US3846153A - Heat sensitive composition and thermal recording sheet containing the same - Google Patents

Heat sensitive composition and thermal recording sheet containing the same Download PDF

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Publication number
US3846153A
US3846153A US00274618A US27461872A US3846153A US 3846153 A US3846153 A US 3846153A US 00274618 A US00274618 A US 00274618A US 27461872 A US27461872 A US 27461872A US 3846153 A US3846153 A US 3846153A
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US
United States
Prior art keywords
color
recording sheet
thermal recording
compound
lactone
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.)
Expired - Lifetime
Application number
US00274618A
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English (en)
Inventor
K Futaki
I Kohmura
K Haino
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Mitsubishi Paper Mills Ltd
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Mitsubishi Paper Mills Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsubishi Paper Mills Ltd filed Critical Mitsubishi Paper Mills Ltd
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Publication of US3846153A publication Critical patent/US3846153A/en
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    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31942—Of aldehyde or ketone condensation product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31942—Of aldehyde or ketone condensation product
    • Y10T428/31949—Next to cellulosic
    • Y10T428/31964—Paper
    • Y10T428/31967—Phenoplast

Definitions

  • the present invention relates to a heat sensitive composition which comprises combination of an ordinarily colorless or light-colored color forming lactone compound and -a phenol compound. Furthermore, the present invention concerns a thermal recording sheet which contains said composition.
  • ground color of the sheet must be colorless or light color
  • it must rapidly form deep color at a certain temperature e.g., a temperature of 70 C.- 200 C.
  • the color formed must be clear and fully stable against light and moisture
  • It is extremely difiicult to produce thermal recording sheet which satisfies all of the above requirements. The most difficult requirement is to improve preservability.
  • This purpose may be attained by setting the color forming temperature of the heat sensitive composition at a high level, but in this case a large amount of heat is required for recording. Thus, a large amount of electric power is required for thermal pen or thermal printer and high speed recording becomes difiicult. Therefore, such method is practically disadvantageous.
  • color forming temperature is set at a low level, recording can be carried out with a small amount of electric power. In this case, however, the stability of the part of the sheet where no color is formed is lowered and the possibility of color-forming during preservation increases.
  • thermal recording sheet as being highly stable at room temperature and having a color-forming temperature of as low as possible is desired, but it is very difiicult to produce a heat sensitive composition which simultaneously meets the above two requirements.
  • the thermal recording sheet is often inadvertently placed near a heater or other heat sources and therefore, special care must be given in handl-ing of the thermal recording sheet which has too low color forming temperature. Therefore, a thermal recording sheet which rapidly forms color at a temperature of about -l00 C. and is highly stable at room temperature has been desired for practical use. To meet such requirements has been technically very difiicult.
  • the color forming temperature has a close relation with melting point of the compounds which constitute the heat sensitive composition.
  • a color forming lactone compound and a phenol which are solid at room temperature are separately ground to a particle size of less than about several microns in solvents which do not dissolve them with use of e.g. a ball mill. Thereafter, they are mixed and the mixture is applied together with a binder to a paper and is dried to obtain a thermal recording sheet.
  • the preservability and stability of the thermal recording sheet are low and not only it gradually forms color at room temperature, but it has the s-o-called phenol smell.
  • Diphenols include compounds excellent for thermal recording sheet and when 4,4'-cyclohexylidene diphenol (melting point: C.) or 4,4- is'opropylidene diphenol (melting point: 156 C.) is used, such sheet as having clear thermal color formation and practically high stability can be obtained.
  • the color forming temperature is too high and in case of the latter compound, the color forming temperature is sometimes also too high. Therefore, the recording sheet having lower color forming temperature without damaging practical stability and preservability has been demanded.
  • this heat sensitive composition comprises combination of at least one of ordinarily colorless or light-colored color forming lactone compounds, namely, Leuco Lactone dye and P,'P'-(l-rnethyl-normal hexylidene)diphenol having the following chemical formula,
  • the color forming lactone compounds used in the present invention mean the ordinarily colorless or light-colored lactone compounds capable of reacting with said phenol compound to form color.
  • the representative examples of such lactone compounds are the following triphenylmethane l'actones, fluorans, benzofluorans, etc., but the present invention is not limited to use of only these compounds.
  • Crystal Violet lactone Malachite Green lactone, 3,3-bis (paradimethyl aminophenyl)-6-aminophthalide, 3,3 bis (paradimethylaminophenyl) 6 (paratoluenesulfonamide)phthalide, 3 diethylamino-7-dibenzylamino-fluoran, 3-diethylamino 7 (N-methylanilino)-fiuoran, 3-diethyl amino 7 (N-methyl-p-toluidino)-fluoran, B-dimethylamino 6 methoxy-fluoran, 3-diethylamino-6-methyl-7- chloro-fiuoran, 3-dibutylarnino-6-methyl-7-chloro-fluoran, 3-diethylamino-7-phenylfluoran, 3-morpholino-5,6-benzofluoran.
  • the general method for producing the thermal recording sheet of the present invention is as follows: The phenol compound as mentioned above and the ordinarily colorless or light-colored color forming lactone compound are separately ground together with a binder in a medium which does not dissolve said compounds by ball mill to obtain dispersion liquids. Then, these liquids are mixed. The mixture is applied to a substrate sheet and dried. Alternatively, each dispersion liquid is applied to a substrate sheet in order or one of them is contained in a substrate sheet and the other is applied to the substrate sheet.
  • the substrate sheet is paper, fine powders of both compounds may be incorporated into the paper at paper making step or one of them may be impregnated in paper as a solution and the other dispersion may be applied to the paper.
  • water or petroleums are suitable.
  • binder water soluble high polymer compounds such as polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, styrene, butadiene or acrylic latex may be employed in case of using water as the medium and terpene resins, cyclized rubber, etc. may be used in case of using petroleums as the medium.
  • Suitable amounts of the lactone compound, the phenol compound and the binder are 13()% by Weight, 45-94% by Weight and -40% by weight (these are dry weight percent), resepectively. If necessary, talc, waxes, surface active agents, defoaming agents etc. may be added to improve application state and recording state. Furthermore, a protective layer may be provided onto the heat sensitive layer to further improve the stability.
  • EXAMPLE 1 Liquid A G. Crystal Violet lactone 1 5% Aqueous solution of hydroxyethyl cellulose (HEC BL-lS manufactured by Fuji Chemical Co.) 5 Water 4.4
  • Liquid B P,P'-(lmethyl-normal hexylidene)diphenol 5 5% Aqueous solution of hydroxyethyl cellulose Water 22 Said liquids A and B were separately ground for 2 days in ball mill to produce two dispersion liquids. Then, the two were mixed and the mixed liquid was applied to an ordinary paper having a basis weight of 50 g./m. and dried. The amount of the applied liquid was about 3 g./m. expressed by dry weight.
  • thermal recording sheet was stable at room temperature and the ground color of the applied layer was substantially white and rapidly formed blue color at about 90 C. When a letter was copied with heating, a clear recording of the letter was obtained.
  • FIG. 1 shows the relation between color forming temperature at which color is formed in high density for a short period of time and density of ground color formed after lapse of one week at 40 C. of thermal recording sheets using various phenol compounds. In other words, it shows the relation between color forming temperature and stability (density of ground color after one Week at 40 C.).
  • white dot indicates that the color forming speed was high (i.e.: quick response) and black dot indicates that the color forming speed was low (i.e.: slow response).
  • the recording sheet containing the present phenol compound (X) formed color at the preferred temperature of relatively lower temperature as compared with the recording sheets containing compounds (I) and (II).
  • the sheets formed color at a preferred temperature of relatively low temperature, but had practically fatal defects. That is, in case of the compounds (111) and (VIII), when liquids A and B were mixed, the liquid severely formed color and hence the liquid when applied to sheet caused formation of deep ground color, which was not practically desired.
  • Example 1 was repeated except that 3-dibutylamino-6- methyl-7-chlorofluoran was substituted for Crystal Violet lactone to obtain an excellent thermal recording sheet which formed red color with heat in substantially white ground.
  • a thermal recording sheet which contains the phenol compound having the formula:
  • a heat sensitive room temperature stable composition comprising the phenol compound having the formula:
  • composition comprising 1-30% by weight of the lactone compound

