CN1606508A - Heat-sensitive recording material - Google Patents

Heat-sensitive recording material Download PDF

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Publication number
CN1606508A
CN1606508A CNA028258002A CN02825800A CN1606508A CN 1606508 A CN1606508 A CN 1606508A CN A028258002 A CNA028258002 A CN A028258002A CN 02825800 A CN02825800 A CN 02825800A CN 1606508 A CN1606508 A CN 1606508A
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China
Prior art keywords
recording medium
mentioned
thermal recording
heat sensitive
sensitive recording
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Pending
Application number
CNA028258002A
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Chinese (zh)
Inventor
岩崎正幸
渡边努
满尾博文
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Fujifilm Corp
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Fujifilm Corp
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Publication date
Priority claimed from JP2001387597A external-priority patent/JP2003182226A/en
Priority claimed from JP2001388128A external-priority patent/JP3833935B2/en
Priority claimed from JP2001387677A external-priority patent/JP2003182228A/en
Priority claimed from JP2001387593A external-priority patent/JP3526294B2/en
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of CN1606508A publication Critical patent/CN1606508A/en
Pending legal-status Critical Current

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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
    • 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
    • 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
    • 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
    • B41M5/3377—Inorganic compounds, e.g. metal salts of organic acids
    • 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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • 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
    • 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
    • B41M5/3372—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
    • B41M5/337—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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/41—Base layers supports or substrates
    • 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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes
    • 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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds

Abstract

The present invention provides a heat-sensitive recording material having a support, and a heat-sensitive recording layer containing an electron-donating colorless dye and an electron-accepting compound for coloring by reacting with the electron-donating colorless dye on the support. The above-mentioned electron-accepting compound is preferably a compound represented by R<SUP>1</SUP>-Ph-SO<SUB>2</SUB>R<SUP>2</SUP>. The maximum value of the curl height of the material is preferably 5.0 mm or less. The image density formed by thermal printing by energy application at 15.2 mJ/mm<SUP>2 </SUP>from the heat-sensitive recording layer side of the support is preferably 1.20 or more. The static friction coefficient and the dynamic friction coefficient of the material are preferably in the range of 0.2 to 0.5 in the case where the outermost surface of the front side having at least one heat-sensitive recording layer and the outermost surface of the rear side are rubbed against each other. The pigment preferably has the boiled linseed oil absorption amount of 30 to 200 ml/100 g and an volume average particle diameter of 0.5 to 3 mum, and the heat-sensitive recording material is preferably used for a recording apparatus capable of thermal printing at speed of 10 cm/sec or more.

Description

Thermal recording medium
Technical field
The present invention relates to thermal recording medium, relate to a kind of like this thermal recording medium particularly, the device durability that can not cause thermal head wearing and tearing etc. of having this thermal recording medium reduces, good device adaptability, and has print adaptability, stability as recording medium, also have printing adaptability simultaneously, the adaptability of affixing one's seal and environmental suitability etc., the recording medium that can be used as resemble the common paper uses.
Background technology
About the thermal photography technology, developed a kind of heat-sensitive paper of dyestuff system of the acidic materials that use colourless leuco dye and phenol system with nineteen sixty generation by NCR society in history, this system has become the main flow of present thermal photography mode.Afterwards, 1. be that background is developed thermal head with the semiconductor technology, aspect cost performance, obtained significant improvement, can do the miniaturization and the low price of auto levelizer; Subsequently, 2. realized the high quality (raising of high sensitivityization, thermal head matching etc.) of heat-sensitive paper (thermal recording medium) itself; And then, 3. compare with the various recording modes of electrostatic recording, ink mist recording, PPC record etc., the thermal photography mode has convenience (being simplicity), low price, non-maintaining etc. advantage, because these evaluations, make the demand by leaps and bounds growth of people to heat-sensitive paper (hereinafter referred to as " thermal recording medium ").
Yet because the convenience of thermal recording medium makes it be applied to becoming the material that has personal relation with daily life in the equipment such as FAX and various printers, but there is its shortcoming in known thermal recording medium.For example, people point out:
Meet the light time variable color;
(placement in automobile etc.) meeting variable color when at high temperature preserving;
Owing to the effect of chemical reagent (organic solvent in the plasticizer in the film, grease class, the sign pen, ink-jet printer with printing ink etc.) is faded document image;
Not the sensation resemble the common paper (have drying property when lid seal etc. well and not ooze adaptability, the recording surface tarnish of the lid seal of profit etc. be beneficial to read, good with the notes of pencil etc., be difficult for taking place that friction is polluted etc.; Down together) etc.
Therefore, people require to develop and provide a kind of and can overcome the existing above-mentioned shortcoming of thermal recording medium in the past, the thermal recording medium that added value is high.
In recent years, because thermal recording medium generally all is less expensive, its recording equipment is compact and be non-maintaining, has therefore obtained to use in very wide scope.In light of this situation, recently, the sales contest of thermal recording medium is very fierce, people are more and more higher to the requirement of the fierce material of temperature-sensitive, for example require the higher multifunction of function of product in the past of its function ratio, the stability when particularly requiring to have color development concentration or background white, clarity, preservation, the full-colour image during with records such as ink-jetting styles have the tone of good distinctness etc.According to these requirements, people carry out deep research to various performances such as the color emissivity of thermal recording medium, keeping qualities.
As thermal recording medium the various performances that should have, can enumerate: (1) high sensitivity (can obtain high concentration); (2) white good (photographic fog of background is light) of background part (non-image part); (3) the image keeping quality after the print is good; (4) light resistance is good; (5) resistance to chemical reagents is good; (6) clear and excellent images quality; (7) even under the situation with ink-jetting style record full-colour image, versicolor color and luster is all good and distinct; (8) matching of thermal head is good, has the few anti-thermal head adaptability of thermal head wearing and tearing; (9) has the sensation of the common paper of resembling; (10) has the printing adaptability that can on heat sensitive recording layer, print and do not ooze the adaptability of affixing one's seal of profit; (11) to the adaptability of the high-performance printer of high-speed printer etc.; (12) have environmental suitability etc., people's requirement, any performance in these performances should not lost, and various performances must satisfy all simultaneously.Yet, up to now, can not provide the thermal recording medium that can satisfy above-mentioned whole various performances simultaneously as yet, this is present present situation.
In addition, if in manufacture process, coatings such as heat sensitive recording layer are formed on the support, then then it is cut into the occasion of the thermal recording medium of individual (for example square or rectangular-shaped) in dry run after this or by coiling into the cylinder shape, four angles after cutting out will be the bending crimping and towards heat sensitive recording layer one side perk ((13) edge-rolling).When this crimping shape is obvious, just not only can damage commodity value or quality, when record, cause the reason of carrying bad grade but also can become.
On the other hand, be extensive use of 2 traditionally, two (4-hydroxyphenyl) propane of 2-(so-called " bisphenol-A ") react and the electronic acceptance compound of color development as the electron donability leuco dye that is used for using with thermal recording medium, but this system still can not meet the demands in sensitivity, background fog, image keeping quality several respects.
In addition, aspect following (14) ink-jet adaptability problem is being arranged also.Promptly, sometimes need on thermal recording medium, write down full-color information or use ink for inking to carry out record, but when using the conventional thermal recording medium that contains bisphenol-A on its recording surface, to carry out ink mist recording, can not verily reproduce the color and luster of printing ink, or can not obtain distinct color and luster, or cause that the document image that has carried out thermal photography fades.In addition, with the thermal recording medium of above-mentioned routine according to ink-jet printer in the contacted state of the recording medium occasion of placing, also tend to cause the generation of background fog or fading of document image.
On the other hand, in the fields such as reception purposes of the self-recorder of POS system, require to realize lettering at a high speed, still, usually cause easily when carrying out the high speed lettering that thermal head pollutes, when serious even can cause the deterioration of lettering quality owing to thermal head is contaminated.Particularly in recent years, for the suppression equipment investment, the target that a kind of printer is arranged is optionally to use thermal photography and heat copying record, in this printer, in order to have heat copying record adaptability, can use thermal head,, exist the tendency that thermal head pollutes takes place easily when the occasion of using such thermal head on thermal recording medium, to carry out high-speed record with so-called parts of fine crackle structure.
Usually, thermal recording medium is less expensive, and its recording equipment is compact and be non-maintaining, has therefore obtained to use in very wide scope.Wherein, recently, the sales contest of heat-sensitive paper (thermal recording medium) is very fierce, people require to reach and in the past the function further high performance of thermal recording medium of difference to some extent, so people carry out deep research to the color development concentration of thermal recording medium, image keeping quality, resistance to chemical reagents (particularly plasticizer resistance properties), high speed lettering adaptability etc.Especially in above-mentioned fields such as reception purposes, image keeping quality and resistance to chemical reagents (particularly plasticizer resistance properties) are extremely important.
In addition, open the spy and to have put down in writing a kind of use in the flat 6-135159 communique and have aryloxy group alcoxyl base as substituent salicyclic acid derivatives and/or its slaine recording materials as electronic acceptance compound, wherein also put down in writing the improvement aspect resistance to chemical reagents, but, also having further room for improvement aspect image color and the high speed lettering adaptability (thermal head pollution).
Summary of the invention
Problem of the present invention is to solve the above-mentioned variety of issue that in the past existed, and reaches following purpose.That is,
The purpose of this invention is to provide a kind of like this thermal recording medium, this thermal recording medium especially with the distortion of bead-like seldom, can high-quality and write down well and carry, can be suppressed to the photographic fog concentration (background fog) of this bottom (non-image portion) low-level, can form high-density images (print adaptability is good) by high sensitivity, image keeping quality after the print, resistance to chemical reagents is good, can not follow the color and luster that ink jet image takes place bad or ooze profit and because the image fade that ink for inking causes, just has ink-jet adaptability, even be applied to high speed or having the occasion of the high-performance printer of parts of fine crackle structure etc., also can reach matching good and the wearing and tearing of thermal head or the pollution few (the thermal head adaptability when the high speed lettering is good) of thermal head of thermal head; In addition; the purpose of this invention is to provide a kind of like this thermal recording medium; this thermal recording medium is on the basis of above-mentioned advantage; can also obtain clear and high-quality image; the light resistance that forms image is good; can on heat sensitive recording layer or protective layer, not ooze the printing of profit and affix one's seal, can form image at low cost, can have the sensation of the common paper of resembling as required yet with few coating weight (environmental suitability).
Present inventors for can be high-level ground satisfy the various performances that thermal recording medium institute should have simultaneously and carried out repeatedly and deep research the understanding below the result has obtained.
(high sensitivityization)
In order to reach high sensitivityization, following (1)～(3) point is important, that is:
The first, (1) improves that to transmit to the heat of heat sensitive recording layer from thermal head be important, for this reason, improve thermal recording medium recording surface surface smoothing and to give resiliency to recording surface be effective.The second, (2) effectively utilize the heat that sends from thermal head is important, and for this reason, it is effective making heat insulationization of support and making the heat sensitive recording layer refinement.The 3rd, (3) for sensitizer, and the dissolution velocity that improves electron donability leuco dye and electronic acceptance compound is important, and the particle diameter that for this reason, improves solubility, reduces melt viscosity and reduce raw material is effective.Carry out specific description below.
(1) improves by the heat transmission of thermal head to heat sensitive recording layer
In order to make the heat sensitive recording layer color development to finite concentration, need certain heat, and in order to make the thermal recording medium high sensitivityization, it is important how making heat from thermal head be sent to recording layer efficiently.Herein, the pyroconductivity of solid is more much higher than gas, even compare with radiant heat, the conductivity of conduction heat is also much higher.Therefore, the surface (hereinafter being sometimes referred to as " recording surface ") of the heat sensitive recording layer when improving print is effectively with the contact rate of thermal head, so just can be sent to heat sensitive recording layer to the heat from thermal head efficiently.
In order to improve the contact rate of recording surface and thermal head, as to the desired rerum natura of thermal recording medium, 1. improve the flatness of recording surface in advance, 2. improve the resiliency of thermal recording medium, these measures etc. are effective especially.
1. in order to improve the flatness of recording surface, effective method is the flatness that improves support.Specifically, except using the good body paper of flatness, preferably being provided with oil absorption pigment is the priming coat of principal component, concavo-convexly buries the measure such as grade to what formed by paper pulp.In addition, the coating heat sensitive recording layer, to be dried after, it is applied hot calender is handled or supercalender is handled, so also can improve flatness effectively.
In addition, why effective the resiliency (giving resiliency) that 2. improves thermal recording medium is, can be based on following understanding.Promptly, when using thermal head on thermal recording medium, to carry out the occasion of hot stamping phase, can use platen (platen roller) to apply appropriate pressure, still, owing under the state of exerting pressure, improve the contact rate of thermal head and record, so make the thermal recording medium easy deformation.Therefore, as the concrete grammar of giving resiliency, being provided with oil absorption pigment is the priming coat of principal component, makes that to contain the high pigment of oil suction degree (for example amorphous carbon/silicon dioxide) in the heat sensitive recording layer be effective.Also can be effective especially even if this method of giving resiliency has the occasion that the thermal head of parts of fine crackle structure writes down in use to high sensitivityization.Herein, parts of fine crackle structure is meant the structure that the section configuration of the checking lamina of heating body constitutes by convex (chevron) on substrate.
(2) to effective utilization of the heat that sends by thermal head
In order to effectively utilize the heat that sends from thermal head, giving thermal insulation to support is effectively, and as its concrete grammar, it is effective forming space as much as possible in support.In the occasion of thermal recording medium, can enumerate: the priming coat that contains the high pigment of oil suction degree for example is set, reduces the amount of the adhesive that in this priming coat, uses as far as possible, make and contain hollow granule etc. in the priming coat.
In addition, in order to effectively utilize heat, it also is effective making the heat sensitive recording layer refinement.Can give sensitivity if consider the thermal capacity of heat sensitive recording layer, then should in heat sensitive recording layer, contain more amount and can not cause the color development composition, this thermal capacity is invalidly consumed.As this composition, suitable has, be used to suppress thermal head and recording layer adhesion releasing agent or paraffin class, be used to absorb the oil absorption pigment of molten component, the adhesive class etc. that is used to make raw material to disperse and gives coating strength.It is about 20～30% that heat exhaustion is fallen, and reduces by half by the use amount with these compositions, can expect to improve about 10～15% sensitivity.
According to present inventors' result of study,, can improve sensitivity by the pigment in the minimizing recording layer and the content of adhesive.Why sensitivity can be brought up to the above level of anticipation by reducing amount of binder, can think to cause, but reason it be unclear that owing to the reason beyond the thermal capacity.But, if merely reduce the content of adhesive, then can cause deteriorations such as a matching of thermal head and coating strength, therefore, as far as possible effective raw material proportioning, that is, it is important using minimum neccessary composition in necessary layer.
(3) for sensitizer, the raising of the dissolution velocity of electron donability leuco dye and electronic acceptance compound
In the initial stage about the technological development of thermal recording medium, sensitizer is as the fusing point depressant of electron donability leuco dye and electronic acceptance compound, can select according to the purpose of color development at a lower temperature.But, according to this idea, improve sensitivity keeping under the condition that color development begins temperature, its effect is limited, take into account background fog and sensitivity two aspects are difficult.Therefore, present inventors study sensitizer, searching is used to dissolve the material of electron donability leuco dye and electronic acceptance compound as sensitizer, do not allowing its fusing point be reduced to more than the necessary level, promptly background fog is being maintained under the low-level condition, realizing high sensitivity, the result of study of such sensitizer is being shown, the diffusion in the sensitizer of fusion of electron donability leuco dye and electronic acceptance compound is fast more, helps high sensitivityization more.That is, not only solubility is big to select those, and the little sensitizer of melt viscosity, and the dispersion particle diameter that reduces electron donability leuco dye and electronic acceptance compound, and is very effective to high sensitivityization.In addition, if above-mentioned dispersion particle diameter is too small, then can make the background fog deterioration, therefore, it is important selecting a suitable scope.
(with the matching of thermal head and giving of thermal head durability)
Thermal recording medium is directly to contact with its recording surface (surface of heat sensitive recording layer) and print (lettering) is carried out on this surface that rubs by making as the thermal head of heater element.Therefore, the composition in the fusion recording layer tends to get up as contaminant accumulation attached on the thermal head.In addition, because effects such as physical property wearing and tearing or corrosion are born on the surface of thermal head, made the lost of life of thermal head itself.
Therefore, preferably adopt following method, that is:
1) from preventing the thermal head point of view of contamination, make material one side absorb and to keep because the measure of materials such as the dyestuff of heat and fusion, developer, sensitizer is important, therefore, in recording layer, use the good pigment of oil absorption or be provided with that to use the priming coat of the good pigment of oil absorption be effective.
2) in addition, in the composition that constitutes recording materials, suppress to become easily the ion (Na that produces the thermal head corrosion +, K +Deng) content be important.
3) from alleviating the viewpoint of physical abrasion as far as possible, the hardness of consideration pigment, shape, particle diameter etc. are important.
(image keeping quality (and resistance to chemical reagents) is taken into account with background fog)
The chromophoric principle of thermal recording medium is to cause chemical reaction by leuco dye is contacted with the developer heat fusing, because this chemical reaction is reversible reaction, therefore, chromophore image causes back reaction owing to contacting with chemicals such as grease class, plasticizer easily, thereby makes picture drop-out.Therefore, in daily life, when touching chromophore image with the hand of embrocating hand lotion or other toiletrieses or grease class, perhaps with chromophore image according to the plastic products of plasticizer-containing or the goods, leather goods (the desktop mat of rubber, polyvinyl chloride system or food package film, sign pen, ink for inking, wallet or regularly ticket etc.) that contain organic solvent when state of contact is placed, just cause that easily chromophore image disappearance etc. is in the problem aspect image keeping quality and the resistance to chemical reagents.
In order to overcome the phenomenon that caused by above-mentioned chromophoric principle (disappearance of image, fade), people are carrying out all research, for example, 1. form diaphragm in order to realize the purpose that physics hides on recording layer, are called as to cover to be coated with the membranous type diaphragm; 2. in recording layer, add the additive of bridging property etc.But; even be provided with protective layer; oil or plasticizer also can permeate at leisure, along with the process of time, fade inevitably; the use that sticks on metering label on the fresh food etc. at the supermarket can only be defined in the purposes of short time; even added the bridging property material, also need considerable time from color development to presenting effect, these all are the problems that exists; just being called as does not have keeping quality, can not satisfy basic performance requirement.
Therefore, present inventors study in order to improve above-mentioned keeping quality, found that, specific electronic acceptance compound can be used for improving the keeping quality of image, and can take into account background fog, also find in addition,, can further improve background fog by with electronic acceptance compound and specific sensitizer or the combination of electron donability leuco dye.Also find in addition, by with specific image stabilizing agent combination, can be so that background fog almost have deterioration, and can further improve image keeping quality and light resistance.Find according to these, also might all bring up to higher level to image keeping quality, the adaptability of affixing one's seal and operability simultaneously, and this is unapproachable for the traditional keeping quality technology of giving that relies on face coat.In sum, can take into account affix one's seal adaptability and image keeping quality simultaneously.
(sunproof raising)
According to the difference of purposes, require thermal recording medium to have good light resistance sometimes, still, the leuco dye that is used for load image decomposes when being subjected to irradiation such as ultraviolet ray easily, therefore, and when for a long time in natural daylight etc. during exposure, still can cause and fade that this is the problem of light resistance aspect.
In order to improve light resistance, provide a kind of and be used to prevent that leuco dye is subjected to the effect of light and the method for decomposing is important.For this reason; the measure that fits into the ultraviolet ultra-violet absorber (image stabilizing agent) that is used to prevent the extra-high-speed energy in heat sensitive recording layer or protective layer is effective; particularly before arriving heat sensitive recording layer, ultraviolet ray just the viewpoint of its blocking is considered, more effective when in protective layer, containing the liquid ultra-violet absorber that is contained by micro-capsule.
(giving of printing adaptability)
According to the difference of purposes, need on the recording surface (surface of heat sensitive recording layer) of thermal recording medium, carry out hectographic printing sometimes.For this purposes, must have and to tolerate surface strength and the dumping processing solution absorbability that rotary-type form printing machine surpasses the 100m/min print speed printing speed, therefore, it is important the cooperation ratio of pigment in the heat sensitive recording layer and adhesive being adjusted to the optimum scope.For this reason, as above-mentioned pigment, the oil absorption pigment of calcium carbonate etc. preferably; as above-mentioned adhesive; polyvinyl alcohol (PVA) preferably, wherein, especially preferably sulfo group modified polyvinylalcohol, diacetone modified polyvinylalcohol, acetoacetyl modified polyvinylalcohol.
(resembling giving of common paper sensation)
The record-paper that thermal recording medium is used as facsimile machine in office or family or various printer and being widely used, its result, compare with paper (PPC with paper or notes, report with good quality papers such as paper) with at one's side some, has uncomfortable sensation, that is, its smooth surface, pen has a poor memory; very thin paper is shortcoming such as stiffening inadequately when holding with hand, is subjected to people's criticism for this reason.The facsimile machine that these problems just become nearest office will change over one of reason of the PPC type that uses common paper.From these problems, it is important and to accomplish: 1. increase as the thickness of the body paper of support and strengthen its hardness; 2. make it have low gloss surface, the property taken down notes and the adaptability etc. of affixing one's seal by giving protective layer, and the easiness that makes its hand touch sense and use approach the level of good quality paper.
