and dried.
本発明を実施例により更に具体的に説明するが、本発明はこれらに限定されるものではない。実施例中「部」は重量部、溶液の説明における「％」は重量％である。 The present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. In the examples, “parts” are parts by weight, and “%” in the description of the solution is% by weight.
実施例１
（感熱記録材料の作製）
下記組成でサンドグラインダーを用いて平均粒径が１μｍ以下になるように粉砕、分散化して［Ａ］液を調製した。Example 1
(Preparation of thermal recording material)
A [A] solution was prepared by pulverizing and dispersing using a sand grinder with the following composition so that the average particle size was 1 μm or less.
［Ａ］液：ビス（ｐ−アリルオキシフェニル）スルホン ２５部
２５％ＰＶＡ水溶液 ２０部
水 ５５部[A] Liquid: 25 parts of bis (p-allyloxyphenyl) sulfone
20 parts of 25% PVA aqueous solution
55 parts of water
下記組成の混合物をサンドグラインダーを用いて平均粒径が１μｍ以下になるように粉砕、分散化してそれぞれ［Ｂ］液、［Ｃ］液を調製した。
［Ｂ］液：
３−ジブチルアミノ−６−メチル−７−アニリノフルオラン ３５部
１５％ＰＶＡ水溶液 ４０部
水 ２５部
［Ｃ］液：
α型結晶のビス（３−アリル−４−ヒドロキシフェニル）スルホン
（特開平１１−２９５４９号を参照） ２５部
２５％ＰＶＡ水溶液 ２０部
水 ５５部A mixture of the following composition was pulverized and dispersed using a sand grinder so that the average particle size was 1 μm or less to prepare a [B] solution and a [C] solution, respectively.
[B] Liquid:
3-dibutylamino-6-methyl-7-anilinofluorane 35 parts 15% PVA aqueous solution 40 parts water 25 parts [C] solution:
α-type bis (3-allyl-4-hydroxyphenyl) sulfone (see JP-A-11-29549) 25 parts 25% PVA aqueous solution 20 parts water 55 parts
次いで、上記で得られた［Ａ］乃至［Ｃ］液と、６７％炭酸カルシウム水分散液、変性スチレン・ブタジエン共重合体ラテックス及び水とを下記の割合で混合して感熱記録材料を調製し、坪量５０ｇ／ｍ２の上質紙上に乾燥時の重量が５ｇ／ｍ２となるように塗布、乾燥して本発明の感熱記録材料を含む感熱記録層を有する試料を作製した。なおこの場合のα型の結晶を有するビス（３−アリル−４−ヒドロキシフェニル）スルホンとビス（ｐ−アリルオキシフェニル）スルホンの重量比は７：３である。
［Ａ］液 ７．２部
［Ｂ］液 ８．６部
［Ｃ］液 １６．８部
６７％炭酸カルシウム水分散液 ９．０部
４８％変性スチレン・ブタジエン共重合体ラテックス ６．３部
水 ５２．１部Next, the [A] to [C] liquid obtained above, 67% calcium carbonate aqueous dispersion, modified styrene / butadiene copolymer latex and water are mixed in the following ratio to prepare a heat sensitive recording material. A sample having a heat-sensitive recording layer containing the heat-sensitive recording material of the present invention was prepared by applying and drying on a high-quality paper having a basis weight of 50 g / m 2 so that the weight upon drying was 5 g / m 2 . In this case, the weight ratio of bis (3-allyl-4-hydroxyphenyl) sulfone and bis (p-allyloxyphenyl) sulfone having α-type crystals is 7: 3.
[A] liquid 7.2 parts [B] liquid 8.6 parts [C] liquid 16.8 parts 67% calcium carbonate aqueous dispersion 9.0 parts 48% modified styrene / butadiene copolymer latex 6.3 parts water 52.1 copies
（保護層の形成）
次に下記組成からなる保護層塗布液を前記の感熱記録層上に乾燥時の重量が２ｇ／ｍ２となるように塗布、乾燥して保護層付きの感熱記録層を有する試料を得た。
４０％スチレン／アクリル酸エステル共重合体エマルジョン １１５部
５％ベントナイト水分散液 １７部
４５％スチレン・アクリル共重合体水性エマルジョン ４４部
３９％ステアリン酸亜鉛水分散液 １０３部
６７％炭酸カルシウム水分散液 １５部(Formation of protective layer)
Next, a protective layer coating solution having the following composition was applied onto the heat-sensitive recording layer so that the weight upon drying was 2 g / m 2 and dried to obtain a sample having a heat-sensitive recording layer with a protective layer.
40% styrene / acrylic ester copolymer emulsion 115 parts 5% bentonite aqueous dispersion 17 parts 45% styrene / acrylic copolymer aqueous emulsion 44 parts 39% zinc stearate aqueous dispersion 103 parts 67% calcium carbonate aqueous dispersion 15 copies
実施例２及び３
感熱記録材料の組成を下表１に記載の組成に変更した以外は実施例１と同様にして、本発明の感熱記録材料を有する試料を得た。Examples 2 and 3
A sample having the heat-sensitive recording material of the present invention was obtained in the same manner as in Example 1 except that the composition of the heat-sensitive recording material was changed to the composition shown in Table 1 below.
比較例１及び２
感熱記録材料の組成を下表１に記載の組成に変更した以外は実施例１と同様にして、比較用の感熱記録材料を有する試料を得た。Comparative Examples 1 and 2
A sample having a comparative thermal recording material was obtained in the same manner as in Example 1 except that the composition of the thermal recording material was changed to the composition shown in Table 1 below.