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  • 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)
  • Coloring (AREA)
US00274618A 1971-08-05 1972-07-24 Heat sensitive composition and thermal recording sheet containing the same Expired - Lifetime US3846153A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP5914371A JPS5412819B2 (en, 2012) 1971-08-05 1971-08-05

Publications (1)

Publication Number Publication Date
US3846153A true US3846153A (en) 1974-11-05

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ID=13104796

Family Applications (1)

Application Number Title Priority Date Filing Date
US00274618A Expired - Lifetime US3846153A (en) 1971-08-05 1972-07-24 Heat sensitive composition and thermal recording sheet containing the same

Country Status (4)

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US (1) US3846153A (en, 2012)
JP (1) JPS5412819B2 (en, 2012)
DE (1) DE2237288C3 (en, 2012)
GB (1) GB1354058A (en, 2012)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4321309A (en) * 1979-06-01 1982-03-23 Sanyo-Kokusaku Pulp Co., Ltd. Heat-sensitive recording material
US4420538A (en) * 1981-01-13 1983-12-13 Murata Manufacturing Co., Ltd. Heat-sensitive recording materials
US4531141A (en) * 1983-01-17 1985-07-23 Minnesota Mining And Manufacturing Company Heat-sensitive composition and imaging sheet incorporating same
US4631084A (en) * 1983-01-17 1986-12-23 Minnesota Mining And Manufacturing Company Heat-sensitive composition and imaging sheet incorporating same
US4808565A (en) * 1986-08-14 1989-02-28 Minnesota Mining And Manufacturing Company Thermal imaging material
US4829046A (en) * 1987-10-15 1989-05-09 Minnesota Mining And Manufacturing Company Positive-acting thermographic materials
US4902668A (en) * 1988-08-25 1990-02-20 Minnesota Mining And Manufacturing Company Pressure sensitive carbonless imaging system incorporating uncolored ferric organophosphates and colored chelates
US4902667A (en) * 1988-08-25 1990-02-20 Minnesota Mining And Manufacturing Company Pressure sensitive carbonless imaging system incorporating uncolored ferric organophosphates and uncolored chelates
US4910186A (en) * 1987-10-15 1990-03-20 Minnesota Mining And Manufacturing Company Positive-acting thermographic materials
WO2004043704A1 (en) 2002-11-12 2004-05-27 Sherwood Technology Limited Use of transition metal compounds in imageable coatings