Herein; what is called has the thermal recording medium of the common paper of resembling sensation; can think that it should have following various performance, that is: can overcome in the past heat-sensitive paper as the shortcoming that converted paper had, its surface is matt shape; there is not smooth feeling when touching with hand; being not easy to take place friction and polluting, document image is fugitive color etc. not, up to now; in order thermal recording medium to be reached resemble the purpose of common paper, the someone has proposed to be provided with the scheme of protective layer on recording layer.But, for traditional protective layer, aspects such as its feel of people's worry about, outward appearance (matt shape), notes property, and do not consider for the adaptability of affixing one's seal.
Yet, be background with the custom of Japan, the adaptability of affixing one's seal (do not ooze profit, seal etc. dry good) is considered to particular importance, therefore, the improvement of the protective layer that is used to reach the thermal recording medium resemble the common paper is studied.
The result of research shows, affixes one's seal adaptability in the interior sensation that resembles common paper in order to obtain to comprise, and pigment or adhesive that following material is suitable as protective layer use.
As above-mentioned pigment, in order to pay attention to affix one's seal adaptability, outward appearance (matt shape) and notes property, the material that preferably has appropriate particle diameter and oil absorption.When above-mentioned particle diameter was excessive, picture quality tended to take place deterioration, and when particle diameter was too small, notes property and outward appearance tended to variation.In addition, when oil absorption was excessive, the opacity of protective layer increased, thereby record concentration is reduced, and when oil absorption was too small, the adaptability of affixing one's seal (drying) had the tendency of variation.
As above-mentioned adhesive,, preferably press the mixture that proper proportion forms with starch especially by PVA for the purpose of adaptability variation (the oozing profit) that prevent to affix one's seal.As above-mentioned PVA, consider the PVA of preferably so-called fully saponified type (saponification degree is more than about 93%) from the viewpoint of giving the adaptability of affixing one's seal (drying).
(reaching high sensitivityization and thermal head matching) by combination with device
In recent years, in a lot of fields with purposes in, thermal recording medium not only has miniaturization, low operating cost and is called as the advantage of non-maintaining thermal photography mode, and can improve in the technology aspect printer (hardware) and the record-paper (medium) two under the background that can adopt.At above-mentioned hardware aspect, the high-performance printer of a kind of performance unlike traditional impact printer or laser printer difference appearred, for example, its writing speed reaches 10 inches of per seconds (about 25cm), record width and reaches maximum A0 size (about 900mm), resolution ratio and reach 600dpi (24 points/mm), therefore, importantly, various technical combinations are got up, make it have optimum design and control method according to different purposes.
Promptly, as above-mentioned high-performance printer, preferably can enumerate, particularly writing speed reaches above high-speed printer 10cm/ second, possesses printer of a kind of thermal head that has a parts of fine crackle structure etc., with the occasion of these printers combination, for writing speed at the high-speed printer of 10cm/ more than second, the sensitivity of traditional thermal recording medium does not often catch up with, and for the printer that possesses the thermal head that has parts of fine crackle structure, then exist the tendency that thermal head pollutes takes place easily.
Therefore, aspect thermal recording medium, carried out the optimization study of design, found that, by selecting to use specific developer (electronic acceptance compound), even with writing speed be 10cm/ more than second high-speed printer or possess under the combined situation of the printer of the thermal head that has the parts of fine crackle, also can satisfy high-levelly, and can bring into play high sensitivityization and good thermal head matching the desired performance of above-mentioned thermal recording medium.
(raising of picture quality)
In the hardware (device) that uses thermal recording medium, the situations such as fax during for example as the reception photo, picture quality is important often.About the improvement of recording image quality, learn, by being coated with the priming coat that mainly contains oil absorption pigment, particularly forming above-mentioned priming coat and can make the image high quality effectively by curtain stream rubbing method or scraper plate rubbing method (particularly scraper plate rubbing method) coating.
(alleviating of carrying capacity of environment)
In recent years, require in the society to use those systems that can make environment bear less load, even no exception in the field of thermal recording medium.In order to alleviate carrying capacity of environment, it is important the performance that will meet the demands with still less raw material use amount and energy consumption still less.And learn, be coated with by curtain stream rubbing method that to form heat sensitive recording layer be effectively for the raising of color development concentration, and the many layers of overlapping coating simultaneously can reduce the energy consumptions when drying process is handled effectively.That is to say, under the condition of identical color development concentration, might use the raw material and the consumption energy still less of less amount than conventional art.
(operability)
When carrying out print with printer by drum-shape or thin slice shape, when perhaps after print, it being stacked by thin slice shape, its four angles are the bending crimping and upwards float the occasion of the maximum of height (height of flange) partly greater than 5.0mm, recording materials undulate in printer in the course of conveying advances even can complications advance, thereby causes conveying bad.In addition, after print recording materials by the laminar occasion that stacks, cause the ground that staggers mutually, position overlapping, even the recording materials that cause stacking owing to the balance variation collapse, cause stack bad.
Have been found that from the viewpoint that prevents that conveying as described above is bad, stacks bad generation and improve operability and consider that it is effective that the maximum that laminar four angles are the height of flange that the bending crimping upwards floats is suppressed at below the 5.0mm.
The present invention finishes on the basis of above-mentioned discovery, and the concrete grammar that is used to solve above-mentioned problem is as follows:
＜1〉a kind of thermal recording medium, it is to possess to contain electron donability leuco dye and can be by the thermal recording medium of the heat sensitive recording layer of the electronic acceptance compound of color development with the reaction of this electron donability leuco dye on support, it is characterized in that, above-mentioned electronic acceptance compound is the compound by following general formula (1) expression, and the maximum of height of flange is below 5.0mm
R 1-Ph-SO 2R 2General formula (1)
In following formula, R 1Expression hydroxyl, alkyl, R 2Expression-Ph ,-NH-Ph ,-Ph-OH ,-NH-CO-NH-Ph, Ph represents phenyl, also can be contained-SO 2R 2Substituting group replace.
According to above-mentioned＜1〉described thermal recording medium, owing to use by the electronic acceptance compound of above-mentioned general formula (1) expression a side as the color development composition, therefore can realize high sensitivityization owing to keeping low background fog, can also improve simultaneously a matching of the long preservation (image keeping quality, down together), resistance to chemical reagents and the thermal head that have formed image.And, thermal recording medium leaves standstill the maximum that the plane is the height of flange (for example with the thermal recording medium surface of the plane contact distance to this planar side surface of the come-up part of this thermal recording medium) of the thermal recording medium that bending upwards floats from it and is suppressed in below the 5.0mm, therefore the conveying in the printer, the long-pending folded property of the thin slice after the print (thermal recording medium) can be improved, the thermal recording medium of good operability can be made.
＜2〉as above-mentioned＜1〉described thermal recording medium, wherein, be coated with heat sensitive recording layer, the drying coated quantity not sufficient 6g/cm after the coating 2
According to above-mentioned＜2〉described thermal recording medium, its heat sensitive recording layer is the not enough 6g/cm of coating weight at the coating fluid of this layer of coating formation usefulness 2Condition under form and formed film, therefore, drying load is few, does not damage the whiteness or the image keeping quality of background part, can give the sensation that resembles common paper.
＜3〉as above-mentioned＜1〉or＜2〉described thermal recording medium, wherein, the compound of being represented by general formula (1) is a 4-hydroxy benzenes sulfonanilide.
According to above-mentioned＜3〉described thermal recording medium, wherein, owing to contain 4-hydroxy benzenes sulfonanilide as electronic acceptance compound, therefore high sensitivityization more effectively, and can seek the raising of conservatory raising of image and thermal head matching, can not cause the rising of the background fog (the photographic fog concentration of background part) of background part simultaneously.
＜4〉as above-mentioned＜1 〉～＜3 each described thermal recording medium, wherein, heat sensitive recording layer contains image stabilizing agent, and this image stabilizing agent is 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane and 1,1, at least one side in 3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane.
According to above-mentioned＜4〉described thermal recording medium, because its heat sensitive recording layer contains specific image stabilizing agent, therefore can suppress color development reaction (positive reaction) and shift to back reaction, thereby can further improve the image keeping quality.Simultaneously can also give sunproof raising.
＜5〉as above-mentioned＜1 〉～＜4 each described thermal recording medium, wherein, heat sensitive recording layer contains inorganic pigment, and this inorganic pigment is to be selected from least a in calcite class (lightweight) calcium carbonate, amorphous silica and the aluminium hydroxide.
According to above-mentioned＜5〉described thermal recording medium, because its heat sensitive recording layer contains specific inorganic pigment, therefore can improve the matching with the thermal head that contacts biglyyer, the while can also be given the adaptability of affixing one's seal.
＜6〉as above-mentioned＜1 〉～＜5 each described thermal recording medium; wherein; heat sensitive recording layer contains adhesive, and this adhesive is to be selected from least a in sulfo group modified polyvinylalcohol, the pure and mild acetoacetyl modified polyvinylalcohol of diacetone modified poly ethylene.
According to above-mentioned＜6〉described thermal recording medium, because its heat sensitive recording layer contains specific water-soluble resin as adhesive, therefore can reach the further reduction of higher levels of high sensitivityization and background fog simultaneously.In addition, according to this formation, also can give printing adaptability simultaneously.And then, by making up, also can give resistance to water with crosslinking agent.
＜7〉as above-mentioned＜1 〉～＜6 each described thermal recording medium, wherein, support contains old paper stock.
According to above-mentioned＜7〉described thermal recording medium, owing in support, use old paper stock, therefore can realize the utilization again of resource and save resource.
＜8〉as above-mentioned＜1 〉～＜7 each described thermal recording medium; wherein; on heat sensitive recording layer, have protective layer, and this protective layer contains at least a inorganic pigment and the water soluble polymer that is selected from aluminium hydroxide, kaolin and the amorphous silica.
According to above-mentioned＜8〉described thermal recording medium; because the protective layer that contains specific inorganic pigment is set on heat sensitive recording layer; therefore the oil absorption by protective layer etc. can improve keeping quality, also can realize the operability and adaptive the giving of affixing one's seal (resembling giving of common paper sensation) simultaneously.
＜9〉as above-mentioned＜1 〉～＜8 each described thermal recording medium, wherein, Na +Ion and K +The total concentration of ion is below 1500ppm.
According to above-mentioned＜9〉described thermal recording medium, owing to select to use the few raw material of ion concentration, the result makes the total ion concentration that is occupied in support that constitutes thermal recording medium and layer etc. all be suppressed to low-level, therefore can suppress attached to the ionic weight on the thermal head, thereby can improve the corrosion resistance (durability) of thermal head.
＜10〉as above-mentioned＜1 〉～＜9 each described thermal recording medium, wherein, after the distilled water that on the surface of heat sensitive recording layer, drips through the contact angle after 0.1 second more than 20 °.
According to above-mentioned＜10〉described thermal recording medium, because the contact angle of thermal photography laminar surface is more than 20 °, therefore the profit of oozing of printing ink can be suppressed effectively at ink mist recording or when affixing one's seal, thereby the adaptive adaptive improvement of giving and affix one's seal of ink-jet can be realized.
＜11〉as above-mentioned＜1 〉～＜10 each described thermal recording medium, wherein, the image that forms after print is after placing 24 hours under the environmental condition of 60 ℃ of temperature, relative humidity 20%, and the concentration survival rate in above-mentioned formation image is more than 65%.
According to above-mentioned＜11〉described thermal recording medium, owing to can keep high concentration to the image that forms for a long time, therefore go for the keeping, presell ticket, receipt, bank note etc. of vital document need have the image reliability in long-time field.
＜12〉as above-mentioned＜1 〉～＜11 each described thermal recording medium, wherein, heat sensitive recording layer contains sensitizer, and this sensitizer be selected from 2-benzyloxy naphthalene, oxalic acid dimethylbenzyl ester, a terphenyl, ethylene glycol 4-tolyl ether, to benzylbiphenyl, 1,2-hexichol oxygen ylmethyl benzene, 1, at least a in 2-biphenoxyl ethane and the diphenyl sulphone (DPS).
According to above-mentioned＜12〉described thermal recording medium, because heat sensitive recording layer contains specific sensitizer, therefore can reduce melt viscosity, thereby the color development composition is spread well, can not cause the background fog deterioration, and high sensitivityization effectively.
＜13〉as above-mentioned＜12〉described thermal recording medium, wherein, with respect to compound 100 mass parts by general formula (1) expression, the amount of sensitizer is 75～200 mass parts.
According to above-mentioned＜13〉described thermal recording medium, because sensitizer is to contain by the amount of optimum range according to the amount of electronic acceptance compound, therefore can bring infringement to other various performances, thereby can seek effective high sensitivityization.
＜14〉as above-mentioned＜1 〉～＜13 each described thermal recording medium, wherein, the electron donability leuco dye is to be selected from least a in 2-anilino--3-methyl-6-lignocaine fluorane, 2-anilino--3-methyl-6-dibutylamino fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-isoamylamino) fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-third amino) fluorane, 2-anilino--3-methyl-6-two pentylamine base fluoranes and 2-anilino--3-methyl-6-(N-ethyl-N-p-methylphenyl amino) fluorane.
According to above-mentioned＜14〉described thermal recording medium, because heat sensitive recording layer contains specific electron donability inorganic dyestuff, therefore can satisfy the reduction and the conservatory raising of higher levels of high sensitivityization, background fog simultaneously.
＜15〉as above-mentioned＜1 〉～＜14 each described thermal recording medium, wherein, the one deck at least on the support is coated with formation by curtain stream rubbing method.
According to above-mentioned＜15〉described thermal recording medium, because one deck at least in the multilayer particularly heat sensitive recording layer is coated with by curtain stream rubbing method, therefore constituent is concentrated on the recording surface, thereby use the raw material of less amount just can improve color development concentration, can also improve picture quality (figure matter) simultaneously.In addition, many layers being carried out the occasion that the while lamination is coated with, also can reach the reduction of energy consumption during fabrication by curtain stream rubbing method.
＜16〉a kind of thermal recording medium, it is to possess to contain electron donability leuco dye and can be by the thermal recording medium of the heat sensitive recording layer of the electronic acceptance compound of color development with the reaction of this electron donability leuco dye on support, it is characterized in that, above-mentioned electronic acceptance compound is the compound by following general formula (1) expression, and is applying 15.2mJ/mm by a side that has heat sensitive recording layer from above-mentioned support 2Energy carry out image color (reflection density that utilizes Macbeath (マ Network ベ ス) reflection of the concentration RD-918 (Macbeath " マ Network ベ ス " society's system) to record) that the hot stamping phase time obtains more than 1.20,
General formula (1):
R 1-Ph-SO 2R 2
In following formula, R 1Expression hydroxyl, alkyl, R 2Expression-Ph ,-NH-Ph ,-Ph-OR 3,-NH-CO-NH-Ph, R 3The expression alkyl, Ph represents phenyl, also can be contained-SO 2R 2Substituting group replace.
According to above-mentioned＜16〉described thermal recording medium, owing to use by the electronic acceptance compound of above-mentioned general formula (1) expression a side as the color development composition, therefore can realize high sensitivityization owing to keeping low background fog, can also improve simultaneously a matching of the long preservation (image keeping quality, down together), resistance to chemical reagents and the thermal head that have formed image.And by applying 15.2mJ/mm 2Energy carry out the hot stamping phase time image color more than 1.20, therefore, even the chromophore image distinctness is through also guaranteeing easily to recognize the identification identity of recorded information after long-time.
＜17〉as above-mentioned＜16〉described thermal recording medium, wherein, be coated with heat sensitive recording layer, the drying coated quantity not sufficient 6g/cm after the coating 2
According to above-mentioned＜17〉described thermal recording medium, its heat sensitive recording layer is the not enough 6g/cm of coating weight at the coating fluid of this layer of coating formation usefulness 2Condition under form and formed film, therefore, drying load is few, does not damage the whiteness or the image keeping quality of background part, can give the sensation that resembles common paper.
＜18〉as above-mentioned＜16〉or＜17〉described thermal recording medium, wherein, the compound of being represented by general formula (1) is a 4-hydroxy benzenes sulfonanilide.
According to above-mentioned＜17〉described thermal recording medium, wherein, owing to contain 4-hydroxy benzenes sulfonanilide as electronic acceptance compound, therefore high sensitivityization more effectively, and can seek the raising of conservatory raising of image and thermal head matching, can not cause the rising of the background fog (the photographic fog concentration of background part) of background part simultaneously.
＜19〉as above-mentioned＜16 〉～＜18 appoint-a described thermal recording medium, wherein, heat sensitive recording layer contains image stabilizing agent, and this image stabilizing agent is 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane and 1,1, at least one side in 3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane.
According to above-mentioned＜19〉described thermal recording medium, because its heat sensitive recording layer contains specific image stabilizing agent, therefore can suppress color development reaction (positive reaction) and shift to back reaction, thereby can further improve the image keeping quality.Simultaneously can also give sunproof raising.
＜20〉as above-mentioned＜16 〉～＜19 each described thermal recording medium, wherein, heat sensitive recording layer contains inorganic pigment, and this inorganic pigment is to be selected from least a in calcite class (lightweight) calcium carbonate, amorphous silica and the aluminium hydroxide.
According to above-mentioned＜20〉described thermal recording medium, because its heat sensitive recording layer contains specific inorganic pigment, therefore can improve the matching with the thermal head that contacts biglyyer, the while can also be given the adaptability of affixing one's seal.
＜21〉as above-mentioned＜16 〉～＜20 each described thermal recording medium; wherein; heat sensitive recording layer contains adhesive, and this adhesive is to be selected from least a in sulfo group modified polyvinylalcohol, the pure and mild acetoacetyl modified polyvinylalcohol of diacetone modified poly ethylene.
According to above-mentioned＜21〉described thermal recording medium, because its heat sensitive recording layer contains specific water-soluble resin as adhesive, therefore can reach the further reduction of higher levels of high sensitivityization and background fog simultaneously.In addition, according to this formation, also can give printing adaptability simultaneously.And then, by making up, also can give resistance to water with crosslinking agent.
＜22〉as above-mentioned＜16 〉～＜21 each described thermal recording medium, wherein, support contains old paper stock.
According to above-mentioned＜22〉described thermal recording medium, owing in support, use old paper stock, therefore can realize the utilization again of resource and save resource.
＜23〉as above-mentioned＜16 〉～＜22 each described thermal recording medium; wherein; on heat sensitive recording layer, have protective layer, and this protective layer contains at least a inorganic pigment and the water soluble polymer that is selected from aluminium hydroxide, kaolin and the amorphous silica.
According to above-mentioned＜23〉described thermal recording medium; because the protective layer that contains specific inorganic pigment is set on heat sensitive recording layer; therefore the oil absorption by protective layer etc. can improve keeping quality, also can realize the operability and adaptive the giving of affixing one's seal (resembling giving of common paper sensation) simultaneously.
＜24〉as above-mentioned＜16 〉～＜23 each described thermal recording medium, wherein, Na +Ion and K +The total ion concentration of ion is below 1500ppm.
According to above-mentioned＜24〉described thermal recording medium, owing to select to use the few raw material of ion concentration, the result makes the total ion concentration that is occupied in support that constitutes thermal recording medium or layer etc. all be suppressed to low-level, therefore can suppress attached to the ionic weight on the thermal head, thereby can improve the corrosion resistance (durability) of thermal head.
＜25〉as above-mentioned＜16 〉～＜24 each described thermal recording medium, wherein, after the distilled water that on the surface of heat sensitive recording layer, drips through the contact angle after 0.1 second more than 20 °.
According to above-mentioned＜25〉described thermal recording medium, because the contact angle of thermal photography laminar surface is more than 20 °, therefore the profit of oozing of printing ink can be suppressed effectively at ink mist recording or when affixing one's seal, thereby the adaptive adaptive improvement of giving and affix one's seal of ink-jet can be realized.
＜26〉as above-mentioned＜16 〉～＜25 each described thermal recording medium, wherein, the image that forms after print is after placing 24 hours under the environmental condition of 60 ℃ of temperature, relative humidity 20%, and the concentration survival rate in above-mentioned formation image is more than 65%.
According to above-mentioned＜26〉described thermal recording medium, owing to can keep high concentration to the image that forms for a long time, therefore go for the keeping, presell ticket, receipt, bank note etc. of vital document need have the image reliability in long-time field.
＜27〉as above-mentioned＜16 〉～＜26 each described thermal recording medium, wherein, heat sensitive recording layer contains sensitizer, and this sensitizer be selected from 2-benzyloxy naphthalene, oxalic acid dimethylbenzyl ester, a terphenyl, ethylene glycol 4-tolyl ether, to benzylbiphenyl, 1,2-hexichol oxygen ylmethyl benzene, 1, at least a in 2-biphenoxyl ethane and the diphenyl sulphone (DPS).
According to above-mentioned＜27〉described thermal recording medium, because heat sensitive recording layer contains specific sensitizer, therefore can reduce melt viscosity, thereby the color development composition is spread well, can not cause the background fog deterioration, and high sensitivityization effectively.
＜28〉as above-mentioned＜27〉described thermal recording medium, wherein, with respect to compound 100 mass parts by general formula (1) expression, the amount of sensitizer is 75～200 mass parts.
According to above-mentioned＜28〉described thermal recording medium, because sensitizer is to contain by the amount of optimum range according to the amount of electronic acceptance compound, therefore can bring infringement to other various performances, thereby can seek effective high sensitivityization.
＜29〉as above-mentioned＜16 〉～＜28 each described thermal recording medium, wherein, the electron donability leuco dye is to be selected from least a in 2-anilino--3-methyl-6-lignocaine fluorane, 2-anilino--3-methyl-6-dibutylamino fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-isoamylamino) fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-third amino) fluorane, 2-anilino--3-methyl-6-two pentylamine base fluoranes and 2-anilino--3-methyl-6-(N-ethyl-N-p-methylphenyl amino) fluorane.