表１中の比率とは、α型の結晶を有するビス（３−アリル−４−ヒドロキシフェニル）スルホンとビス（ｐ−アリルオキシフェニル）スルホンの重量比を示す。
The ratio in Table 1 indicates the weight ratio of bis (3-allyl-4-hydroxyphenyl) sulfone and bis (p-allyloxyphenyl) sulfone having α-type crystals.
［発色性試験］
上記実施例１〜３により得られた本発明の感熱記録材料、比較例１及び２により得られた比較用の感熱記録材料、を含む感熱記録層を有する各試料を、市販のサーマルプリンター（イシダＬ−２０００）で印字し、印字部分（発色部）のマクベス反射濃度をマクベス反射濃度計（ＲＤ−９１４型、マクベス社製）で測定した。結果を下表２に示す。なお、マクベス反射濃度が高い程、発色性に優れていることがわかる。
［耐可塑剤性試験］
上記実施例１〜３により得られた本発明の感熱記録材料、比較例１及び２により得られた比較用の感熱記録材料、を含む感熱記録層を有する各試料を、市販のサーマルプリンター（イシダＬ−２０００）で印字し、各試料をＰＶＣラップフィルムで挟んで室温で２４時間放置した。試験前後の各試料の発色部のマクベス反射濃度をマクベス反射濃度計（ＲＤ−９１４型、マクベス社製）で測定した。結果を下表２に示す。
なお、残存率が高い程、耐可塑剤性に優れることがわかる。残存率は以下の計算式で求めた。
残存率（％）＝試験後の試料の発色部のマクベス反射濃度／試験前の試料の発色部のマクベス反射濃度×１００[Color development test]
Each sample having a heat-sensitive recording layer containing the heat-sensitive recording material of the present invention obtained in Examples 1 to 3 and the heat-sensitive recording material for comparison obtained in Comparative Examples 1 and 2 was used as a commercially available thermal printer (Ishida). L-2000), and the Macbeth reflection density of the printed portion (color development portion) was measured with a Macbeth reflection densitometer (RD-914 type, manufactured by Macbeth Co.). The results are shown in Table 2 below. It can be seen that the higher the Macbeth reflection density, the better the color developability.
[Plasticizer resistance test]
Each sample having a heat-sensitive recording layer containing the heat-sensitive recording material of the present invention obtained in Examples 1 to 3 and the heat-sensitive recording material for comparison obtained in Comparative Examples 1 and 2 was used as a commercially available thermal printer (Ishida). L-2000), and each sample was sandwiched between PVC wrap films and allowed to stand at room temperature for 24 hours. The Macbeth reflection density of the colored portion of each sample before and after the test was measured with a Macbeth reflection densitometer (RD-914 type, manufactured by Macbeth Co.). The results are shown in Table 2 below.
In addition, it turns out that it is excellent in plasticizer resistance, so that a residual rate is high. The residual rate was calculated by the following formula.
Residual rate (%) = Macbeth reflection density of the coloring part of the sample after the test / Macbeth reflection density of the coloring part of the sample before the test × 100
表２中の比率とは、α型の結晶を有するビス（３−アリル−４−ヒドロキシフェニル）スルホンとビス（ｐ−アリルオキシフェニル）スルホンの重量比を示す。
The ratio in Table 2 indicates the weight ratio of bis (3-allyl-4-hydroxyphenyl) sulfone and bis (p-allyloxyphenyl) sulfone having α-type crystals.
表２の結果から、発色性及び耐可塑剤性において、実施例１〜３の試料は比較例１及び２の試料と比べて極めて優れることが分かる。 From the results in Table 2, it can be seen that the samples of Examples 1 to 3 are extremely superior to the samples of Comparative Examples 1 and 2 in terms of color developability and plasticizer resistance.
以上の通り、発色性化合物と、α型の結晶を有するビス（３−アリル−４−ヒドロキシフェニル）スルホンと、ビス（ｐ−アリルオキシフェニル）スルホンとを含み、α型の結晶を有するビス（３−アリル−４−ヒドロキシフェニル）スルホンと、ビス（ｐ−アリルオキシフェニル）スルホンとの重量比が７：３〜６：４の範囲である感熱記録材料は、従来の感熱記録材料に比べて発色性に優れ、且つ及び発色記録部の耐可塑剤性（保存安定性）に優れている。 As described above, the bis (3-allyl-4-hydroxyphenyl) sulfone having a chromogenic compound, α-type crystals, and bis (p-allyloxyphenyl) sulfone, and having α-type crystals ( The thermosensitive recording material in which the weight ratio of 3-allyl-4-hydroxyphenyl) sulfone and bis (p-allyloxyphenyl) sulfone is in the range of 7: 3 to 6: 4 is compared with the conventional thermosensitive recording material. Excellent color developability and excellent plasticizer resistance (storage stability) of the color recording part.
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| JP2014031649 | 2014-02-21 | ||
| JP2014031649 | 2014-02-21 | ||
| PCT/JP2015/054604 WO2015125861A1 (en) | 2014-02-21 | 2015-02-19 | Heat-sensitive recording material |
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| JPH08175024A (en) * | 1994-12-26 | 1996-07-09 | Mitsubishi Paper Mills Ltd | Thermal recording material |
| JP3992252B2 (en) * | 1997-05-14 | 2007-10-17 | 日本化薬株式会社 | Thermosensitive recording material and new crystals of bisphenol S derivative |
| JP2002079758A (en) * | 2000-09-05 | 2002-03-19 | Nippon Kayaku Co Ltd | Thermal recording material |
| JP2005066881A (en) * | 2003-08-27 | 2005-03-17 | Mitsubishi Paper Mills Ltd | Double-sided recording medium |
| JP2006044093A (en) * | 2004-08-05 | 2006-02-16 | Nicca Chemical Co Ltd | Thermosensitive recording material |
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