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2186516A1 (en) * 1972-05-30 1974-01-11 Pilot Ink Co Ltd Thermochromatic temp. indicating compsns. - contg. org. electron donors and phenolic cpds.
CH578432A5 (en, 2012) * 1973-03-05 1976-08-13 Ciba Geigy Ag
JPS5925674B2 (ja) * 1976-09-22 1984-06-20 神崎製紙株式会社 感熱記録シ−ト
US4151748A (en) * 1977-12-15 1979-05-01 Ncr Corporation Two color thermally sensitive record material system
JPS54155059A (en) * 1978-05-26 1979-12-06 Mitsubishi Paper Mills Ltd Heat sensitive paper preventing ground color generation
JPS5581769A (en) * 1978-12-16 1980-06-20 Satake Eng Co Ltd Automatic controller of oscillating cereal selecting disc
JPS55104742A (en) * 1979-02-02 1980-08-11 Satake Eng Co Ltd Measuring device of mixed rate of different kind grain mixture
JPS55157366A (en) * 1979-05-28 1980-12-08 Satake Eng Co Ltd Discharger for oscillation selecting machine
JPS56100678A (en) * 1980-01-12 1981-08-12 Satake Eng Co Ltd Automatic controller for cereal grain selector
JPS56100679A (en) * 1980-01-16 1981-08-12 Satake Eng Co Ltd Automatic controller for cereal selector
JPS56108576A (en) * 1980-02-01 1981-08-28 Satake Eng Co Ltd Controller for movement of separating wall of cereal selector
JPS56130284A (en) * 1980-03-18 1981-10-13 Iseki Agricult Mach Extractor for separated cereal grain in oscillation type cereal specific gravity selector
JPS5743896A (en) * 1980-08-29 1982-03-12 Mitsui Toatsu Chem Inc Recording material
JPS5898178A (ja) * 1981-12-04 1983-06-10 セイレイ工業株式会社 揺動選別機の仕切板制御装置
JPS5973084A (ja) * 1982-10-18 1984-04-25 セイレイ工業株式会社 殻粒選別選粒装置
JPS5980380A (ja) * 1983-09-22 1984-05-09 株式会社　サタケ 揺動選別機の穀粒検出装置
JPS60216876A (ja) * 1984-04-12 1985-10-30 セイレイ工業株式会社 粒選別機における整粒取出し方法とその装置
JPH01167380U (en, 2012) * 1988-05-11 1989-11-24

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1135540A (en) * 1966-06-01 1968-12-04 Ncr Co Temperature responsive record material

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4321309A (en) * 1979-06-01 1982-03-23 Sanyo-Kokusaku Pulp Co., Ltd. Heat-sensitive recording material
US4420538A (en) * 1981-01-13 1983-12-13 Murata Manufacturing Co., Ltd. Heat-sensitive recording materials
US4531141A (en) * 1983-01-17 1985-07-23 Minnesota Mining And Manufacturing Company Heat-sensitive composition and imaging sheet incorporating same
US4631084A (en) * 1983-01-17 1986-12-23 Minnesota Mining And Manufacturing Company Heat-sensitive composition and imaging sheet incorporating same
US4808565A (en) * 1986-08-14 1989-02-28 Minnesota Mining And Manufacturing Company Thermal imaging material
US4829046A (en) * 1987-10-15 1989-05-09 Minnesota Mining And Manufacturing Company Positive-acting thermographic materials
US4910186A (en) * 1987-10-15 1990-03-20 Minnesota Mining And Manufacturing Company Positive-acting thermographic materials
US4902668A (en) * 1988-08-25 1990-02-20 Minnesota Mining And Manufacturing Company Pressure sensitive carbonless imaging system incorporating uncolored ferric organophosphates and colored chelates
US4902667A (en) * 1988-08-25 1990-02-20 Minnesota Mining And Manufacturing Company Pressure sensitive carbonless imaging system incorporating uncolored ferric organophosphates and uncolored chelates
WO2004043704A1 (en) 2002-11-12 2004-05-27 Sherwood Technology Limited Use of transition metal compounds in imageable coatings

Also Published As

Publication number Publication date
JPS5412819B2 (en, 2012) 1979-05-25
DE2237288C3 (de) 1981-12-24
JPS4826146A (en, 2012) 1973-04-05
DE2237288B2 (de) 1975-09-04
DE2237288A1 (de) 1973-02-15
GB1354058A (en) 1974-06-05

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