According to above-mentioned＜29〉described thermal recording medium, because heat sensitive recording layer contains specific electron donability inorganic dyestuff, therefore can satisfy the reduction and the conservatory raising of higher levels of high sensitivityization, background fog simultaneously.
＜30〉as above-mentioned＜16 〉～＜29 each described thermal recording medium, wherein, the one deck at least on the support is coated with formation by curtain stream rubbing method.
According to above-mentioned＜30〉described thermal recording medium, because one deck at least in the multilayer particularly heat sensitive recording layer is coated with by curtain stream rubbing method, therefore constituent is concentrated on the recording surface, thereby use the raw material of less amount just can improve color development concentration, can also improve picture quality (figure matter) simultaneously.In addition, many layers being carried out the occasion that the while lamination is coated with, also can reach the reduction of energy consumption during fabrication by curtain stream rubbing method.
＜31〉a kind of thermal recording medium, it is to possess to contain electron donability leuco dye and can be by the thermal recording medium of the heat sensitive recording layer of the electronic acceptance compound of color development with the reaction of this electron donability leuco dye on support, it is characterized in that, applying 15.2mJ/mm 2The image color (reflection density that utilizes Macbeath reflection of the concentration RD-918 (Macbeath society system) to record) that obtains when utilizing thermal head to carry out lettering of energy more than 1.20, and in the confficient of static friction and the scope of the coefficient of kinetic friction when mantle friction 0.2～0.5 with the most surperficial and dorsal part of the table side of the above-mentioned heat sensitive recording layer of one deck at least.
According to above-mentioned＜31〉described thermal recording medium, because by applying 15.2mJ/mm 2Energy carry out the hot stamping phase time image color more than 1.20, therefore, even the chromophore image distinctness is through also guaranteeing easily to recognize the identification identity of recorded information after long-time.In addition, because in the confficient of static friction and the scope of the coefficient of kinetic friction when mantle friction 0.2～0.5 with the most surperficial and dorsal part of the table side of the above-mentioned heat sensitive recording layer of one deck at least, therefore, with the frictional force of conveying devices such as rubber rollers be enough, when carrying thermal recording medium, can prevent to carry damage, thereby can improve conveying owing to the conveying device slip causes.In addition, a side of one deck heat sensitive recording layer (for example, only is provided with the occasion of heat sensitive recording layer, refers to the recording surface side on a side surface because thermal recording medium is provided with at least; Hereinafter be sometimes referred to as " table side ") a most surperficial opposite side with it (for example, the occasion of thermal recording medium only is set on a side surface, refers to not be provided with a side of heat sensitive recording layer; Hereinafter be sometimes referred to as " dorsal part ") frictional force be in the suitable scope, therefore,, can slide between each material in the occasion that each thermal recording medium is used with stacking.Therefore, thermal recording medium of the present invention is being pressed the occasion that single-sheet stationery is carried, can prevented the several pages conveying that overlaps, thereby can improve conveying.Should illustrate that in thermal recording medium of the present invention, when the two sides at support is provided with the occasion of heat sensitive recording layer, the surface that can select any side is as the table side, and with the surface of its opposite side as dorsal part.
＜32〉as above-mentioned＜31〉described thermal recording medium, wherein, electronic acceptance compound is the compound by following general formula (1) expression,
General formula (1):
R 1-Ph-SO 2R 2
In above-mentioned general formula (1), R 1Expression hydroxyl, alkyl, R 2Expression-Ph ,-NH-Ph ,-Ph-OR 3,-NH-CO-NH-Ph, R 3The expression alkyl, Ph represents phenyl, also can be contained-SO 2R 2Substituting group replace.
According to above-mentioned＜32〉described thermal recording medium, owing to use by the electronic acceptance compound of above-mentioned general formula (1) expression a side as the color development composition, therefore can realize high sensitivityization owing to keeping low background fog, can also improve simultaneously a matching of the long preservation (image keeping quality, down together), resistance to chemical reagents and the thermal head that have formed image.
＜33〉as above-mentioned＜31〉or＜32〉described thermal recording medium, wherein, the compound of being represented by general formula (1) is a 4-hydroxy benzenes sulfonanilide.
According to above-mentioned＜33〉described thermal recording medium, wherein, owing to contain 4-hydroxy benzenes sulfonanilide as electronic acceptance compound, therefore high sensitivityization more effectively, and can seek the raising of conservatory raising of image and thermal head matching, can not cause the rising of the background fog (the photographic fog concentration of background part) of background part simultaneously.
＜34〉as above-mentioned＜31 〉～＜33 each described thermal recording medium, wherein, heat sensitive recording layer contains image stabilizing agent, and this image stabilizing agent is 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane and 1,1, at least one side in 3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane.
According to above-mentioned＜34〉described thermal recording medium, because its heat sensitive recording layer contains specific image stabilizing agent, therefore can suppress color development reaction (positive reaction) and shift to back reaction, thereby can further improve the image keeping quality.Simultaneously can also give sunproof raising.
＜35〉as above-mentioned＜31 〉～＜34 each described thermal recording medium, wherein, heat sensitive recording layer contains inorganic pigment, and this inorganic pigment is to be selected from least a in calcite class (lightweight) calcium carbonate, amorphous silica and the aluminium hydroxide.
According to above-mentioned＜35〉described thermal recording medium, because its heat sensitive recording layer contains specific inorganic pigment, therefore can improve the matching with the thermal head that contacts biglyyer, the while can also be given the adaptability of affixing one's seal.
＜36〉as above-mentioned＜31 〉～＜35 each described thermal recording medium; wherein; heat sensitive recording layer contains adhesive, and this adhesive is to be selected from least a in sulfo group modified polyvinylalcohol, the pure and mild acetoacetyl modified polyvinylalcohol of diacetone modified poly ethylene.
According to above-mentioned＜36〉described thermal recording medium, because its heat sensitive recording layer contains specific water-soluble resin as adhesive, therefore can reach the further reduction of higher levels of high sensitivityization and background fog simultaneously.In addition, according to this formation, also can give printing adaptability simultaneously.And then, by making up, also can give resistance to water with crosslinking agent.
＜37〉as above-mentioned＜31 〉～＜36 each described thermal recording medium, wherein, support contains old paper stock.
According to above-mentioned＜37〉described thermal recording medium, owing in support, use old paper stock, therefore can realize the utilization again of resource and save resource.
＜38〉as above-mentioned＜31 〉～＜37 each described thermal recording medium; wherein; on heat sensitive recording layer, have protective layer, and this protective layer contains at least a inorganic pigment and the water soluble polymer that is selected from aluminium hydroxide, kaolin and the amorphous silica.
According to above-mentioned＜38〉described thermal recording medium; because the protective layer that contains specific inorganic pigment is set on heat sensitive recording layer; therefore the oil absorption by protective layer etc. can improve keeping quality, also can realize the operability and adaptive the giving of affixing one's seal (resembling giving of common paper sensation) simultaneously.
＜39〉as above-mentioned＜31 〉～＜38 each described thermal recording medium, wherein, Na +Ion and K +The total ion concentration of ion is below 1500ppm.
According to above-mentioned＜39〉described thermal recording medium, owing to select to use the few raw material of ion concentration, the result makes the total ion concentration that is occupied in support that constitutes thermal recording medium or layer etc. all be suppressed to low-level, therefore can suppress attached to the ionic weight on the thermal head, thereby can improve the corrosion resistance (durability) of thermal head.
＜40〉as above-mentioned＜31 〉～＜39 each described thermal recording medium, wherein, after the distilled water that on the surface of heat sensitive recording layer, drips through the contact angle after 0.1 second more than 20 °.
According to above-mentioned＜40〉described thermal recording medium, because the contact angle of thermal photography laminar surface is more than 20 °, therefore the profit of oozing of printing ink can be suppressed effectively at ink mist recording or when affixing one's seal, thereby the adaptive adaptive improvement of giving and affix one's seal of ink-jet can be realized.
＜41〉as above-mentioned＜31 〉～＜40 each described thermal recording medium, wherein, the image that forms after print is after placing 24 hours under the environmental condition of 60 ℃ of temperature, relative humidity 20%, and the concentration survival rate in above-mentioned formation image is more than 65%.
According to above-mentioned＜41〉described thermal recording medium, owing to can keep high concentration to the image that forms for a long time, therefore go for the keeping, presell ticket, receipt, bank note etc. of vital document need have the image reliability in long-time field.
＜42〉as above-mentioned＜31 〉～＜41 each described thermal recording medium, wherein, heat sensitive recording layer contains sensitizer, and this sensitizer be selected from 2-benzyloxy naphthalene, oxalic acid dimethylbenzyl ester, a terphenyl, ethylene glycol 4-tolyl ether, to benzylbiphenyl, 1,2-hexichol oxygen ylmethyl benzene, diphenyl sulphone (DPS) and 1, at least a in the 2-biphenoxyl ethane.
According to above-mentioned＜42〉described thermal recording medium, because heat sensitive recording layer contains specific sensitizer, therefore can reduce melt viscosity, thereby the color development composition is spread well, can not cause the background fog deterioration, and high sensitivityization effectively.
＜43〉as above-mentioned＜42〉described thermal recording medium, wherein, with respect to compound 100 mass parts by general formula (1) expression, the amount of sensitizer is 75～200 mass parts.
According to above-mentioned＜43〉described thermal recording medium, because sensitizer is to contain by the amount of optimum range according to the amount of electronic acceptance compound, therefore can bring infringement to other various performances, thereby can seek effective high sensitivityization.
＜44〉as above-mentioned＜31 〉～＜43 each described thermal recording medium, wherein, the electron donability leuco dye is to be selected from least a in 2-anilino--3-methyl-6-lignocaine fluorane, 2-anilino--3-methyl-6-dibutylamino fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-isoamylamino) fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-third amino) fluorane, 2-anilino--3-methyl-6-two pentylamine base fluoranes and 2-anilino--3-methyl-6-(N-ethyl-N-p-methylphenyl amino) fluorane.
According to above-mentioned＜44〉described thermal recording medium, because heat sensitive recording layer contains specific electron donability inorganic dyestuff, therefore can satisfy the reduction and the conservatory raising of higher levels of high sensitivityization, background fog simultaneously.
＜45〉as above-mentioned＜31 〉～＜44 each described thermal recording medium, wherein, the one deck at least on the support is coated with formation by curtain stream rubbing method.
According to above-mentioned＜45〉described thermal recording medium, because one deck at least in the multilayer particularly heat sensitive recording layer is coated with by curtain stream rubbing method, therefore constituent is concentrated on the recording surface, thereby use the raw material of less amount just can improve color development concentration, can also improve picture quality (figure matter) simultaneously.In addition, many layers being carried out the occasion that the while lamination is coated with, also can reach the reduction of energy consumption during fabrication by curtain stream rubbing method.
＜46〉a kind of thermal recording medium, it is the thermal recording medium that possesses the heat sensitive recording layer that contains electron donability leuco dye and electronic acceptance compound that can be by the color development with the reaction of this electron donability leuco dye and pigment on support, it is characterized in that, above-mentioned pigment is 30～200ml/100g to the oil absorption of boiling (boiled) Linseed oil, volume average particle size is 0.5～3 μ m, and can use in the tape deck more than writing speed is per second 10cm.
According to above-mentioned＜46〉described thermal recording medium, because using a kind of in heat sensitive recording layer is 30～200ml/100g to the oil absorption of boiling Linseed oil, volume average particle size is the pigment of 0.5～3 μ m, can prevent that therefore the thermal head when the high speed lettering from polluting.In addition, the tape deck of print speed more than 10cm/sec during owing to a kind of record of use, therefore good to the hot transfer efficiency of heat sensitive recording layer, the loss of heat can be suppressed, thereby the chromophore image of high concentration can be obtained.Its result can reduce the required energy that applies when record, and can prevent because the caused change in concentration of variation of hot transfer efficiency.
＜47〉as above-mentioned＜31〉described thermal recording medium, wherein, electronic acceptance compound is the compound by following general formula (1) expression,
General formula (1):
R 1-Ph-SO 2R 2
In above-mentioned general formula (1), R 1Expression hydroxyl, alkyl, R 2Expression-Ph ,-NH-Ph ,-Ph-OR 3,-NH-CO-NH-Ph, R 3The expression alkyl, Ph represents phenyl, also can be contained-SO 2R 2Substituting group replace.
According to above-mentioned＜47〉described thermal recording medium, owing to use by the electronic acceptance compound of above-mentioned general formula (1) expression a side as the color development composition, therefore can realize high sensitivityization owing to keeping low background fog, can also improve simultaneously a matching of the long preservation (image keeping quality, down together), resistance to chemical reagents and the thermal head that have formed image.
＜48〉as above-mentioned＜47〉described thermal recording medium, wherein, the compound of being represented by general formula (1) is a 4-hydroxy benzenes sulfonanilide.
According to above-mentioned＜48〉described thermal recording medium, wherein, owing to contain 4-hydroxy benzenes sulfonanilide as electronic acceptance compound, therefore high sensitivityization more effectively, and can seek the raising of conservatory raising of image and thermal head matching, can not cause the rising of the background fog (the photographic fog concentration of background part) of background part simultaneously.
＜49〉as above-mentioned＜46 〉～＜48 each described thermal recording medium, wherein, above-mentioned pigment is to be selected from least a in calcite class (lightweight) calcium carbonate, amorphous silica and the aluminium hydroxide.
According to above-mentioned＜49〉described thermal recording medium, because its heat sensitive recording layer contains specific inorganic pigment, therefore can improve the matching with the thermal head that contacts biglyyer, the while can also be given the adaptability of affixing one's seal.
＜50〉as above-mentioned＜46 〉～＜49 each described thermal recording medium, wherein, heat sensitive recording layer contains image stabilizing agent, and this image stabilizing agent is 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane and 1,1, at least one side in 3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane.
According to above-mentioned＜50〉described thermal recording medium, because its heat sensitive recording layer contains specific image stabilizing agent, therefore can suppress color development reaction (positive reaction) and shift to back reaction, thereby can further improve the image keeping quality.Simultaneously can also give sunproof raising.
＜51〉as above-mentioned＜46 〉～＜50 each described thermal recording medium; wherein; heat sensitive recording layer contains adhesive, and this adhesive is to be selected from least a in sulfo group modified polyvinylalcohol, the pure and mild acetoacetyl modified polyvinylalcohol of diacetone modified poly ethylene.
According to above-mentioned＜51〉described thermal recording medium, because its heat sensitive recording layer contains specific water-soluble resin as adhesive, therefore can reach the further reduction of higher levels of high sensitivityization and background fog simultaneously.In addition, according to this formation, also can give printing adaptability simultaneously.And then, by making up, also can give resistance to water with crosslinking agent.
＜52〉as above-mentioned＜46 〉～＜51 each described thermal recording medium, wherein, support contains old paper stock.
According to above-mentioned＜52〉described thermal recording medium, owing in support, use old paper stock, therefore can realize the utilization again of resource and save resource.
＜53〉as above-mentioned＜46 〉～＜52 each described thermal recording medium; wherein; on heat sensitive recording layer, have protective layer, and this protective layer contains at least a inorganic pigment and the water soluble polymer that is selected from aluminium hydroxide, kaolin and the amorphous silica.
According to above-mentioned＜53〉described thermal recording medium; because the protective layer that contains specific inorganic pigment is set on heat sensitive recording layer; therefore the oil absorption by protective layer etc. can improve keeping quality, also can realize the operability and adaptive the giving of affixing one's seal (resembling giving of common paper sensation) simultaneously.
＜54〉as above-mentioned＜46 〉～＜53 each described thermal recording medium, wherein, Na +Ion and K +The total ion concentration of ion is below 1500ppm.
According to above-mentioned＜54〉described thermal recording medium, owing to select to use the few raw material of ion concentration, the result makes the total ion concentration that is occupied in support that constitutes thermal recording medium or layer etc. all be suppressed to low-level, therefore can suppress attached to the ionic weight on the thermal head, thereby can improve the corrosion resistance (durability) of thermal head.
＜55〉as above-mentioned＜46 〉～＜54 each described thermal recording medium, wherein, after the distilled water that on the surface of heat sensitive recording layer, drips through the contact angle after 0.1 second more than 20 °.
According to above-mentioned＜55〉described thermal recording medium, because the contact angle of thermal photography laminar surface is more than 20 °, therefore the profit of oozing of printing ink can be suppressed effectively at ink mist recording or when affixing one's seal, thereby the adaptive adaptive improvement of giving and affix one's seal of ink-jet can be realized.
＜56)〉as above-mentioned＜46 〉～＜55 each described thermal recording medium, wherein, the image that forms after print is after placing 24 hours under the environmental condition of 60 ℃ of temperature, relative humidity 20%, and the concentration survival rate in above-mentioned formation image is more than 65%.
According to above-mentioned＜56〉described thermal recording medium, owing to can keep high concentration to the image that forms for a long time, therefore go for the keeping, presell ticket, receipt, bank note etc. of vital document need have the image reliability in long-time field.
＜57〉as above-mentioned＜46 〉～＜56 each described thermal recording medium, wherein, heat sensitive recording layer contains sensitizer, and this sensitizer be selected from 2-benzyloxy naphthalene, oxalic acid dimethylbenzyl ester, a terphenyl, ethylene glycol 4-tolyl ether, to benzylbiphenyl, 1,2-hexichol oxygen ylmethyl benzene, diphenyl sulphone (DPS) and 1, at least a in the 2-biphenoxyl ethane.
According to above-mentioned＜57〉described thermal recording medium, because heat sensitive recording layer contains specific sensitizer, therefore can reduce melt viscosity, thereby the color development composition is spread well, can not cause the background fog deterioration, and high sensitivityization effectively.
＜58〉as above-mentioned＜57〉described thermal recording medium, wherein, with respect to compound 100 mass parts by general formula (1) expression, the amount of sensitizer is 75～200 mass parts.
According to above-mentioned＜58〉described thermal recording medium, because sensitizer is to contain by the amount of optimum range according to the amount of electronic acceptance compound, therefore can bring infringement to other various performances, thereby can seek effective high sensitivityization.
＜59〉as above-mentioned＜46 〉～＜58 each described thermal recording medium, wherein, the electron donability leuco dye is to be selected from least a in 2-anilino--3-methyl-6-lignocaine fluorane, 2-anilino--3-methyl-6-dibutylamino fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-isoamylamino) fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-third amino) fluorane, 2-anilino--3-methyl-6-two pentylamine base fluoranes and 2-anilino--3-methyl-6-(N-ethyl-N-p-methylphenyl amino) fluorane.
According to above-mentioned＜59〉described thermal recording medium, because heat sensitive recording layer contains specific electron donability inorganic dyestuff, therefore can satisfy the reduction and the conservatory raising of higher levels of high sensitivityization, background fog simultaneously.
The specific embodiment
[the 1st embodiment]
In the 1st embodiment of thermal recording medium of the present invention, have the heat sensitive recording layer that combines the color development system by electron donability leuco dye and electronic acceptance compound, wherein contain by R 1-Ph-SO 2R 2The compound of expression is as above-mentioned electronic acceptance compound, and the maximum of the height of flange of thermal recording medium itself is below 5.0mm.
Explain the 1st embodiment of thermal recording medium of the present invention below.
The 1st embodiment of thermal recording medium of the present invention be have on the support one deck or two-layer more than heat sensitive recording layer, preferably have protective layer.In addition, as required, can also have other layer such as intermediate layer.
＜heat sensitive recording layer 〉
Above-mentioned heat sensitive recording layer contain at least the electron donability leuco dye, can be by the electronic acceptance compound of color development with the reaction of this electron donability leuco dye, preferably contain image stabilizing agent (ultraviolet ray prevents agent), inorganic pigment, adhesive, sensitizer, as required, can also contain other compositions.
-electron donability leuco dye-
In the said heat sensitive recording layer of the 1st embodiment of the present invention, contain at least a electron donability leuco dye as the color development composition.As above-mentioned electron donability leuco dye, can from the leuco dye of conventional known, select aptly, for example can enumerate: 2-anilino--3-methyl-6-lignocaine fluorane, 2-anilino--3-methyl-6-dibutylamino fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-isoamylamino) fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-third amino) fluorane, 2-anilino--3-methyl-6-two pentylamine base fluoranes, and 2-anilino--3-methyl-6-(N-ethyl-N-p-methylphenyl amino) fluorane, the amino fluorane of 2-anilino--3-methyl-6-N-ethyl-N-Zhong Ding, 3-two (pentylamine base)-6-methyl-7-anilino fluorane, 3-(N-isopentyl-N-ethylamino)-6-methyl-7-anilino fluorane, 3-(N-n-hexyl-N-ethylamino)-6-methyl-7-anilino fluorane, 3-[N-(3-ethoxy propyl group)-N-ethylamino]-6-methyl-7-anilino fluorane, 3-two (n-butyl amine base)-7-(2-chloroanilino) fluorane, 3-lignocaine-7-(2-chloroanilino) fluorane, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilino fluorane etc.
Wherein, especially preferably contain and be selected from least a in 2-anilino--3-methyl-6-lignocaine fluorane, 2-anilino--3-methyl-6-dibutylamino fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-isoamylamino) fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-third amino) fluorane, 2-anilino--3-methyl-6-two pentylamine base fluoranes and 2-anilino--3-methyl-6-(N-ethyl-N-p-methylphenyl amino) fluorane.In addition, above-mentioned electron donability leuco dye can be used for single heat sensitive recording layer by separately a kind of, also can be two or more and use.
Be selected from the above-mentioned thing group at least aly owing to contain, particularly can under the condition that keeps low background fog, improve color development concentration, can improve the image keeping quality of established image section simultaneously further as the electron donability dyestuff.
When the preparation heat sensitive recording layer forms with coating fluid (hereinafter being sometimes referred to as " heat sensitive recording layer coating fluid "), as the particle diameter of above-mentioned electron donability leuco dye, average grain diameter meter by volume, preferably below 1.0 μ m, 0.4～0.7 μ m more preferably.If this volume average particle size surpasses 1.0 μ m, heat sensitivity is reduced, and if less than 0.4 μ m then can make the background fog deterioration.
Above-mentioned volume average particle size can easily use laser diffraction formula particle size distribution device (for example LA500 (ホ リ バ (strain) system)) etc. to record.
Coating weight as above-mentioned electron donability leuco dye is preferably 0.1～1.0g/m 2, consider from color development concentration and background fog aspect, more preferably 0.2～0.5g/m 2
-electronic acceptance compound-
In the said heat sensitive recording layer of the present invention's the 1st embodiment, contain by at least a conduct in the compound of following general formula (1) expression by meeting thermal response and the electronic acceptance compound of color development with above-mentioned electron donability leuco dye.Owing to contain this compound as electronic acceptance compound, therefore can realize high sensitivityization owing to keeping low background fog, can also improve a matching of the long preservation (image keeping quality), resistance to chemical reagents, ink-jet adaptability and the thermal head that have formed image simultaneously.
General formula (1):
R 1-Ph-SO 2R 2
In above-mentioned general formula (1), R 1Expression hydroxyl, alkyl.R 2Expression-Ph ,-NH-Ph ,-Ph-OH ,-NH-CO-NH-Ph.Ph represents phenyl, also can be contained-SO 2R 2Substituting group replace.
As by above-mentioned R 1The alkyl of expression, preferably the alkyl of carbon number 1～3 is more preferably methyl, ethyl, isopropyl etc.Wherein, as above-mentioned R 1, hydroxyl especially preferably.
Above-mentioned Ph represents phenyl, but it can be contained-SO 2R 2The substituted-phenyl that replaces of substituting group, and this substituent R 2Can also be by replacements such as methyl, halogen atoms.As this substituting group, can enumerate-CH 2-C 6H 5-NHCONH-SO 2-C 6H 5,-SO 2-C 6H 5-,-SO 2-C 6H 4-CH 3,-SO 2-C 6H 4-Cl etc.
Wherein, as above-mentioned R 2, preferably-NH-Ph, especially preferably-NH-C 6H 5
Preferred concrete example as the compound of representing by above-mentioned general formula (1); can enumerate: 4-hydroxy benzenes sulfonanilide (=right-N-phenyl sulfamoyl phenol); right-N-(2-chlorphenyl) sulfonamides phenol; right-N-3-tolyl sulfonamides phenol; right-N-2-tolyl sulfonamides phenol; right-N-(3-anisyl) sulfonamides phenol; right-N-(3-hydroxyphenyl) sulfonamides phenol; right-N-(4-hydroxyphenyl) sulfonamides phenol; 2-chloro-4-N-phenyl sulfamoyl phenol; 2-chloro-4-N-(3-hydroxyphenyl) sulfonamides phenol; 4 '-hydroxyl para toluene sulfonamide; 4; 4 '-two (tolysulfonyl amido carbonamido) diphenyl methane (=BTUM); 2, two (benzenesulfonyl) phenol of 4-etc.But, be not limited to these concrete examples in the present invention.
In electronic acceptance compound by above-mentioned general formula (1) expression, consider from two aspects of taking into account image keeping quality and background fog, most preferably be 4-hydroxy benzenes sulfonanilide.
As the amount of the electronic acceptance compound in single heat sensitive recording layer, with respect to the quality of above-mentioned electron donability leuco dye, be preferably 50～400 quality %, more preferably 100～300 quality %.
Can be electronic acceptance compound and other known electronic acceptance compounds and usefulness in the scope of not damaging effect of the present invention (the particularly raising of the alleviating of background fog, high sensitivityization and image keeping quality, resistance to chemical reagents and thermal head matching) by above-mentioned general formula (1) expression.
As above-mentioned known electronic acceptance compound, can select aptly to use, particularly consider, preferably phenol type compound or salicyclic acid derivatives and multivalent metal salt thereof from the viewpoint that suppresses background fog.
As above-mentioned phenol type compound, for example can enumerate: 2,2 '-two (4-hydroxyl phenol) propane (bisphenol-A), the 4-tert-butyl phenol, the 4-phenylphenol, 4-hydroxyl two phenates, 1,1 '-two (4-hydroxyphenyl) cyclohexane, 1,1 '-two (3-chloro-4-hydroxyphenyl) cyclohexane, 1,1 '-two (3-chloro-4-hydroxyphenyl)-2-ethyl butane, 4, the inferior octyl group biphenol of 4 '-Zhong Yi, 4,4 '-sec-butylidene biphenol, the 4-tert-octyl phenol, 4-p-methylphenyl phenol, 4,4 '-methyl cyclohexylene phenol, 4,4 '-isopentylidene phenol, 4-hydroxyl-4-isopropyl hydroxy diphenyl sulfone, benzyl p-hydroxybenzoate etc.
As above-mentioned salicyclic acid derivatives, for example can enumerate: 4-pentadecyl salicylic acid, 3,5-two (α-Jia Bianji) salicylic acid, 3,5-two (uncle's octyl group) salicylic acid, 5-octadecyl salicylic acid, 5-α-(right-the α-Jia Bianji phenyl) ethyl salicylic acid, 3-α-Jia Bianji-uncle's 5-octyl group salicylic acid, 5-myristyl salicylic acid, 4-hexyl hydroxyl salicylic acid, 4-cyclohexyl hydroxyl salicylic acid, 4-decyl oxygen salicylic acid, 4-dodecyl oxygen salicylic acid, 4-pentadecyl oxygen salicylic acid, 4-octadecyl oxygen salicylic acid and their zinc, aluminium, calcium, copper, lead salt etc.
And with the occasion of above-mentioned known electronic acceptance compound, amount as the electronic acceptance compound of representing by above-mentioned general formula (1), with respect to the gross mass of electronic acceptance compound, preferably more than 50 quality %, more preferably more than 70 quality %.
When the preparation heat sensitive recording layer forms the coating fluid of usefulness, as the particle diameter of above-mentioned electronic acceptance compound, by volume average grain diameter preferably below 1.0 μ m, 0.4～0.7 μ m more preferably.If this volume average particle size surpasses 1.0 μ m, its heat sensitivity tends to reduce.In addition, if less than 0.4 μ m then tends to cause the background fog deterioration.
Above-mentioned volume average particle size can easily utilize laser diffraction formula particle size distribution device (for example LA500 (ホ リ バ (strain) system)) etc. to record.
-sensitizer-
In the said heat sensitive recording layer of the 1st embodiment of the present invention, preferably contain sensitizer.Particularly consider from the viewpoint that can improve sensitivity biglyyer, preferably contain from 2-benzyloxy naphthalene, oxalic acid dimethylbenzyl ester, a terphenyl, ethylene glycol 4-tolyl ether, to benzyl bis-phenol, 1, that selects in the 2-hexichol oxygen ylmethyl benzene, 1, the thing group of 2-biphenoxyl ethane and diphenyl sulfone (hereinafter being sometimes referred to as " said sensitizer among the present invention ") is at least a.
In heat sensitive recording layer,,, be preferably 75～200 mass parts, more preferably 100～150 mass parts with respect to above-mentioned electronic acceptance compound (preferred 4-hydroxy benzenes sulfonanilide) 100 mass parts as the total content of the sensitizer of above-mentioned selection.
In the time of in above-mentioned amount is in above-mentioned scope, can increases the raising effect of sensitivity, but also can improve the image keeping quality.
Except from the sensitizer of above-mentioned thing group selection, in the scope of not damaging effect of the present invention, can and use other sensitizers of from known sensitizer in the past, selecting aptly.
And with the occasion of above-mentioned other sensitizers, as amount, preferably be equivalent to be more preferably more than the 70 quality % more than the 50 quality % of total amount of the sensitizer that in layer, contains from the sensitizer of above-mentioned thing group selection.
As above-mentioned other sensitizer, for example can enumerate: the aliphatic monamide, the aliphatic diamides, stearic uride, two (2-methylphenoxy) ethane, two (2-methoxyl group phenoxy group) ethane, betanaphthol (to methyl-benzyl) ether, the Alpha-Naphthyl benzylic ether, 1,4-butanediol p-methylphenyl ether, 1,4-butanediol p-isopropyl phenyl ether, 1, the 4-butanediol is to uncle's octyl phenyl ether, 1-phenoxy group-2-(4-ethyl phenoxy group) ethane, 1-phenoxy group-2-(chlorophenoxy) ethane, 1,4-butanediol phenyl ether, diethylene glycol (DEG) two (4-anisyl) ether, 1,2-hexichol oxygen ylmethyl benzene, 1,4-two (phenoxymethyl) benzene etc.
-image stabilizing agent (ultra-violet absorber)-
In the said heat sensitive recording layer of the present invention's the 1st embodiment, preferably contain image stabilizing agent (containing ultra-violet absorber).Ultra-violet absorber can be microencapsulation.By containing image stabilizing agent, can improve the keeping quality (image keeping quality) of established chromophore image biglyyer.
As above-mentioned image stabilizing agent, phenolic compounds for example, particularly hindered phenol compound is effective, for example can enumerate: 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,1,3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane, 1,1,3-three (2-ethyl-4-hydroxyl-5-cyclohexyl phenyl) butane, 1,1,3-three (3,5-di-t-butyl-4-hydroxyphenyl) butane, 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) propane, 2,2 '-methylene two (the 6-tert-butyl group-4-methylphenol), 2,2 '-methylene two (the 6-tert-butyl group-4-ethyl-phenol), 4,4 '-butylidene two (the 6-tert-butyl group-3-methylphenol), 4,4 '-sulfo--two (3 methy 6 tert butyl phenol) etc.In addition, image stabilizing agent can use separately, and is also can be with it two or more and use.
Wherein, particularly preferably be 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,1,3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane.
Total content as the image stabilizing agent in single heat sensitive recording layer, from suppressing background fog and improving the conservatory viewpoint of image effectively and consider, with respect to above-mentioned electron donability leuco dye 100 mass parts, be preferably 10～100 mass parts, more preferably 20～60 mass parts.
In addition, with 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane and/or 1,1,3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane and other the above-mentioned image stabilizing agent and the occasion of usefulness, in single heat sensitive recording layer, as 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane and/or 1,1, the amount of 3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane is with respect to the gross mass of image stabilizing agent, preferably more than 50 quality %, more preferably more than 70 quality %.
As above-mentioned ultra-violet absorber, can enumerate the ultra-violet absorber that illustrates below.
Figure A0282580000361
In single heat sensitive recording layer,, consider,, be preferably 10～300 mass parts, more preferably 30～200 mass parts with respect to above-mentioned electron donability leuco dye 100 mass parts from improving the conservatory viewpoint of image effectively as the amount of ultra-violet absorber.
-inorganic pigment-
In the said heat sensitive recording layer of the 1st embodiment of the present invention, especially preferably contain at least a (the said inorganic pigment among the present invention) from calcite class calcium carbonate, amorphous silica and aluminium hydroxide, selected as inorganic pigment.By containing these inorganic pigments, can further improve and a matching that contacts thermal head, can also give simultaneously printing adaptability and with the similitude of common paper.
In (lightweight) calcium carbonate, the crystal type calcium carbonate that calcite, aragonite, vaterite etc. are generally arranged, but, color development concentration when thermal head writes down and prevent viewpoint that thermal head pollutes and consider from the viewpoint of absorbability, hardness etc., calcite class (lightweight) calcium carbonate preferably, wherein, particularly preferably be shape of particle and be spindle shape or the planar calcium carbonate of scalenohedron.Calcite class (lightweight) calcium carbonate can be made by known manufacture method.
As the average grain diameter of above-mentioned calcite class (lightweight) calcium carbonate, by volume average grain diameter is preferably 1～3 μ m.Volume average particle size can be according to recording with same method such as above-mentioned electron donability leuco dye.
In single heat sensitive recording layer, amount as above-mentioned " said inorganic pigment among the present invention ", from improving color development concentration and preventing that sediment is attached to the viewpoint consideration on the thermal head, with respect to electronic acceptance compound 100 mass parts, be preferably 50～500 mass parts, more preferably 70～350 mass parts are preferably 90～250 mass parts especially.
In addition, in the scope of not damaging effect of the present invention (particularly thermal head matching, printing adaptability and with the raising of common paper similitude), can and use said inorganic pigment in the invention described above and other inorganic pigment.
As other above-mentioned inorganic pigments, except calcite class (lightweight) calcium carbonate, can enumerate: calcium carbonate, barium sulfate, lithopone, pyrophyllite, kaolin, burn till kaolin, amorphous silica, kaolin, magnesium carbonate, magnesia etc.
As the volume average particle size of above-mentioned other inorganic pigments (with laser diffraction formula particle size distribution device (for example LA500 (ホ リ バ (strain) system) etc.) mensuration), be preferably 0.3～1.5 μ m, more preferably 0.5～0.9 μ m.
The occasion of said inorganic pigment and above-mentioned other inorganic pigments and usefulness in the present invention, as the gross mass (V) of " said inorganic pigment among the present invention " ratio (V/W) with the gross mass (W) of above-mentioned other inorganic pigments, be preferably 100/0～60/40, more preferably 100/0～80/20.
In addition, consider from the viewpoint of the abrasiveness that suppresses thermal head, preferably the inorganic pigment of Mohs' hardness below 3." Mohs' hardness " is meant in " Britain and Japan's plastics industry dictionary " the 5th edition Mohs' hardness (Mohs Hardness) of record in (coulee is stretched work, census of manufacturing meeting (strain) distribution) p.616.In the inorganic pigment of Mohs' hardness below 3, contain calcium carbonate, aluminium hydroxide etc.
Said inorganic pigment is with magnesium carbonate, when magnesia mixes in the present invention, can alleviate background fog effectively, this is favourable aspect, in this case, as magnesium carbonate and/or magnesian amount, 3～50 quality % that preferably are equivalent to the inorganic pigment gross mass, especially preferably 5～30 quality %.
-adhesive-
In the said heat sensitive recording layer of the 1st embodiment of the present invention; preferably contain at least a (that is the modified polyvinylalcohol (hereinafter being sometimes referred to as " specific modified PVA ")) that be selected from sulfo group modified polyethylene alcohol, the pure and mild acetoacetyl modified polyethylene of the diacetone modified polyethylene alcohol as adhesive (the perhaps protecting colloid when disperseing).By in heat sensitive recording layer, containing above-mentioned particular modification PVA as adhesive, can give the sensation that resembles common paper, can increase simultaneously the bonding force between heat sensitive recording layer and the support, therefore the trouble of the picking that when hectographic printing etc., produces etc. can be prevented, thereby printing adaptability can be improved.And then, can be suppressed to background fog the color development concentration that improves under the lower condition when writing down with thermal head.
Above-mentioned particular modification PVA can use separately, also can merge use, in addition, also can merge use with other modified PVA or polyvinyl alcohol (PVA).
With above-mentioned other modified PVA or the occasion of PVA and usefulness, as the shared ratio of above-mentioned particular modification PVA, with respect to the gross mass of adhesive ingredients, preferably more than 10 quality %, more preferably more than 20 quality %.
As above-mentioned particular modification PVA, preferably saponification degree is the PVA of 85～99mol%.
If the not enough 85mol% of above-mentioned saponification degree, then insufficient for the resistance to water of the damping liquid medicine that uses when the hectographic printing, its result, cause so-called picking easily, when increasing the addition of modified PVA for fear of this phenomenon, though can prevent picking, tend to cause color development concentration to reduce.In addition, if above-mentioned saponification degree surpasses 99mol%, then be easy to generate not dissolved matter when the preparation coating fluid, this just becomes and produces the bad major reason of filming.
Should illustrate that even if in the scope of not damaging effect of the present invention and with the occasion of other modified PVAs or PVA, the saponification degree of these other modified PVA or PVA is also preferably in above-mentioned scope.
And then the degree of polymerization as above-mentioned particular modification PVA is preferably 200～2000.
If picking then takes place, and when increasing addition for fear of picking, then tends to cause color development concentration to reduce in above-mentioned degree of polymerization less than 200 easily when hectographic printing.In addition, if the above-mentioned degree of polymerization surpasses 2000, then modified PVA is difficult to dissolving in solvent (water), makes that the solution viscosity when preparation increases, and therefore tends to meet difficulty when preparation or coating heat sensitive recording layer form with coating fluid.
In addition, in order not damage effect of the present invention with other the modified PVA or the occasion of PVA and usefulness, the degree of polymerization of these other modified PVA or PVA is preferably in above-mentioned scope.
Should illustrate that the said degree of polymerization is meant the average degree of polymerization of obtaining according to the method for record among the JIS-K6726 (1994) herein.
In heat sensitive recording layer, amount as particular modification PVA, consider from improving the viewpoint that concentration takes place and give hectographic printing adaptability (preventing picking etc.), with respect to electron donability leuco dye 100 mass parts, be preferably 30～300 mass parts, more preferably 70～200 mass parts are preferably 100～170 mass parts especially.
Above-mentioned particular modification PVA except the function as the binding agent that is used to improve interlayer adhesion, also plays the function of dispersant and bond etc.
Explain the various PVA among the particular modification PVA below, that is: sulfo group modified polyvinylalcohol, diacetone modified polyvinylalcohol and acetoacetyl modified polyethylene alcohol.
Above-mentioned sulfo group modified polyvinylalcohol can make by following method, these methods comprise: with the alkene sulfonic acid of ethylene-sulfonic acid, allyl sulphonic acid, metering system sulfonic acid etc. or vinyl esters polymerization in alcohol or alcohol/water mixed solvent of its salt and vinylacetate etc., then with the method for the polymer saponification that obtained; The vinyl esters of (ミ De) sodium salt and vinylacetate etc. carries out copolymerization in the middle of making, then with the method for the polymer saponification that obtained; With processing such as PVA bromine, iodine, then with its method in the heated in water solution of acid sodium sulfite; With the method for PVA in the heated in water solution of the concentrated sulfuric acid; Handle PVA so that the method for its acetalation etc. with containing sulfonic aldehyde compound.
Above-mentioned diacetone modified polyvinylalcohol be a kind of in the copolymer that forms by monomer with diacetone base and vinyl esters partly or fully saponified product, it can carry out copolymerization by making monomer and vinyl esters with diacetone base, and the method with the resin saponification that obtained makes then.
In above-mentioned diacetone modified polyvinylalcohol, the ratio of monomer (repeat unit structure) with diacetone base there is not particular determination.
Above-mentioned acetoacetyl modified polyvinylalcohol generally can be made by being added into the acetyl group ketenes of liquid state or gaseous state and it is reacted in solution, dispersion liquid or the powder of polyvinyl alcohol resin.The acetyl group degree of this acetoacetyl modified polyvinylalcohol can be selected aptly according to the quality as the thermal recording medium of target.
-other compositions-
In the said heat sensitive recording layer of the present invention's the 1st embodiment, except mentioned component, can also contain other compositions of crosslinking agent, other pigment, metallic soap, wax, surfactant, adhesive, antistatic additive, defoamer, fluorescent dye etc. according to purpose or needs.
[crosslinking agent]
In heat sensitive recording layer, can contain the crosslinking agent that in the particular modification PVA that uses as above-mentioned adhesive (perhaps protecting colloid) and other modified PVAs etc., plays crosslinked action.By containing this crosslinking agent, can improve the resistance to water of thermal recording medium.
As above-mentioned crosslinking agent, can make the crosslinked material of particular modification PVA (preferably with other modified PVAs etc.) from those and select aptly, wherein, particularly preferably be the dihydrazide compound of the aldehyde compound, adipic dihydrazide etc. of glyoxal etc.
In heat sensitive recording layer,,, be preferably 1～50 mass parts, more preferably 3～20 mass parts with respect to as 100 mass parts such as the particular modification PVA of crosslinked object and other modified PVAs the amount of crosslinking agent.The amount of this crosslinking agent just can improve resistance to water effectively as long as in above-mentioned scope.
[mordant]
In order to prevent the profit of oozing when the ink mist recording, can in heat sensitive recording layer, contain mordant.
As above-mentioned mordant, can enumerate those and contain and be selected from amide groups, imide, primary amino radical, secondary amino group, uncle's amino, uncle's ammonium salt base, secondary ammonium alkali, tertiary amine alkali, the quaternary ammonium salt base at least-compound of kind of cation group.
As object lesson, can enumerate: polyamide-based epoxychloropropane, many vinyl benzyls of chlorination trimethylammonium, many diallyls of chlorination dimethylammonium, chlorination polymethyl acyloxy ethyl-beta-hydroxyethyl dimethylammonium, poly-dimethylamino methyl ethyl acrylate hydrochloride, polymine, polyallylamine, polyallylamine hydrochloride, polyamide-polyamino resin, cationic starch, dicyano diamides base formaldehyde condensation products, dimethyl-2-hydroxypropyl ammonium salt polymer etc.
Except above-mentioned example, cation type polymer also is suitable for.As this cation type polymer, for example can enumerate: polymine, polydiene propyl group amine, polyallylamine, many diallyls of chlorination dimethylammonium, chlorination polymethyl acyloxy ethyl-beta-hydroxyethyl dimethylammonium, polyallylamine hydrochloride, polyamide-polyamino resin, cationic starch, dicyano diamides base formaldehyde condensation products, dimethyl-2-hydroxypropyl ammonium salt polymer, poly-amidine, polyvinylamine etc.
The molecular weight of above-mentioned mordant is preferably about 1000～200000.During this molecular weight less than 1000, resistance to water has inadequate tendency, and is surpassing at 200000 o'clock, viscosity is increased, thereby make the suitability variation of operation.
In addition, above-mentioned cation type polymer also can add in arbitrary layer of heat sensitive recording layer and following protective layer.
[metallic soap, wax, surfactant]
As metallic soap, can enumerate the higher fatty acids slaine, can enumerate zinc stearate, calcium stearate, aluminum stearate etc. particularly.
As wax, for example can enumerate: paraffin, microwax, Brazil wax, methylol stearamide, Tissuemat E, polystyrene wax and fatty acid acyl amine wax etc., these waxes can a kind of independent uses, also can two or more mixing use.
As surfactant, for example can enumerate alkali metal salt, fluorine-containing surfactant of sulfosuccinic acids etc.
[adhesive]
The dispersion of above-mentioned electron donability leuco dye, electronic acceptance compound, inorganic pigment, adhesive, sensitizer and other compositions can be carried out in water miscible adhesive aptly.Herein, the adhesive as being suitable for preferably can dissolve the compound more than the 5 quality % in 25 ℃ water.For example can enumerate particularly: polyvinyl alcohol, methylcellulose, carboxymethyl cellulose, starch based (containing modified starch), gelatin, gum arabic, casein, styrene-maleic anhydride copolymer saponified etc.
Above-mentioned adhesive is just not useful when disperseing, but also has the function of the film-strength that improves heat sensitive recording layer, in order to bring into play this function, also can and use the adhesive of the synthetic high polymer latex system of SB, vinyl acetate co-polymer, acrylonitrile-butadiene copolymer, methyl acrylate butadiene copolymer, Vingon etc.
-other-
Can utilize the stirring pulverizer of ball mill, grater, puddle mixer etc. that above-mentioned electron donability leuco dye, electronic acceptance compound, inorganic pigment, adhesive and sensitizer are disperseed at the same time or separately, be mixed with coating fluid.As required, can in this coating fluid, be added into other above-mentioned compositions, that is: crosslinking agent, mordant, metallic soap, wax, surfactant, adhesive, antistatic additive, defoamer and fluorescent dye etc.
After being mixed with coating fluid as stated above, this coating fluid is applied on the surface of support to form heat sensitive recording layer.Method as the above-mentioned coating fluid of coating is not particularly limited, and for example can select aptly from using air knife doctor knife coater, roll coater, scraper plate to be coated with the rubbing method of machine, curtain flow coater etc., is dried after the coating.After the drying, preferably carry out smoothing and handle, use is provided then by calender.
In the occasion of coating formation heat sensitive recording layer, as the drying coated amount of coating fluid, preferably less than 6g/m 2, particularly preferably in 5g/m 2Below.
In the 1st embodiment of the present invention, from obtaining high concentration (high sensitivity), also can improve the viewpoint of picture quality (figure matter) simultaneously and consider with less raw material use amount, preferably use the curtain stream rubbing method of curtain stream coating machine especially.In addition, as described below, except heat sensitive recording layer, going back the occasion of lamination protective layer etc., by with the many layers of curtain stream rubbing method lamination coating simultaneously, can reduce the energy consumption when making.As described below particularly.
Thermal recording medium is preferably made as follows, promptly, by curtain stream rubbing method single or multiple coating fluid is coated on the surface of support,, thereby makes thermal recording medium then part or all drying single or that be formed at the many layers on the support.Kind as the layer that forms by curtain flow coat cloth does not have particular determination, for example can enumerate priming coat, heat sensitive recording layer, protective layer etc.The a series of layer that these adjoin each other preferably forms by the mode that multilayer is coated with simultaneously by curtain stream rubbing method.
The concrete example of the combination of the layer that the occasion that is coated with simultaneously as multilayer forms can be enumerated: the combination of priming coat and heat sensitive recording layer; The combination of heat sensitive recording layer and protective layer; The combination of priming coat, heat sensitive recording layer and protective layer; The combination of diverse two-layer above protective layer etc., unqualified to this.
As the curtain flow coat cloth apparatus that uses when the curtain flow coat cloth, there is not particular determination, for example can enumerate and extrude funnel type curtain flow coat cloth apparatus, sliding hopper type curtain flow coat cloth apparatus etc., wherein, particularly preferably be sliding hopper type curtain flow coat cloth apparatus that use and that in the public clear 49-24133 communique of spy, put down in writing when making sensitive photographic material etc.By using this class sliding hopper type curtain flow coat cloth apparatus, coating when can easily carry out multilayer.
In the 1st embodiment of thermal recording medium of the present invention, conveying from be suppressed at printer is bad, bad etc. the viewpoint that stacks of the paper after the print is considered, thermal recording medium is the maximum of the height of flange that bending upwards floats from its plane of leaving standstill should be below 5.0mm.Herein, said height of flange is meant, thermal recording medium is from the plane that one side surface (side surface that does not for example have heat sensitive recording layer) leaves standstill closely, to the distance on the surface (this part does not have a side surface of heat sensitive recording layer) of the part (for example four of thermal recording medium angles) that is this thermal recording medium that bending floats upward on this plane.This distance equals not have from the plane surface of crooked heat sensitive recording layer haply, to the distance of the thermal photography laminar surface that is the part that bending upwards floats from this plane.
Maximum by making above-mentioned height of flange can be made and a kind ofly can improve the conveying in the printer, the stacking property of the paper after the print (thermal recording medium), the thermal recording medium of good operability below 5.0mm.As above-mentioned height of flange, more preferably below 4.0mm.
For above-mentioned height of flange is adjusted in the above-mentioned scope, preferably undertaken by the method that on the side surface that heat sensitive recording layer is not set on the support, is coated with back coating liquid (バ Star Network liquid) etc.Below back coating liquid is described in detail.
[back coating liquid]
As above-mentioned back coating liquid, except water, preferably in this water, contain adhesive, surfactant, antistatic additive etc. and the aqueous solution of formation.As above-mentioned adhesive, for example can enumerate: the latex of the hydrolysate of polyvinyl alcohol, carboxy-modified polyvinyl alcohol, vinyl acetate-acrylamide copolymer, silicon modified polyvinylalcohol, starch, modified starch, methylcellulose, carboxymethyl cellulose, CMC, gelatin, gum arabic, casein, styrene-maleic acid copolymer, polyacrylamide derivative, polyvinylpyrrolidone, SBR styrene butadiene rubbers latex, acrylonitrile-butadiene rubber latex, methyl acrylate-butadiene rubber latex, vinyl acetate emulsion etc. etc.
As above-mentioned surfactant, for example can enumerate: the sulfosuccinic acid alkyl ester salt of the alkylbenzenesulfonate of neopelex etc., dioctyl sodium sulphosuccinate etc., polyoxyethylene alkyl ether phosphate, calgon, perfluoroalkyl carboxylate etc.In addition, as above-mentioned antistatic additive, for example can enumerate the conductive metal compound etc. of the anionic polyelectrolyte, electroconductive zinc oxide, tin oxide etc. of the inorganic salts, kayexalate etc. of sodium chloride etc.
Absolute value to the coating weight of above-mentioned back coating liquid is unqualified, can become in the maximum of the height of flange that can make thermal recording medium (particularly its four angles) in the scope below the 5.0mm to select aptly.
When being coated with above-mentioned back coating liquid, can use known rubbing method.Can enumerate the method for using air knife doctor knife coater, roll coater, groove roll coater etc. particularly, wherein, preferably use the rubbing method of air knife doctor knife coater or groove roll coater.In the method for above-mentioned use coating machine, can use off-machine coater to be coated with, also can the use machine on coating machine be coated with.
＜protective layer 〉
At least the protective layer of one deck preferably is set on heat sensitive recording layer, and this protective layer can constitute according to the mode of the micropowder that contains organic or inorganic, adhesive, surfactant, hot melt material etc.
As above-mentioned micropowder, for example can enumerate: the mineral-type micropowder of calcium carbonate, silica-based, zinc oxide, titanium oxide, aluminium hydroxide, zinc hydroxide, barium sulfate, kaolin, clay, talcum, surface treated calcium or silica etc., in addition, can also enumerate: organic class micropowder of urea-formaldehyde resin, styrene/methacrylic acid copolymer, polystyrene etc. etc.
As the adhesive that in protective layer, contains, for example can enumerate: polyvinyl alcohol; carboxy-modified polyvinyl alcohol; vinyl acetate-acrylamide copolymer; the silicon modified polyvinylalcohol; starch; modified starch; methylcellulose; carboxymethyl cellulose; CMC; the gelatin class; gum arabic; casein; the styrene-maleic acid copolymer hydrolysate; polyacrylamide derivative; polyvinylpyrrolidone; and SBR styrene butadiene rubbers latex; acrylonitrile-butadiene rubber latex; methyl acrylate-butadiene rubber latex; the latex class of vinyl acetate emulsion etc. etc.
In addition, preferably add anti-hydrated agent, thereby improve the embodiment of the storage stability of thermal recording medium further so that make the adhesive ingredients in the protective layer crosslinked.As this anti-hydrated agent, for example can enumerate: the twain-aldehyde compound compounds of the water-soluble initial stage condensation product of N-methylolurea, N-methylol melamine, urea-formaldehyde etc., glyoxal, glutaraldehyde etc., the mineral-type crosslinking agent of boric acid, borax, colloidal silica etc., polyamide-based epoxychloropropane etc.
In above-mentioned composition, as particularly preferred protective layer, preferably a kind of containing is selected from the inorganic pigment at least a in aluminium hydroxide, kaolin and the amorphous silica and the embodiment of water soluble polymer.By constituting protective layer by this embodiment, can improve keeping quality, can also give the operability and the adaptability of affixing one's seal simultaneously.In addition, can also contain surfactant, hot melt material etc.
As the volume average particle size of the inorganic pigment that in protective layer, contains, be preferably 0.5～3 μ m, more preferably 0.7～2.5 μ m.Wherein, consider, be preferably the aluminium hydroxide of 0.5～1.2 μ m, consider, preferably use amorphous silica from improving the adaptive viewpoint of ink-jet from affix one's seal adaptive viewpoint of raising.Herein, to the mensuration of volume average particle size according to carrying out with same method such as above-mentioned electron donability inorganic dyestuff.
As the total amount that is selected from the inorganic pigment in aluminium hydroxide, kaolin and the amorphous silica, the whole solid contents (quality) with respect in the coating fluid of protective layer formation usefulness are preferably 10～90 quality %, more preferably 30～70 quality %.In addition, can in the scope of not damaging effect of the present invention (particularly conservatory raising and operability and adaptive the giving of affixing one's seal), merge other pigment that use barium sulfate, zinc sulfate, talcum, clay, colloidal silica etc.
As above-mentioned water soluble polymer, can enumerate: the modified starch of polyvinyl alcohol in above-mentioned adhesive or modified polyvinylalcohol (hereinafter it being referred to as " polyvinyl alcohol "), starch or oxidized starch, urea organic phosphate starch etc., styrene-maleic anhydride copolymer, styrene-maleic anhydride copolymer alkyl carboxylate, styrene-propene acid copolymer etc. contain the polymer of carboxyl etc.Wherein, adaptive viewpoint is considered from affixing one's seal, preferably polyvinyl alcohol, oxidized starch, urea organic phosphate starch especially preferably mix use with polyvinyl alcohol (x) and oxidized starch and/or urea organic phosphate starch (y) by 90/10～10/90 mass ratio (x/y).Particularly above-mentioned polyvinyl alcohol, oxidized starch and urea organic phosphate starch are all merged when using oxidized starch (y 1) and urea organic phosphate starch (y 2) mass ratio (y 1/ y 2) be preferably 10/90～90/10.
As above-mentioned modified polyvinylalcohol; preferably acetoacetyl modified polyvinylalcohol, diacetone modified polyvinylalcohol, silicon modified polyvinylalcohol, acid amides modified polyvinylalcohol; in addition, also can use sulfo group modified polyvinylalcohol, carboxy-modified polyvinyl alcohol etc.
In addition, by be used in combination can with the crosslinking agent of these polyvinyl alcohol reaction, can improve keeping quality, operability and the adaptability of affixing one's seal further.
As the ratio that contains of above-mentioned water soluble polymer, form whole solid contents (quality) of using coating fluid with respect to protective layer, be preferably 10～90 quality %, more preferably 30～70 quality %.
As the crosslinking agent that is used to make above-mentioned water soluble polymer crosslinked, for example can enumerate: the polyamine compound of ethylenediamine etc.; The polyaldehyde compound of glyoxal, glutaraldehyde, dialdehyde etc.; The dihydrazide compound of adipic dihydrazide, phthalic acid two hydrazides etc.; Water-soluble methylol compound (urea, melamine, phenol); The multi-functional epoxy compound; Multivalent metal salt (Al, Ti, Zr, Mg) etc.Wherein, preferably many aldehyde compounds, dihydrazide compound.
As the ratio that contains of above-mentioned crosslinking agent,, be preferably about 2～30 quality %, more preferably 5～20 quality % with respect to the quality of above-mentioned water soluble polymer.By containing this crosslinking agent, can improve film-strength and resistance to water etc. further.
In addition; in protective layer; mixing ratio as inorganic pigment that is selected from aluminium hydroxide, kaolin and amorphous silica and water soluble polymer; should be according to the difference of the kind of inorganic pigment and particle diameter thereof, water soluble polymer kind and different; but; with respect to the quality of inorganic pigment, the content of water soluble polymer is preferably 50～400 quality %, more preferably 100～250 quality %.
In addition, the gross mass of inorganic pigment in protective layer and water soluble polymer preferably is equivalent to more than the 50 quality % of all solids composition quality in the protective layer.
In addition, consider, preferably in above-mentioned protective layer, just in the coating fluid (hereinafter being sometimes referred to as " protective layer used coating fluid ") of protective layer formation usefulness, add surfactant from improving the adaptive viewpoint of ink-jet.
As above-mentioned surfactant, for example preferably use: the sulfosuccinic acid alkyl ester salt of the alkylbenzenesulfonate of neopelex etc., dioctyl sodium sulphosuccinate etc., polyoxyethylene alkyl ether phosphate, calgon, perfluoroalkyl carboxylate etc., wherein, be more preferably the sulfosuccinic acid alkyl ester salt.
As the ratio that contains of above-mentioned surfactant, form whole solid contents (quality) of using coating fluid with respect to protective layer, be preferably 0.1～5 quality %, more preferably 0.5～3 quality %.
The coating fluid that protective layer forms usefulness can be dissolved or dispersed in the required water solvent and prepare by with the above-mentioned inorganic pigment that is selected from aluminium hydroxide, kaolin and amorphous silica and water soluble polymer and the crosslinking agent that adds as required, surfactant etc.Also can in the scope of not damaging effect of the present invention (particularly conservatory raising and operability and adaptive the giving of affixing one's seal), in above-mentioned coating fluid, add lubricant, defoamer, fluorescent whitening agent, colored organic pigment etc. herein.
As above-mentioned lubricant, for example can enumerate: the metallic soap of zinc stearate, calcium stearate etc.; The wax class of paraffin, microwax, Brazil wax synthetic high polymer wax etc. etc.
-support-
As above-mentioned support, can use known traditionally support.Can enumerate particularly: the paper support of good quality paper etc., the support of coating resin or pigment and coated paper, the resin layered paper that forms, good quality paper, synthetic paper, plastic sheeting etc. on paper with priming coat.Also can use and mainly contain old paper stock, just old paper stock occupies the support more than the 50 quality % in support.
As above-mentioned support, consider from the viewpoint of a repeatability, preferably press smoothness that JIS-P8119 the stipulates level and smooth support in 300 seconds～500 seconds scopes.And then, according to above-mentioned same reason, according to the above-mentioned smoothness of JIS-P8119 regulation more preferably more than 100 seconds, particularly preferably in more than 150 seconds.
Above-mentioned old paper stock generally can be by following 1)～3) the combination of three operations prepare.
1) dissociates ... place pulper to handle to resolve into waste paper fibrous and printing-ink is peeled off from fiber in waste paper with mechanical force and medicine.
2) dedusting ... remove foreign matter contained in the waste paper (plastics etc.) and dust.
3) deinking ... the printing-ink of peeling off from fiber is scavenged into outside the system with floatation or washing method.
In addition, as required, can in deinking or in other operation, bleach.
Using the content that so obtains is the old paper stock of 100 quality % or by old paper stock and the mixture that the fresh paper pulp that contains quantity not sufficient 50 quality % forms, and forms the support that thermal recording medium is used according to a conventional method.
Can on above-mentioned support, priming coat be set.In the case, preferably on degree of sizing is the surface of the support more than 5 seconds priming coat being set, is the priming coat of principal component with pigment and adhesive preferably.
Pigment as priming coat is used can all use general inorganic or organic pigment, preferably presses the oil absorption pigment of oil suction degree more than 40ml/100g (cc/100g) of JIS-K5101 regulation especially.As the concrete example of this oil absorption pigment, can enumerate: burn till kaolin, aluminium oxide, magnesium carbonate, burn till diatomite, alumina silicate, aluminium oxide, magnesium silicate, calcium carbonate, barium sulfate, aluminium hydroxide, kaolin, burn till kaolin, amorphous silica, urea-formaldehyde resin powder etc.Wherein, special preferably above-mentioned oil suction degree is the kaolin that burns till of 70ml/100g～80ml/100g.
When coating on support forms the occasion of priming coat, as the coating weight of above-mentioned pigment, preferably at 2g/m 2More than, more preferably at 4g/m 2More than, be preferably 7～12g/m2 especially.
As the adhesive that priming coat is used, can enumerate water soluble polymer, aqueous binder.These adhesives can a kind of independent use, also can be two or more and use.
As above-mentioned water soluble polymer, for example can enumerate: starch, polyvinyl alcohol, polyacrylamide, carboxymethyl cellulose, methylcellulose, casein etc.As above-mentioned aqueous binder, general is synthetic rubber latex, synthetic resin emulsion, for example can enumerate: SBR styrene butadiene rubbers latex, acrylonitrile-butadiene rubber latex, methyl acrylate-butadiene rubber latex, vinyl acetate emulsion etc.
As the use amount of priming coat with adhesive, this two aspect of heat sensitivity that can take into account film-strength and temperature-sensitive chromonic layer decides, still, with respect to the quality of priming coat with pigment, be preferably 3～100 quality %, more preferably 5～50 quality % are preferably 8～15 quality % especially.In addition, also can in priming coat, add wax, fading prevents agent, surfactant etc.
Priming coat forms the coating of the coating fluid of usefulness and can be undertaken by known rubbing method.Can enumerate particularly, use air knife doctor knife coater, roll coater, scraper plate to be coated with the rubbing method of machine, groove roll coater, curtain flow coater etc., wherein, preferably use curtain flow coater or scraper plate to be coated with the rubbing method of machine, be more preferably the rubbing method that uses scraper plate to be coated with machine.In coating, after the drying, and then can also use calender etc. to apply smoothing processing as required.
Be coated with the method for machine as above-mentioned use scraper plate, be not limited to use the rubbing method of ramp type scraper plate or bending-type scraper plate, also comprise bar-shaped scraper plate rubbing method and than land scraper plate (PVC Le Block レ-De) rubbing method etc., in addition, be not limited to use off-machine coater to be coated with, can use also that coating machine is coated with on the machine that is arranged on the paper machine.In addition, the time give flowability in order to obtain good flatness and surface configuration so that carrying out the scraper plate coating, can in forming the coating fluid (coating liquid for undercoat layer) of usefulness, priming coat be added into 1～5 quality % that is equivalent to above-mentioned amount of pigment, preferred 1～3 quality % and degree of etherification falling are 0.6～0.8, and weight average molecular weight is 20000～200000 carboxymethyl cellulose.
Coating weight to priming coat is not particularly limited, and still, according to the characteristic of thermal recording medium, the coating weight of priming coat is preferably at 2g/m 2More than, more preferably at 4g/m 2More than, be preferably 7～12g/m especially 2
In the present invention, consider from a matching that improves thermal head and the viewpoint of seeking high sensitivityization and high image qualityization, the priming coat body paper that preferably has priming coat (the special preferably good priming coat of oil absorption, effect of heat insulation and flatness) preferably has especially and uses scraper plate to be coated with the priming coat body paper of the priming coat that contains oil absorption pigment of machine coating.
As the Na that in thermal recording medium, contains +Ion and K +The total ion concentration of ion is considered from the viewpoint that the thermal head generation thermal head that prevents to contact with thermal recording medium corrodes, preferably below 1500ppm, more preferably below 1000ppm, below 800ppm.
Above-mentioned Na +Ion and K +The ion concentration of ion can be measured as follows,, with the thermal recording medium hot water extracting, measures Na in this extraction water by the quantitative analysis method that uses the atom light absorption method then that is +Ion and K +The mass of ion of ion.Above-mentioned total ion concentration is represented with the ppm number with respect to the thermal recording medium gross mass.
In the 1st embodiment of thermal recording medium of the present invention, the surface wettability of this heat sensitive recording layer, behind the distilled water that just on the surface of heat sensitive recording layer, drips through the contact angle after 0.1 second, preferably more than 20 °, more preferably more than 50 °.By above-mentioned contact angle is in the above-mentioned scope, can prevent when using the ink-jet printer lettering that the literal that prints off from oozing profit (give and improve ink-jet adaptability).
By containing electronic acceptance compound (preferred 4-hydroxy benzenes sulfonanilide) by above-mentioned general formula (1) expression, can obtain above-mentioned contact angle, in addition, keep the material of bigger numerical as the contact angle that can make recording surface and distilled water, preferably by the method that contains the said sensitizer of the present invention, paraffin etc. in the heat sensitive recording layer is prepared.
Above-mentioned measurement of contact angle can be carried out as follows, that is, the distilled water that drips on the surface (recording surface) of the heat sensitive recording layer of thermal recording medium is measured the contact angle that begins from dripping through after 0.1 second then according to a conventional method.For example can use FIBRO system (the dynamics contact angle absorption testers of DAT1100 (ab society system) etc.) etc. to measure.
The 1st embodiment of thermal recording medium of the present invention make the image keeping quality good aspect be useful, after the image that forms after print was placed 24 hours under the environmental condition of 60 ℃ of temperature and relative humidity 20%, the concentration survival rate in above-mentioned formation image was more than 65%.As mentioned above,, preferably contain image stabilizing agent etc., above-mentioned concentration survival rate is in the above-mentioned scope by containing electronic acceptance compound (especially preferably 4-hydroxy benzenes sulfonanilide) by general formula (1) expression.So just can make established image in long-time, keep high concentration, and also can be suitable in requirement such as the keeping of vital document, presell ticket, receipt, bank note have an image reliability in for a long time field.
The image color survival rate is by the expression of following image color ratio, promptly, after print, use Macbeath (マ Network ベ ス) reflection of the concentration (for example RD-918) to measure the concentration of the image that obtains immediately, lettering under the same conditions in addition, then be placed in 60 ℃, the atmosphere of relative humidity 20% and placed 24 hours, measure its image color then, with the concentration survival rate of ratio (%) presentation video of above-mentioned two kinds of image colors.
Concentration survival rate=[(image color after the placement)/(image color that records immediately behind the lettering)] * 100
[the 2nd embodiment]
In the 2nd embodiment of thermal recording medium of the present invention, have the heat sensitive recording layer that combines the color development system by electron donability leuco dye and electronic acceptance compound, wherein contain by R 1-Ph-SO 2R 3The compound of expression and carries out the hot stamping phase time as above-mentioned electronic acceptance compound on heat sensitive recording layer, be 15.2mJ/mm at the energy that is applied by thermal head 2Condition under the image color that obtains more than 1.20.
Explain the 2nd embodiment of thermal recording medium of the present invention below.
The 2nd embodiment of thermal recording medium of the present invention be have on the support one deck or two-layer more than heat sensitive recording layer, preferably have protective layer.In addition, as required, can also have other layer such as intermediate layer.
＜heat sensitive recording layer 〉
Above-mentioned heat sensitive recording layer contain at least the electron donability leuco dye, can be by the electronic acceptance compound of color development with the reaction of this electron donability leuco dye, preferably contain image stabilizing agent (ultraviolet ray prevents agent), inorganic pigment, adhesive, sensitizer, as required, can also contain other compositions.
-electron donability leuco dye-
In the said heat sensitive recording layer of the 2nd embodiment of the present invention, contain at least a electron donability leuco dye as the color development composition.Explanation to the electron donability leuco dye that contains in the explanation of above-mentioned electron donability leuco dye and the said heat sensitive recording layer of the 1st embodiment of the present invention is identical.
-electronic acceptance compound-
Containing in the said heat sensitive recording layer of the present invention's the 2nd embodiment can be by meeting thermal response and the electronic acceptance compound of color development with above-mentioned electron donability leuco dye by at least a conduct in the compound of following general formula (1) expression.Owing to contain this compound as electronic acceptance compound, therefore can realize high sensitivityization owing to keeping low background fog, can also improve a matching of the long preservation (image keeping quality), resistance to chemical reagents, ink-jet adaptability and the thermal head that have formed image simultaneously.
General formula (1):
R 1-Ph-SO 2R 2
In above-mentioned general formula (1), R 1Expression hydroxyl, alkyl.R 2Expression-Ph ,-NH-Ph ,-Ph-OR 3,-NH-CO-NH-Ph, R 3The expression alkyl.Ph represents phenyl, also can be contained-SO 2R 2Substituting group replace.
As by above-mentioned R 1The alkyl of expression, preferably the alkyl of carbon number 1～3 is more preferably methyl, ethyl, isopropyl etc.Wherein, as above-mentioned R 1, hydroxyl especially preferably.
Above-mentioned R 3The expression alkyl, as this alkyl, the preferably alkyl of carbon number 1～4, especially preferably isopropyl.In addition, Ph represents phenyl, but it can be contained-SO 2R 2The substituted-phenyl that replaces of substituting group, and this substituent R 2Can also be by replacements such as methyl, halogen atoms.As this substituting group, can enumerate-CH 2-C 6H 5-NHCONH-SO 2-C 6H 5,-SO 2-C 6H 5-,-SO 2-C 6H 4-CH 3,-SO 2-C 6H 4-Cl etc.
Wherein, as above-mentioned R 2, preferably-NH-Ph, especially preferably-NH-C 6H 5
Preferred concrete example as the compound of representing by above-mentioned general formula (1); can enumerate: 4-hydroxy benzenes sulfonanilide (=right-N-phenyl sulfamoyl phenol); right-N-(2-chlorphenyl) sulfonamides phenol; right-N-3-tolyl sulfonamides phenol; right-N-2-tolyl sulfonamides phenol; right-N-(3-anisyl) sulfonamides phenol; right-N-(3-hydroxyphenyl) sulfonamides phenol; right-N-(4-hydroxyphenyl) sulfonamides phenol; 2-chloro-4-N-phenyl sulfamoyl phenol; 2-chloro-4-N-(3-hydroxyphenyl) sulfonamides phenol; 4 '-hydroxyl para toluene sulfonamide; 4; 4 '-two (tolysulfonyl amido carbonamido) diphenyl methane (=BTUM); 4-hydroxyl-4 '-isopropoxy diphenyl sulphone (DPS); 2, two (benzenesulfonyl) phenol of 4-etc.But, be not limited to these concrete examples in the present invention.
In electronic acceptance compound by above-mentioned general formula (1) expression, consider from two aspects of taking into account image keeping quality and background fog, most preferably be 4-hydroxy benzenes sulfonanilide.
As the amount of the electronic acceptance compound in single heat sensitive recording layer, with respect to the quality of above-mentioned electron donability leuco dye, be preferably 50～400 quality %, more preferably 100～300 quality %.
Can be electronic acceptance compound and other known electronic acceptance compounds and usefulness in the scope of not damaging effect of the present invention (the particularly raising of the alleviating of background fog, high sensitivityization and image keeping quality, resistance to chemical reagents and thermal head matching) by above-mentioned general formula (1) expression.
As above-mentioned known electronic acceptance compound, can select aptly to use, particularly consider, preferably phenol type compound or salicyclic acid derivatives and multivalent metal salt thereof from the viewpoint that suppresses background fog.
To the explanation of above-mentioned phenol type compound and salicyclic acid derivatives, with identical in the present invention's the 1st embodiment to the explanation of phenol type compound and salicyclic acid derivatives.
And with the occasion of above-mentioned known electronic acceptance compound, amount as the electronic acceptance compound of representing by above-mentioned general formula (1), with respect to the gross mass of electronic acceptance compound, preferably more than 50 quality %, more preferably more than 70 quality %.
When the preparation heat sensitive recording layer forms the coating fluid of usefulness, as the particle diameter of above-mentioned electronic acceptance compound, by volume average grain diameter preferably below 1.0 μ m, 0.4～0.7 μ m more preferably.If this volume average particle size surpasses 1.0 μ m, its heat sensitivity tends to reduce.In addition, if less than 0.4 μ m then tends to cause the background fog deterioration.
Above-mentioned volume average particle size can easily utilize laser diffraction formula particle size distribution device (for example LA500 (ホ リ バ (strain) system)) etc. to record.
-sensitizer-
In the said heat sensitive recording layer of the 2nd embodiment of the present invention, preferably contain sensitizer.To identical in the explanation of above-mentioned sensitizer and the 1st embodiment of the present invention to the explanation of sensitizer.
-image stabilizing agent (ultra-violet absorber)-
In the said heat sensitive recording layer of the 2nd embodiment of the present invention, preferably contain image stabilizing agent (containing ultra-violet absorber).To identical in the explanation of above-mentioned image stabilizing agent (containing ultra-violet absorber) and the 1st embodiment of the present invention to the explanation of image stabilizing agent (containing ultra-violet absorber).
-inorganic pigment-
In the said heat sensitive recording layer of the 2nd embodiment of the present invention, especially preferably contain at least a (the said inorganic pigment among the present invention) from calcite class calcium carbonate, amorphous silica and aluminium hydroxide, selected as inorganic pigment.To identical in the explanation of above-mentioned inorganic pigment and the 1st embodiment of the present invention to the explanation of inorganic pigment.
-adhesive-
In the said heat sensitive recording layer of the 2nd embodiment of the present invention; preferably contain at least a (that is the modified polyvinylalcohol (hereinafter being sometimes referred to as " specific modified PVA ")) that be selected from sulfo group modified polyethylene alcohol, the pure and mild acetoacetyl modified polyethylene of the diacetone modified polyethylene alcohol as adhesive (the perhaps protecting colloid when disperseing).To identical in the explanation of above-mentioned adhesive and the 1st embodiment of the present invention to the explanation of adhesive.
-other compositions-
In the said heat sensitive recording layer of the present invention's the 2nd embodiment, except mentioned component, can also contain other compositions of crosslinking agent, other pigment, metallic soap, wax, surfactant, adhesive, antistatic additive, defoamer, fluorescent dye etc. according to purpose or needs.
[crosslinking agent]
In heat sensitive recording layer, can contain the crosslinking agent that in the particular modification PVA that uses as above-mentioned adhesive (perhaps protecting colloid) and other modified PVAs etc., plays crosslinked action.By containing this crosslinking agent, can improve the resistance to water of thermal recording medium.
To identical in the explanation of above-mentioned crosslinking agent and the 1st embodiment of the present invention to the explanation of crosslinking agent.
[mordant]
In order to prevent the profit of oozing when the ink mist recording, can in heat sensitive recording layer, contain mordant.To identical in the explanation of above-mentioned mordant and the 1st embodiment of the present invention to the explanation of mordant.
[metallic soap, wax, surfactant]
To identical in the explanation of metallic soap, wax and surfactant and the 1st embodiment of the present invention to the explanation of metallic soap, wax and surfactant.
[adhesive]
The dispersion of above-mentioned electron donability leuco dye, electronic acceptance compound, inorganic pigment, adhesive, sensitizer and other compositions can be carried out in water miscible adhesive aptly.To identical in the explanation of the adhesive that is suitable for and the 1st embodiment of the present invention herein to the explanation of adhesive.
-other-
Can utilize the stirring pulverizer of ball mill, grater, puddle mixer etc. that above-mentioned electron donability leuco dye, electronic acceptance compound, inorganic pigment, adhesive and sensitizer are disperseed at the same time or separately, be mixed with coating fluid.As required, can in this coating fluid, be added into other above-mentioned compositions, that is: crosslinking agent, mordant, metallic soap, wax, surfactant, adhesive, antistatic additive, defoamer and fluorescent dye etc.
After being mixed with coating fluid as stated above, this coating fluid is applied on the surface of support to form heat sensitive recording layer.
To the coating process that is used to be coated with coating fluid, when coating forms heat sensitive recording layer coating fluid drying coated amount, according to the explanation that the curtain stream rubbing method as preferred coating process carries out multilayer lamination coating simultaneously and uses the curtain flow coat cloth apparatus of curtain stream rubbing method, identical with the explanation in the 1st embodiment of the present invention.
In the 2nd embodiment of the present invention, in order to be 15.2mJ/mm applying energy 2Condition under carry out the hot stamping phase time image color reach more than 1.20; the having or not to wait of formation that can be by selecting above-mentioned each composition in suitable mode or the formation of layer, coating process etc., particularly kind by selecting electron donability leuco dye, electronic acceptance compound, adhesive and sensitizer or amount and coating process, protective layer carries out.
As at the above-mentioned above-mentioned image color that obtains when applying energy, especially preferably 1.25～1.35.
＜protective layer 〉
At least the protective layer of one deck preferably is set on heat sensitive recording layer, and this protective layer can constitute according to the mode of the micropowder that contains organic or inorganic, adhesive, surfactant, hot melt material etc.To identical in the explanation of protective layer and the 1st embodiment of the present invention to the explanation of protective layer.
-support-
As above-mentioned support, can use known traditionally support.Can enumerate particularly: the paper support of good quality paper etc., the support of coating resin or pigment and coated paper, the resin layered paper that forms, good quality paper, synthetic paper, plastic sheeting etc. on paper with priming coat.Also can use and mainly contain old paper stock, just old paper stock occupies the support more than the 50 quality % in support.
To the explanation of above-mentioned support with identical with the explanation in the 1st embodiment of the present invention to the explanation that is arranged on the priming coat on the support.
To the Na that contains in the thermal recording medium +Ion and K +The explanation of the total ion concentration of ion is identical with the explanation in the 1st embodiment of the present invention.
In the 2nd embodiment of thermal recording medium of the present invention, the surface wettability of this heat sensitive recording layer, behind the distilled water that just on the surface of heat sensitive recording layer, drips through the contact angle after 0.1 second, preferably more than 20 °, more preferably more than 50 °.By above-mentioned contact angle is in the above-mentioned scope, can prevent when using the ink-jet printer lettering that the literal that prints off from oozing profit (give and improve ink-jet adaptability).
By containing electronic acceptance compound (preferred 4-hydroxy benzenes sulfonanilide) by above-mentioned general formula (1) expression, can obtain above-mentioned contact angle, in addition, keep the material of bigger numerical as the contact angle that can make recording surface and distilled water, preferably by the method that contains the said sensitizer of the present invention, paraffin etc. in the heat sensitive recording layer is prepared.
Explanation to above-mentioned measurement of contact angle is identical with the explanation in the 1st embodiment of the present invention.
The 2nd embodiment of thermal recording medium of the present invention make the image keeping quality good aspect be useful, after the image that forms after print was placed 24 hours under the environmental condition of 60 ℃ of temperature and relative humidity 20%, the concentration survival rate in above-mentioned formation image was more than 65%.As mentioned above,, preferably contain image stabilizing agent etc., above-mentioned concentration survival rate is in the above-mentioned scope by containing electronic acceptance compound (especially preferably 4-hydroxy benzenes sulfonanilide) by general formula (1) expression.So just can make established image in long-time, keep high concentration, and also can be suitable in requirement such as the keeping of vital document, presell ticket, receipt, bank note have an image reliability in for a long time field.
Explanation to the image color survival rate is identical with the explanation in the 1st embodiment of the present invention.
[the 3rd embodiment]
In the 3rd embodiment of thermal recording medium of the present invention, by having the heat sensitive recording layer that combines the color development system by electron donability leuco dye and electronic acceptance compound, can be so that be 15.2mJ/mm according to applying energy with thermal head 2The condition lettering time image color that obtains more than 1.20, and in the confficient of static friction and the scope of the coefficient of kinetic friction when making mantle friction 0.2～0.5 with the most surperficial and dorsal part of the table side of the above-mentioned heat sensitive recording layer of one deck at least.
Herein, the most surperficial surface that is meant heat sensitive recording layer of so-called table side perhaps, when the occasion that forms other layers such as protective layer on this heat sensitive recording layer, is meant the surface that is arranged on the layer of outermost (from a support side farthest) in this other layer.Similarly, so-called dorsal part the most surperficial is meant the surface of the side that heat sensitive recording layer is not set on support, perhaps, when the dorsal part at heat sensitive recording layer is provided with the occasion of other layers, is meant the surface that is arranged on outermost layer in these other layers.
If above-mentioned confficient of static friction and coefficient of kinetic friction less than 0.2, then can cause frictional force deficiency with conveying devices such as rubber rollers, like this, when carrying thermal recording medium, cause carrying the probability rising of damage on material, thereby make the reduction of conveying property because conveying device is slided.In addition, if the above-mentioned confficient of static friction and the coefficient of kinetic friction surpass 0.5, then in the occasion that each thermal recording medium is used by superposed state, will make the slip variation between each material, therefore, press the occasion that single-sheet stationery is carried to thermal recording medium, the probability that the state that will cause overlaping by multipage paper is carried rises, and this causes the reduction of conveying property equally.Confficient of static friction is preferably in 0.25～0.45 scope, more preferably in 0.30～0.45 scope.Equally, the coefficient of kinetic friction is preferably in 0.25～0.45 scope, more preferably in 0.30～0.45 scope.
The above-mentioned confficient of static friction and the coefficient of kinetic friction can be measured according to the regulation of " ASTM D1894-73 ".Can measure according to following method particularly.
At first, in 23 ℃ thermostatic chamber, be cut into the size (thermal recording medium A) of wide 100mm, long 200mm at the thermal recording medium that has heat sensitive recording layer on the side surface, recording surface is assemblied on the flat runner up a kind of.Similarly, the thermal recording medium B that is cut into wide 60mm, long 120mm size as load weight (W °=1.96N (200g power); Hereinafter referred to as " sled "), reel as the mode of inboard (dorsal part the most surperficial) by its recording surface as the outside, fix with adhesive tape.
Then, sled is connected on the load cell with monofilament, the sled that forms being reeled by thermal recording medium sheet B is placed on the thermal photography face (showing the most surperficial of side) of the thermal recording medium sheet A that is assemblied on the flat runner lightly, flat runner is moved by the test speed that 600mm/ divides, measure the confficient of static friction and the coefficient of kinetic friction.
In the 3rd embodiment of thermal recording medium of the present invention, by being adjusted at the addition of the lubricant that contains in each superficial layer or other metallic soaps, wax, surfactant etc., the most surperficial confficient of static friction and the coefficient of kinetic friction of the most surperficial and dorsal part of table side are in the above-mentioned scope.As lubricant, for example can enumerate: the metallic soap of zinc stearate, calcium stearate etc.; The wax class of paraffin, microwax, Brazil wax synthetic high polymer wax class etc. etc.
Explain the 3rd embodiment of thermal recording medium of the present invention below.
The 3rd embodiment of thermal recording medium of the present invention have on the support one deck or two-layer more than heat sensitive recording layer, preferably have protective layer.In addition, as required, can also have other layers in intermediate layer etc.
＜heat sensitive recording layer 〉
Above-mentioned heat sensitive recording layer contain at least the electron donability leuco dye, can be by the electronic acceptance compound of color development with the reaction of this electron donability leuco dye, preferably contain image stabilizing agent (ultraviolet ray prevents agent), inorganic pigment, adhesive, sensitizer, as required, can also contain other compositions.
-electron donability leuco dye-
In the said heat sensitive recording layer of the 3rd embodiment of the present invention, contain at least a electron donability leuco dye as the color development composition.Explanation to the electron donability leuco dye that contains in the explanation of above-mentioned electron donability leuco dye and the said heat sensitive recording layer of the 1st embodiment of the present invention is identical.
-electronics acceptance leuco dye-
Containing in the said heat sensitive recording layer of the 3rd embodiment of the present invention can be by meeting thermal response and the electronic acceptance compound of color development with above-mentioned electron donability leuco dye by at least a conduct in the compound of following general formula (1) expression.By containing this compound as electronic acceptance compound, can realize high sensitivityization owing to keeping low background fog, can also improve a matching of the long preservation (image keeping quality), resistance to chemical reagents, ink-jet adaptability and the thermal head that have formed image simultaneously.
General formula (1):
R 1-Ph-SO 2R 2
In following formula, R 1Expression hydroxyl, alkyl.R 2Expression-Ph ,-NH-Ph ,-Ph-OR 3,-NH-CO-NH-Ph; R 3The expression alkyl.Ph represents phenyl, also can be contained-SO 2R 2Substituting group replace.
As by above-mentioned R 1The alkyl of expression, preferably the alkyl of carbon number 1～3 is more preferably methyl, ethyl, isopropyl etc.Wherein, as above-mentioned R 1, hydroxyl especially preferably.
Above-mentioned R 3The expression alkyl, as this alkyl, the preferably alkyl of carbon number 1～4, especially preferably isopropyl.In addition, Ph represents phenyl, but it can " be contained-SO 2R 2Substituting group " substituted-phenyl that replaces, and this substituent R 2Can also be by replacements such as methyl, halogen atoms.As this substituting group, can enumerate-CH 2-C 6H 5-NHCONH-SO 2-C 6H 5,-SO 2-C 6H 5-,-SO 2-C 6H 4-CH 3,-SO 2-C 6H 4-Cl etc.
Wherein, as above-mentioned R 2, preferably-NH-Ph, especially preferably-NH-C 6H 5
As the preferred concrete example of the compound of representing by above-mentioned general formula (1), identical with the concrete example of being enumerated in the 2nd embodiment of the present invention.But the present invention is not subjected to the qualification of these concrete examples.
In electronic acceptance compound by above-mentioned general formula (1) expression, consider from two aspects of taking into account image keeping quality and background fog, most preferably be 4-hydroxy benzenes sulfonanilide.
As the amount of the electronic acceptance compound in single heat sensitive recording layer, with respect to the quality of above-mentioned electron donability leuco dye, be preferably 50～400 quality %, more preferably 100～300 quality %.
Can be electronic acceptance compound and other known electronic acceptance compounds and usefulness in the scope of not damaging effect of the present invention (the particularly raising of the alleviating of background fog, high sensitivityization and image keeping quality, resistance to chemical reagents and a matching) by above-mentioned general formula (1) expression.
As above-mentioned known electronic acceptance compound, can select aptly to use, particularly consider, preferably phenol type compound or salicyclic acid derivatives and multivalent metal salt thereof from the viewpoint that suppresses background fog.
To identical in the explanation of above-mentioned phenol type compound and salicyclic acid derivatives and the present invention's the 1st embodiment to the explanation of phenol type compound and salicyclic acid derivatives.
And with the occasion of above-mentioned known electronic acceptance compound, amount as the electronic acceptance compound of representing by above-mentioned general formula (1), with respect to the gross mass of electronic acceptance compound, preferably more than 50 quality %, more preferably more than 70 quality %.
When the preparation heat sensitive recording layer forms the coating fluid of usefulness, as the particle diameter of above-mentioned electronic acceptance compound, by volume average grain diameter preferably below 1.0 μ m, 0.4～0.7 μ m more preferably.If this volume average particle size surpasses 1.0 μ m, its heat sensitivity tends to reduce.In addition, if less than 0.4 μ m then tends to cause the background fog deterioration.
Above-mentioned volume average particle size can easily utilize laser diffraction formula particle size distribution device (for example LA500 (ホ リ バ (strain) system)) etc. to record.
-sensitizer-
In the said heat sensitive recording layer of the 3rd embodiment of the present invention, preferably contain sensitizer.To identical in the explanation of above-mentioned sensitizer and the 1st embodiment of the present invention to the explanation of sensitizer.
-image stabilizing agent-
In the said heat sensitive recording layer of the 3rd embodiment of the present invention, preferably contain image stabilizing agent (containing ultra-violet absorber).To identical in the explanation of above-mentioned image stabilizing agent (containing ultra-violet absorber) and the 1st embodiment of the present invention to the explanation of image stabilizing agent (containing ultra-violet absorber).
-inorganic pigment-
In the said heat sensitive recording layer of the 3rd embodiment of the present invention, especially preferably contain at least a (the said inorganic pigment among the present invention) from calcite class calcium carbonate, amorphous silica and aluminium hydroxide, selected as inorganic pigment.To identical in the explanation of above-mentioned inorganic pigment and the 1st embodiment of the present invention to the explanation of inorganic pigment.
-adhesive-
In the said heat sensitive recording layer of the 3rd embodiment of the present invention; preferably contain at least a (that is the modified polyvinylalcohol (hereinafter being sometimes referred to as " specific modified PVA ")) that be selected from sulfo group modified polyethylene alcohol, the pure and mild acetoacetyl modified polyethylene of the diacetone modified polyethylene alcohol as adhesive (the perhaps protecting colloid when disperseing).To identical in the explanation of above-mentioned adhesive and the 1st embodiment of the present invention to the explanation of adhesive.
-other compositions-
In the said heat sensitive recording layer of the present invention's the 3rd embodiment, except mentioned component, can also contain other compositions of crosslinking agent, other pigment, metallic soap, wax, surfactant, adhesive, antistatic additive, defoamer, fluorescent dye etc. according to purpose or needs.
[crosslinking agent]
In heat sensitive recording layer, can contain the crosslinking agent that in the particular modification PVA that uses as above-mentioned adhesive (perhaps protecting colloid) and other modified PVAs etc., plays crosslinked action.By containing this crosslinking agent, can improve the resistance to water of thermal recording medium.
To identical in the explanation of above-mentioned crosslinking agent and the 1st embodiment of the present invention to the explanation of crosslinking agent.
[mordant]
In order to prevent the profit of oozing when the ink mist recording, can in heat sensitive recording layer, contain mordant.To identical in the explanation of above-mentioned mordant and the 1st embodiment of the present invention to the explanation of mordant.
[metallic soap, wax, surfactant]
To identical in the explanation of metallic soap, wax and surfactant and the 1st embodiment of the present invention to the explanation of metallic soap, wax and surfactant.
[adhesive]
The dispersion of above-mentioned electron donability leuco dye, electronic acceptance compound, inorganic pigment, adhesive, sensitizer and other compositions can be carried out in water miscible adhesive aptly.To identical in the explanation of the adhesive that is suitable for and the 1st embodiment of the present invention herein to the explanation of adhesive.
-other-
Can utilize the stirring pulverizer of ball mill, grater, puddle mixer etc. that above-mentioned electron donability leuco dye, electronic acceptance compound, inorganic pigment, adhesive and sensitizer are disperseed at the same time or separately, be mixed with coating fluid.As required, can in this coating fluid, be added into other above-mentioned compositions, that is: crosslinking agent, mordant, metallic soap, wax, surfactant, adhesive, antistatic additive, defoamer and fluorescent dye etc.
After being mixed with coating fluid as stated above, this coating fluid is applied on the surface of support to form heat sensitive recording layer.Method as the above-mentioned coating fluid of coating is not particularly limited, and for example can select aptly from using air knife doctor knife coater, roll coater, scraper plate to be coated with the rubbing method of machine, curtain flow coater etc., is dried after the coating.After the drying, preferably carry out smoothing and handle, use is provided then by calender.
Be not particularly limited for the coating weight when coating forms heat sensitive recording layer, be preferably 2～7g/m by common dry mass 2About.
In the present invention,, also can improve the viewpoint of picture quality (figure matter) simultaneously and consider, preferably use the curtain stream rubbing method of curtain stream coating machine especially from obtaining high concentration (high sensitivity) with less raw material use amount.In addition, as described below, except heat sensitive recording layer, going back the occasion of lamination protective layer etc., by with the many layers of curtain stream rubbing method lamination coating simultaneously, can reduce the energy consumption when making.
To using concrete curtain stream rubbing method to carry out the explanation that multilayer while lamination is coated with, identical with the explanation in the 1st embodiment of the present invention.
In the 3rd embodiment of the present invention, in order to be 15.2mJ/mm applying energy 2Condition under carry out the hot stamping phase time image color reach more than 1.20; the having or not to wait of formation that can be by selecting above-mentioned each composition in suitable mode or the formation of layer, coating process etc., particularly kind by selecting electron donability leuco dye, electronic acceptance compound, adhesive and sensitizer or amount and coating process, protective layer carries out.
As at the above-mentioned above-mentioned image color that obtains when applying energy, especially preferably 1.25～1.35.
＜protective layer 〉
At least the protective layer of one deck preferably is set on heat sensitive recording layer, and this protective layer can constitute according to the mode of the micropowder that contains organic or inorganic, adhesive, surfactant, hot melt material etc.To identical in the explanation of protective layer and the 1st embodiment of the present invention to the explanation of protective layer.
-support-
As above-mentioned support, can use known traditionally support.Can enumerate particularly: the paper support of good quality paper etc., the support of coating resin or pigment and coated paper, the resin layered paper that forms, good quality paper, synthetic paper, plastic sheeting etc. on paper with priming coat.Also can use and mainly contain old paper stock, just old paper stock occupies the support more than the 50 quality % in support.
To the explanation of above-mentioned support with identical with the explanation in the 1st embodiment of the present invention to the explanation that is arranged on the priming coat on the support.
To the Na that contains in the thermal recording medium +Ion and K +The explanation of the total ion concentration of ion is identical with the explanation in the 1st embodiment of the present invention.
In the 3rd embodiment of thermal recording medium of the present invention, the surface wettability of this heat sensitive recording layer, behind the distilled water that just on the surface of heat sensitive recording layer, drips through the contact angle after 0.1 second, preferably more than 20 °, more preferably more than 50 °.By above-mentioned contact angle is in the above-mentioned scope, can prevent when using the ink-jet printer lettering that the literal that prints off from oozing profit (give and improve ink-jet adaptability).
By containing electronic acceptance compound (preferred 4-hydroxy benzenes sulfonanilide) by above-mentioned general formula (1) expression, can obtain above-mentioned contact angle, in addition, keep the material of bigger numerical as the contact angle that can make recording surface and distilled water, preferably by the method that contains the said sensitizer of the present invention, paraffin etc. in the heat sensitive recording layer is prepared.
Explanation to above-mentioned measurement of contact angle is identical with the explanation in the 1st embodiment of the present invention.
The 3rd embodiment of thermal recording medium of the present invention make the image keeping quality good aspect be useful, after the image that forms after print was placed 24 hours under the environmental condition of 60 ℃ of temperature and relative humidity 20%, the concentration survival rate in above-mentioned formation image was more than 65%.As mentioned above,, preferably contain image stabilizing agent etc., above-mentioned concentration survival rate is in the above-mentioned scope by containing electronic acceptance compound (especially preferably 4-hydroxy benzenes sulfonanilide) by general formula (1) expression.So just can make established image in long-time, keep high concentration, and also can be suitable in requirement such as the keeping of vital document, presell ticket, receipt, bank note have an image reliability in for a long time field.
Explanation to the image color survival rate is identical with the explanation in the 1st embodiment of the present invention.
[the 4th embodiment]
The 4th embodiment of thermal recording medium of the present invention has following feature, promptly, have contain the electron donability leuco dye, can be by the electronic acceptance compound of color development and the heat sensitive recording layer of pigment with the reaction of this electron donability leuco dye, above-mentioned pigment is that 30～200ml/100g, volume average particle size are 0.5～3 μ m to the oil absorption of boiling Linseed oil, and the tape deck that can be used for being undertaken by the speed of 10cm/ more than second the hot stamping word.
Explain the 4th embodiment of thermal recording medium of the present invention below.
The 4th embodiment of thermal recording medium of the present invention be have on the support one deck or two-layer more than heat sensitive recording layer, preferably have protective layer.In addition, as required, can also have other layer such as intermediate layer.
＜heat sensitive recording layer 〉
Above-mentioned heat sensitive recording layer contain at least the electron donability leuco dye, can be by electronic acceptance compound, the pigment of color development with the reaction of this electron donability leuco dye, preferably contain image stabilizing agent (ultraviolet ray prevents agent), adhesive, sensitizer, as required, can also contain other compositions.
-electron donability leuco dye-
In the said heat sensitive recording layer of the 4th embodiment of the present invention, contain at least a electron donability leuco dye as the color development composition.Explanation to the electron donability leuco dye that contains in the explanation of above-mentioned electron donability leuco dye and the said heat sensitive recording layer of the 1st embodiment of the present invention is identical.
-electronic acceptance compound-
Containing in the said heat sensitive recording layer of the present invention's the 4th embodiment can be by meeting thermal response and the electronic acceptance compound of color development with above-mentioned electron donability leuco dye by at least a conduct in the compound of following general formula (1) expression.Owing to contain this compound as electronic acceptance compound, therefore can realize high sensitivityization owing to keeping low background fog, can also improve a matching of the long preservation (image keeping quality), resistance to chemical reagents, ink-jet adaptability and the thermal head that have formed image simultaneously.
General formula (1):
R 1-Ph-SO 2R 2
In above-mentioned general formula (1), R 1Expression hydroxyl, alkyl.R 2Expression-Ph ,-NH-Ph ,-Ph-OR 3,-NH-CO-NH-Ph, R 3The expression alkyl.Ph represents phenyl, also can be contained-SO 2R 2Substituting group replace.
As by above-mentioned R 1The alkyl of expression, preferably the alkyl of carbon number 1～3 is more preferably methyl, ethyl, isopropyl etc.Wherein, as above-mentioned R 1, hydroxyl especially preferably.
Above-mentioned R 3The expression alkyl, as this alkyl, the alkyl of carbon number 1～4 preferably, especially preferably isopropyl etc.In addition, Ph represents phenyl, but it can " be contained-SO 2R 2Substituting group " substituted-phenyl that replaces, and this substituent R 2Can also be by replacements such as methyl, halogen atoms.As this substituting group, can enumerate-CH 2-C 6H 5-NHCONH-SO 2-C 6H 5,-SO 2-C 6H 5,-SO 2-C 6H 4-CH 3,-SO 2-C 6H 4-Cl etc.
Wherein, as above-mentioned R 2, preferably-NH-Ph, especially preferably-NH-C 6H 5
As the preferred concrete example of the compound of representing by above-mentioned general formula (1), can enumerate and the same concrete example of the present invention's the 2nd embodiment.But the present invention is not subjected to the qualification of these concrete examples.
In electronic acceptance compound by above-mentioned general formula (1) expression, consider from two aspects of taking into account image keeping quality and background fog, most preferably be 4-hydroxy benzenes sulfonanilide.
As the amount of the electronic acceptance compound in single heat sensitive recording layer, with respect to the quality of above-mentioned electron donability leuco dye, be preferably 50～400 quality %, more preferably 100～300 quality %.
Can be electronic acceptance compound and other known electronic acceptance compounds and usefulness in the scope of not damaging effect of the present invention (the particularly raising of the alleviating of background fog, high sensitivityization and image keeping quality, resistance to chemical reagents and a matching) by above-mentioned general formula (1) expression.
As above-mentioned known electronic acceptance compound, can select aptly to use, particularly consider, preferably phenol type compound or salicyclic acid derivatives and multivalent metal salt thereof from the viewpoint that suppresses background fog.
To the explanation of above-mentioned phenol type compound and salicyclic acid derivatives, with identical in the present invention's the 1st embodiment to the explanation of phenol type compound and salicyclic acid derivatives.
And with the occasion of above-mentioned known electronic acceptance compound, amount as the electronic acceptance compound of representing by above-mentioned general formula (1), with respect to the gross mass of electronic acceptance compound, preferably more than 50 quality %, more preferably more than 70 quality %.
When the preparation heat sensitive recording layer forms the coating fluid of usefulness, as the particle diameter of above-mentioned electronic acceptance compound, by volume average grain diameter preferably below 1.0 μ m, 0.4～0.7 μ m more preferably.If this volume average particle size surpasses 1.0 μ m, its heat sensitivity tends to reduce.In addition, if less than 0.4 μ m then tends to cause the background fog deterioration.
Above-mentioned volume average particle size can easily utilize laser diffraction formula particle size distribution device (for example LA500 (ホ リ バ (strain) system)) etc. to record.
-pigment-
In the 4th embodiment of the present invention, as mentioned above, the oil absorption of boiling Linseed oil of above-mentioned pigment is 30～200ml/100g, by making the oil absorption of boiling Linseed oil in above-mentioned scope, can make high speed lettering adaptability good, that is,, also be difficult for taking place the pollution of thermal head even in the occasion of high speed lettering.
If the above-mentioned not enough 30ml/100g of oil absorption that boils Linseed oil thermal head then takes place easily pollutes, in addition,, then be difficult to the sensitivity that reaches required if reach more than the 200ml/100g.
The oil absorption of boiling Linseed oil of above-mentioned pigment is 40～150ml/100g more preferably, especially is preferably 50～100ml/100g.
In addition, in the 4th embodiment of the present invention, the volume average particle size of above-mentioned pigment is 0.5～3 μ m, if thermal head then takes place and pollutes in less than 0.5 μ m easily, and if reach more than the 3 μ m, then be difficult to the sensitivity that reaches required.
The volume average particle size of above-mentioned pigment is 0.7～2.5 μ m more preferably, especially is preferably 1.0～2.0 μ m.
In addition, as pigment, more particularly, especially preferably contain at least a (the said pigment among the present invention) from calcite class calcium carbonate, amorphous silica and aluminium hydroxide, selected as pigment.By containing these pigment, can further improve and a matching that contacts thermal head, can also give simultaneously printing adaptability and with the similitude of common paper.
In (lightweight) calcium carbonate, the crystal type calcium carbonate that calcite, aragonite, vaterite etc. are generally arranged, but, color development concentration when thermal head writes down and prevent viewpoint that thermal head pollutes and consider from the viewpoint of absorbability, hardness etc., calcite class (lightweight) calcium carbonate preferably, wherein, particularly preferably be shape of particle and be spindle shape or the planar calcium carbonate of scalenohedron.Calcite class (lightweight) calcium carbonate can be made by known manufacture method.
As the average grain diameter of above-mentioned calcite class (lightweight) calcium carbonate, by volume average grain diameter is preferably 1～3 μ m.Volume average particle size can be according to recording with same method such as above-mentioned electron donability leuco dye.
In single heat sensitive recording layer, amount as above-mentioned " said inorganic pigment among the present invention ", from improving color development concentration and preventing that sediment is attached to the viewpoint consideration on the thermal head, with respect to electronic acceptance compound 100 mass parts, be preferably 50～500 mass parts, more preferably 70～350 mass parts are preferably 90～250 mass parts especially.
In addition, in the scope of not damaging effect of the present invention (particularly a matching, printing adaptability and with the raising of common paper similitude), can and use said pigment in the invention described above and other pigment.
As other above-mentioned pigment, except calcite class (lightweight) calcium carbonate, can enumerate: calcium carbonate, barium sulfate, lithopone, pyrophyllite, kaolin, burn till kaolin, amorphous silica, kaolin, magnesium carbonate, magnesia etc.
As the volume average particle size of above-mentioned other pigment (with laser diffraction formula particle size distribution device (for example LA500 (ホ リ バ (strain) system) etc.) mensuration), be preferably 0.3～1.5 μ m, more preferably 0.5～0.9 μ m.
The occasion of said pigment and above-mentioned other pigment and usefulness in the present invention, as the gross mass (V) of " said pigment among the present invention " ratio (V/W) with the gross mass (W) of above-mentioned other pigment, be preferably 100/0～60/40, more preferably 100/0～80/20.
In addition, consider from the viewpoint of the abrasiveness that suppresses thermal head, preferably the pigment of Mohs' hardness below 3." Mohs' hardness " is meant in " Britain and Japan's plastics industry dictionary " the 5th edition Mohs' hardness (Mohs Hardness) of record in (coulee is stretched work, census of manufacturing meeting (strain) distribution) p.616.In the pigment of Mohs' hardness below 3, contain calcium carbonate, aluminium hydroxide etc.
Said pigment is with magnesium carbonate, when magnesia mixes in the present invention, can alleviate background fog effectively, this is favourable aspect, in this case, as magnesium carbonate and/or magnesian amount, 3～50 quality % that preferably are equivalent to the pigment gross mass, especially preferably 5～30 quality %.
-sensitizer-
In the said heat sensitive recording layer of the 4th embodiment of the present invention, preferably contain sensitizer.To identical in the explanation of above-mentioned sensitizer and the 1st embodiment of the present invention to the explanation of sensitizer.
-image stabilizing agent-
In the said heat sensitive recording layer of the 4th embodiment of the present invention, preferably contain image stabilizing agent (containing ultra-violet absorber).To identical in the explanation of above-mentioned image stabilizing agent (containing ultra-violet absorber) and the 1st embodiment of the present invention to the explanation of image stabilizing agent (containing ultra-violet absorber).
-adhesive-
In the said heat sensitive recording layer of the 4th embodiment of the present invention; preferably contain at least a (that is the modified polyvinylalcohol (hereinafter being sometimes referred to as " specific modified PVA ")) that be selected from sulfo group modified polyethylene alcohol, the pure and mild acetoacetyl modified polyethylene of the diacetone modified polyethylene alcohol as adhesive (the perhaps protecting colloid when disperseing).To identical in the explanation of above-mentioned adhesive and the 1st embodiment of the present invention to the explanation of adhesive.
-other compositions-
In the said heat sensitive recording layer of the present invention's the 4th embodiment, except mentioned component, can also contain other compositions of crosslinking agent, other pigment, metallic soap, wax, surfactant, adhesive, antistatic additive, defoamer, fluorescent dye etc. according to purpose or needs.
[crosslinking agent]
In heat sensitive recording layer, can contain the crosslinking agent that in modified PVA etc., plays crosslinked action at the particular modification PVA that uses as above-mentioned adhesive (perhaps protecting colloid) and other.By containing this crosslinking agent, can improve the resistance to water of thermal recording medium.
To identical in the explanation of above-mentioned crosslinking agent and the 1st embodiment of the present invention to the explanation of crosslinking agent.
[mordant]
In order to prevent the profit of oozing when the ink mist recording, can in heat sensitive recording layer, contain mordant.To identical in the explanation of above-mentioned mordant and the 1st embodiment of the present invention to the explanation of mordant.
[metallic soap, wax, surfactant]
To identical in the explanation of metallic soap, wax and surfactant and the 1st embodiment of the present invention to the explanation of metallic soap, wax and surfactant.
[adhesive]
The dispersion of above-mentioned electron donability leuco dye, electronic acceptance compound, inorganic pigment, adhesive, sensitizer and other compositions can be carried out in water miscible adhesive aptly.To identical in the explanation of the adhesive that is suitable for and the 1st embodiment of the present invention herein to the explanation of adhesive.
-other-
Can utilize the stirring pulverizer of ball mill, grater, puddle mixer etc. that above-mentioned electron donability leuco dye, electronic acceptance compound, pigment, adhesive and sensitizer are disperseed at the same time or separately, be mixed with coating fluid.As required, can in this coating fluid, be added into other above-mentioned compositions, that is: crosslinking agent, mordant, metallic soap, wax, surfactant, adhesive, antistatic additive, defoamer and fluorescent dye etc.
After being mixed with coating fluid as stated above, this coating fluid is applied on the surface of support to form heat sensitive recording layer.Method as the above-mentioned coating fluid of coating is not particularly limited, and for example can select aptly from using air knife doctor knife coater, roll coater, scraper plate to be coated with the rubbing method of machine, curtain flow coater etc., is dried after the coating.After the drying, preferably carry out smoothing and handle, use is provided then by calender.
Be not particularly limited for the coating weight when coating forms heat sensitive recording layer, be preferably 2～7g/m by common dry mass 2About.
In the 4th embodiment of the present invention, from obtaining high concentration (high sensitivity), also can improve the viewpoint of picture quality (figure matter) simultaneously and consider with less raw material use amount, preferably use the curtain stream rubbing method of curtain stream coating machine especially.In addition, as described below, except heat sensitive recording layer, going back the occasion of lamination protective layer etc., by with the many layers of curtain stream rubbing method lamination coating simultaneously, can reduce the energy consumption when making.
Carry out the explanation that multilayer while lamination is coated with to using concrete curtain to flow rubbing method, and to using the explanation of curtain flow coat cloth apparatus, identical with the explanation in the 1st embodiment of the present invention.
＜protective layer 〉
At least the protective layer of one deck preferably is set on heat sensitive recording layer, and this protective layer can constitute according to the mode of the micropowder that contains organic or inorganic, adhesive, surfactant, hot melt material etc.To identical in the explanation of protective layer and the 1st embodiment of the present invention to the explanation of protective layer.
-support-
As above-mentioned support, can use known traditionally support.Can enumerate particularly: the paper support of good quality paper etc., the support of coating resin or pigment and coated paper, the resin layered paper that forms, good quality paper, synthetic paper, plastic sheeting etc. on paper with priming coat.Also can use and mainly contain old paper stock, just old paper stock occupies the support more than the 50 quality % in support.
To the explanation of above-mentioned support with identical with the explanation in the 1st embodiment of the present invention to the explanation that is arranged on the priming coat on the support.
To the Na that contains in the thermal recording medium +Ion and K +The explanation of the total ion concentration of ion is identical with the explanation in the 1st embodiment of the present invention.
In the 4th embodiment of thermal recording medium of the present invention, the surface wettability of this heat sensitive recording layer, behind the distilled water that just on the surface of heat sensitive recording layer, drips through the contact angle after 0.1 second, preferably more than 20 °, more preferably more than 50 °.By above-mentioned contact angle is in the above-mentioned scope, can prevent when using the ink-jet printer lettering that the literal that prints off from oozing profit (give and improve ink-jet adaptability).
By containing electronic acceptance compound (preferred 4-hydroxy benzenes sulfonanilide) by above-mentioned general formula (1) expression, can obtain above-mentioned contact angle, in addition, keep the material of bigger numerical as the contact angle that can make recording surface and distilled water, preferably by the method that contains the said sensitizer of the present invention, paraffin etc. in the heat sensitive recording layer is prepared.Explanation to above-mentioned measurement of contact angle is identical with the explanation in the 1st embodiment of the present invention.
The 4th embodiment of thermal recording medium of the present invention make the image keeping quality good aspect be useful, after the image that forms after print was placed 24 hours under the environmental condition of 60 ℃ of temperature and relative humidity 20%, the concentration survival rate in above-mentioned formation image was more than 65%.As mentioned above,, preferably contain image stabilizing agent etc., above-mentioned concentration survival rate is in the above-mentioned scope by containing electronic acceptance compound (especially preferably 4-hydroxy benzenes sulfonanilide) by general formula (1) expression.So just can make established image in long-time, keep high concentration, and also can be suitable in requirement such as the keeping of vital document, presell ticket, receipt, bank note have an image reliability in for a long time field.
Explanation to the image color survival rate is identical with the explanation in the 1st embodiment of the present invention.
The 4th embodiment of thermal recording medium of the present invention can be used for and can be undertaken in the tape deck of hot stamping word (print) by the speed of 10cm/ more than second; can be directly on the surface of heat sensitive recording layer; perhaps has the occasion of protective layer; then by this protective layer and on this surface; by applying heat to the image style, just can be at lettering (print) on the heat sensitive recording layer as constituted above.
The speed of above-mentioned hot stamping word (print) is preferably at 12cm/ more than second.
[embodiment of the 1st embodiment]
Below by embodiment the 1st embodiment of the present invention is described, but the 1st embodiment of the present invention is not subjected to the qualification of these embodiment." part " in following embodiment and " % " represent " mass parts " and " quality % " respectively.
(embodiment 1)
＜thermal photography the preparation of coating fluid 〉
The preparation of-dispersion liquid A (containing the electron donability leuco dye)-
Each following composition is disperseed, mixes with ball mill, and having obtained volume average particle size is the dispersion liquid A of 0.7 μ m.Volume average particle size uses laser diffraction formula particle size distribution device LA500 (ホ リ バ (strain) system) to measure.
[composition of dispersion liquid A]
2-anilino--3-methyl-6-lignocaine fluorane ... 10 parts
(electron donability leuco dye)
Polyvinyl alcohol 2.5% solution ... 50 parts
(PVA-105, (strain) Network ラ レ system)
The preparation of-dispersion liquid B (containing electronic acceptance compound)-
Each following composition is disperseed, mixes with ball mill, and having obtained volume average particle size is the dispersion liquid B of 0.7 μ m.Volume average particle size is according to similarly measuring with the occasion of dispersion liquid A.
[composition of dispersion liquid B]
4-hydroxy benzenes sulfonanilide ... 20 parts
(by the electronic acceptance compound of above-mentioned general formula (1) expression)
Polyvinyl alcohol 2.5% solution ... 100 parts
(PVA-105, (strain) Network ラ レ system)
The preparation of-dispersion liquid C (containing sensitizer)-
Each following composition is disperseed, mixes with ball mill, and having obtained volume average particle size is the dispersion liquid C of 0.7 μ m.Volume average particle size is according to similarly measuring with the occasion of dispersion liquid A.
[composition of dispersion liquid C]
2-benzyloxy naphthalene (sensitizer) ... 20 parts
Polyvinyl alcohol 2.5% solution ... 100 parts
(PVA-105, (strain) Network ラ レ system)
The preparation of-dispersion liquid D (containing pigment)-
Each following composition is disperseed, mixes with puddle mixer, and having obtained volume average particle size is the dispersion liquid D of 2.0 μ m.Volume average particle size is according to similarly measuring with the occasion of dispersion liquid A.
[composition of dispersion liquid D]
Calcite class precipitated calcium carbonate ... 40 parts
(ュ ニ バ-70, white lapicide's industry (strain) system)
Sodium Polyacrylate ... 1 part
Water ... 60 parts
The preparation of-heat sensitive recording layer usefulness coating fluid-
Following composition is mixed, obtained the heat sensitive recording layer coating fluid.
[the heat sensitive recording layer composition of coating fluid]
Dispersion liquid A ... 60 parts
Dispersion liquid B ... 120 parts
Dispersion liquid C ... 120 parts
Dispersion liquid D ... 101 parts
Zinc stearate 30% dispersion liquid ... 15 parts
Paraffin (30%) ... 15 parts
Neopelex (25%) ... 4 parts
The preparation of＜support coating liquid for undercoat layer 〉
Following each composition is mixed with dissolvers, obtained dispersion liquid.
Burn till kaolin (oil absorption 75ml/100g) ... 100 parts
Calgon ... 1 part
Water ... 110 parts
Then, in the dispersion liquid that obtains, add (25%) 25 part of 20 parts of SBR (SBR styrene butadiene rubbers latex) and oxidized starch, obtained the support coating liquid for undercoat layer.
The manufacturing of＜thermal recording medium 〉
The good quality paper of preparing a kind of smoothness by JIS-P8119 regulation and be 150 seconds is as support, the support coating liquid for undercoat layer that on the surface of this good quality paper, obtains as stated above with the coating of scraper plate coating machine, and controlling dried coating weight is 8g/m 2Thereby, formed priming coat.By being coated with this priming coat, make the JIS-P8119 smoothness of support become 350 seconds.
Then, the thermal photography coating fluid that on above-mentioned priming coat, obtains as stated above with the coating of curtain flow coater, controlling dried coating weight is 4g/m 2, be dried, thereby formed heat sensitive recording layer.Then, a side surface (support dorsal part) that uses the air knife doctor knife coater not form heat sensitive recording layer on support is gone up and is pressed 5g/m 2Amount coating as the water of back coating liquid, be dried and carry out the adjustment of crimping.Then, the surface that forms heat sensitive recording layer is applied calender handle, thereby obtained thermal recording medium of the present invention (1).
According to following (evaluation) same condition and method the thermal recording medium (1) that is obtained being measured, the result records, and is 15.2mJ/mm at the energy that applies of thermal head 2The time color development concentration (use Macbeath reflection of the concentration RD-918) be 1.28.
(embodiment 2)
The preparation of-dispersion liquid E-
Each following composition is disperseed, mixes with ball mill, and having obtained volume average particle size is the dispersion liquid E of 0.7 μ m.Volume average particle size is measured similarly to Example 1.
[composition of dispersion liquid E]
1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane ... 5 parts
(image stabilizing agent)
Polyvinyl alcohol 2.5% solution ... 25 parts
(PVA-105, (strain) Network ラ レ system; Adhesive)
The preparation of-heat sensitive recording layer usefulness coating fluid-
Prepare dispersion liquid A, B, C and D similarly to Example 1, the dispersion liquid E that obtains is as stated above mixed with following composition preparing the heat sensitive recording layer coating fluid, and then operate similarly to Example 1, obtained thermal recording medium of the present invention (2).
[the heat sensitive recording layer composition of coating fluid]
Dispersion liquid A ... 60 parts
Dispersion liquid B ... 120 parts
Dispersion liquid C ... 120 parts
Dispersion liquid E ... 30 parts
Dispersion liquid D ... 101 parts
Zinc stearate 30% dispersion liquid ... 15 parts
Paraffin (30%) ... 15 parts
Neopelex (25%) ... 4 parts
(embodiment 3)
Except using 1,1,3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane replace when preparation dispersion liquid E, using among the embodiment 21,1, butane (image stabilizing agent) in addition for 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl), all the other prepare dispersion liquid E similarly to Example 2, and then operation similarly to Example 2, have obtained thermal recording medium of the present invention (3).
(embodiment 4～5)
Except using amorphous silica (ミ ズ カ ミ Le P832 respectively, marshy land chemical industry (strain) system) 20 part, or calcite class precipitated calcium carbonate (the ユ ニ バ-70 that when preparation dispersion liquid D, uses among 40 parts of replacement embodiment 1 of aluminium hydroxide (Ha イ ジ ラ イ ト H42, clear and electrician's (strain) system); Inorganic pigment) beyond 40 parts, all the other are operated similarly to Example 1, have obtained thermal recording medium of the present invention (4)～(5).
(embodiment 6)
Except using sulfo group modified polyvinylalcohol (go-セ ラ Application L3266, Japan's synthetic chemistry (strain) system) polyvinyl alcohol 2.5% aqueous solution (adhesive) that uses when preparation dispersion liquid A, B and C among 2.5% aqueous solution replacement embodiment 1 in addition, all the other are operated similarly to Example 1, have obtained thermal recording medium of the present invention (6).
(embodiment 7)
Except polyvinyl alcohol 2.5% aqueous solution (adhesive) that uses when preparing dispersion liquid A, B and C among the embodiment 1 is changed into diacetone modified polyvinylalcohol (D500, ユ ニ チ カ society system) 2.5% aqueous solution, and dispersion liquid A, B and the C that will so change the back acquisition mix similarly to Example 1, obtain the heat sensitive recording layer coating fluid, and then in this coating fluid, add beyond 13 parts of adipic dihydrazide 5% aqueous solution (crosslinking agent), all the other are operated similarly to Example 1, have obtained thermal recording medium of the present invention (7).
(embodiment 8)
Except polyvinyl alcohol 2.5% aqueous solution (adhesive) that uses when preparing dispersion liquid A, B and C among the embodiment 1 is changed into acetoacetyl modified polyvinylalcohol (go-セ Off ア イ マ-Z210; Japan's synthetic chemistry (strain) system) 2.5% aqueous solution; and dispersion liquid A, B and the C that will so change the back acquisition mix similarly to Example 1; obtain the heat sensitive recording layer coating fluid; and then in this coating fluid, add beyond 13 parts of glyoxal 5% aqueous solution (crosslinking agent); all the other are operated similarly to Example 1, have obtained thermal recording medium of the present invention (8).
(embodiment 9)
A kind of by old paper stock 70% except using, LBKP 30% formation and JIS-P8119 smoothness are 170 seconds recycled writing paper (50g/m 2) beyond the good quality paper that replaces using as support among the embodiment 1, all the other are operated similarly to Example 1, have obtained thermal recording medium of the present invention (9).
(embodiment 10)
Embodiment 1＜manufacturing of thermal recording medium in; after forming priming coat on the support; do not carry out coating, drying and the calender process of heat sensitive recording layer with coating fluid; replace and after forming priming coat, use the curtain flow coater that the heat sensitive recording layer that obtains in embodiment 1 is carried out lamination coating simultaneously, drying, carries out calender process on the surface of the protective layer of lamination with coating fluid with by the following protective layer used coating fluid that constitutes; in addition; operation has obtained thermal recording medium of the present invention (10) similarly to Example 1.Should illustrate that the drying coated amount of protective layer is 2.0g/m 2
The preparation of-protective layer used coating fluid-
Following composition is disperseed with puddle mixer, and the pigment of dose volume average grain diameter 2 μ m disperses thing.Volume average particle size is measured similarly to Example 1.
Aluminium hydroxide (average grain diameter 1 μ m) ... 40 parts
(Ha イ ジ ラ イ ト H42, clear and electrician's (strain) system)
Sodium Polyacrylate ... 1 part
Water ... 60 parts
In addition; preparation is to urea organic phosphate starch 15% aqueous solution (MS4600; japanese food chemical industry (strain) system) 200 parts and polyvinyl alcohol 15% aqueous solution (PVA-105; (strain) Network ラ レ system) solution that adds 60 parts of entry in 200 parts and form; disperse thing to the pigment that wherein is mixed into by above-mentioned acquisition; and then the zinc stearate emulsification that is mixed into volume average particle size 0.15 μ m disperses thing (Ha イ De リ Application F115; Zhong jing grease (strain) system) 25 parts and sulfosuccinic acid 2-ethylhexyl ester sodium salt 2% aqueous solution are 125 parts, have obtained protective layer used coating fluid.
(embodiment 11～13)
Use aluminium hydroxide (Ha イ ジ ラ イ ト H43 respectively, volume average particle size 0.7 μ m, clear and electrician's (strain) system) 40 parts, kaolin (カ オ Block ラ イ ト, volume average particle size 2.5 μ m, Bai Shigong industry (strain) system) 40 parts or amorphous silica (ミ ズ カ シ Le P707, volume average particle size 2.2 μ m, marshy land chemistry (strain) system) 20 parts replace aluminium hydroxide (the Ha イ ジ ラ イ ト H42 that uses among the embodiment 10 when the protective layer used coating fluid of preparation; Inorganic pigment) 40 parts, in addition, operation has obtained thermal recording medium of the present invention (11)～(13) similarly to Example 1.
(embodiment 14～20)
Use oxalic acid dimethylbenzyl ester (HS3520R-N respectively, big Japanese ink industry (strain) system), a terphenyl, ethylene glycol 4-tolyl ether, to benzylbiphenyl, 1,2-hexichol oxygen ylmethyl benzene, diphenyl sulphone (DPS) or 1, the 2-benzyloxy naphthalene (sensitizer) that when preparation dispersion liquid C, uses among the 2-biphenoxyl ethane replacement embodiment 1, in addition, operation has obtained thermal recording medium of the present invention (14)～(20) similarly to Example 1.
(embodiment 21～25)
Use 2-anilino--3-methyl-6-dibutylamino fluorane respectively, 2-anilino--3-methyl-6-(N-ethyl-N-isoamylamino) fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-third amino) fluorane, 2-anilino--3-methyl-6-two pentylamine base fluoranes, or the 2-anilino--3-methyl-6-lignocaine fluorane (electron donability leuco dye) that when preparation dispersion liquid A, uses among 2-anilino--3-methyl-6-(N-ethyl-N-p-methylphenyl amino) fluorane replacement embodiment 1, in addition, operation has obtained thermal recording medium of the present invention (21)～(25) similarly to Example 1.
(embodiment 26)
The curtain flow coater that uses when being coated with heat sensitive recording layer with coating fluid in using air knife doctor knife coater replacement embodiment 1, all the other are operated similarly to Example 1, have obtained thermal recording medium of the present invention (26).
(embodiment 27～29)
Use N-benzyl-4-hydroxy benzene sulfonamide (=right-N-benzyl sulfonamides phenol), BTUM or 2 respectively; the 4-hydroxy benzenes sulfonanilide (electronic acceptance compound) that when preparation dispersion liquid B, uses among two (phenyl sulfonyl) phenol replacement of the 4-embodiment 1; in addition; operation has obtained thermal recording medium of the present invention (27)～(29) similarly to Example 1.
(comparative example 1～2)
Use 2 respectively, 2 '-two (4-hydroxyl phenol) propane (bisphenol-A) or 4, the 4-hydroxy benzenes sulfonanilide (electronic acceptance compound) that when preparation dispersion liquid B, uses among 4 '-dihydroxydiphenylsulisomer replacement embodiment 1, in addition, operate similarly to Example 1, obtained to be used for thermal recording medium (30)～(31) of comparison.
(comparative example 3)
The 4-hydroxy benzenes sulfonanilide (electronic acceptance compound) that uses when preparing dispersion liquid B among the embodiment 1 is changed into 4 parts for 20 parts, in addition, operate similarly to Example 1, obtained to be used for the thermal recording medium (32) of comparison.
(comparative example 4)
In embodiment 1, except not being coated with back coating liquid, operate similarly to Example 1, obtained to be used for the thermal recording medium (33) of comparison.
(comparative example 5)
In embodiment 1, except the coating weight that makes back coating liquid is excess quantity (12g/m 2) in addition, operate similarly to Example 1, obtained to be used for the thermal recording medium (34) of comparison.
(evaluation)
Carry out following mensuration and evaluation for thermal recording medium of the present invention (1)～(29) of above-mentioned acquisition and thermal recording medium (30)～(34) that are used for comparison.Should illustrate that measures and estimate the results are shown in the following table 1.
(1) mensuration of sensitivity
The temperature-sensitive printing device that use is equipped with the thermal head (KF2003-GD31A, ロ-system (strain) system) with parts of fine crackle structure carries out lettering.Lettering is (to apply energy 15.2mJ/mm at thermal head voltage 24V, lettering cycle 0.98ms/ line (print speed 12.8cm/ second), pulse width 0.375ms 2) condition carry out, with the Macbeath reflection of the concentration (RD-918, Macbeath society system) measure this lettering concentration.
(2) evaluation of background fog
Each thermal recording medium was placed 24 hours under the environmental condition of 60 ℃ of temperature, relative humidity 20%, used Macbeath reflection of the concentration (RD-918, Macbeath society system) to measure the concentration of its this bottom (non-image portion) then.Should illustrate that numerical value is low more, the expression background fog is good more.
(3) the conservatory evaluation of image
Adopt with above-mentioned " mensuration of (1) sensitivity " in identical device and condition, on above-mentioned each thermal recording medium, carry out print, the concentration that is determined at the concentration that is next to this image after the print and identical image is placed this image after 24 hours in the atmosphere of 60 ℃ of temperature, relative humidity 20% with Macbeath reflection of the concentration (RD-918, Macbeath society system).Then, based on following formula, calculate the ratio (% of the image color that image color after the placement records after with respect to print immediately; The concentration survival rate), with this as evaluation map as conservatory index.Should illustrate that numerical value is high more, the presentation video keeping quality is good more.
Concentration survival rate=[(image color after the placement)/(image color that records immediately behind the lettering)] * 100
(4) evaluation of resistance to chemical reagents
Adopt with above-mentioned " mensuration of (1) sensitivity " in identical device and condition, each thermal recording medium is carried out print, (2-is pink for ゼ Block ラ e-Pointer with e-Pointer, ゼ Block ラ (strain) system) takes notes on the surface of its this bottom and print portion, a situation arises and the image color of image portion through the background fog of this bottom of each thermal recording medium after 1 day by visualization, estimates according to following benchmark.
[benchmark]
Zero: confirm that background fog concentration does not rise, the concentration of image portion does not change yet.
△: confirm that background fog concentration has some risings, the concentration of image portion also shoals a little.
*: confirm that background fog concentration significantly rises, image portion almost disappears.
(5) evaluation of thermal head breakage
Use word processor (Le Port 95JV, (strain) Toshiba system), the test resolution of printing rate 20% is printed 1000 pages on A4 paper.Estimate the number of losing of this time point then, as the index of estimating the thermal head breakage.
(6) the adaptive evaluation of ink-jet
1. oil resistant China ink
Same with the occasion of above-mentioned " mensuration of (1) sensitivity ", print on the heat sensitive recording layer of each thermal recording medium is determined at the concentration (D that is next to print image afterwards with Macbeath reflection of the concentration RD-918 (Macbeath society system) 1).Secondly, make the surface (the lettering portion of printing off) of the heat sensitive recording layer of each thermal recording medium that prints off and use ink-jet printer (EPSON MJ930C, the EPSON corporate system) image of the high image quality of Da Yining contact is determined at 25 ℃ of image color (D of each heat sensitive recording layer of placement after 48 hours down with Macbeath reflection of the concentration RD-918 2).Then, calculate the concentration survival rate (% of each thermal recording medium according to each densimeter that obtains; D 2/ D 1* 100), with this index as the tolerance of estimating ink for inking.Should illustrate that numerical value is high more, expression printing ink tolerance is good more.
2. ink mist recording adaptability
Use word processor (Le Port JW-95JU, (strain) Toshiba system) behind printing character on each thermal recording medium, and then print being printed on each heat sensitive recording layer of word with ink-jet printer, ooze profit and the fading extent of the literal portion of printing off with word processor according to the printing ink of following benchmark visual valuation ink mist recording portion.
[benchmark]
Zero: what almost do not have printing ink oozes profit and the fading of literal portion, and identification is not influenced.
△: the part of literal portion shoals, but still can recognize.
*: the complete obiteration of literal portion, can not recognize.
(7) height of flange
It is square that each thermal recording medium is cut into 10cm along cross direction, after under 23 ℃, the environmental condition of relative humidity 45%, carrying out damping, each heat sensitive recording layer is placed on the horizontal plane with facing up or face down, be determined at the maximum (mm) of the height that floats four angular distance horizontal planes going up most on this horizontal plane.
(8) operability
Use word processor (Le Port 95JV, (strain) Toshiba system), on its sheet feeding section, place each 30 pages of each thermal recording mediums of A4 paper shape, estimate according to following benchmark.
Zero: normal lettering, and stack without a doubt behind the lettering.
*: with respect to the direction of paper lettering obliquely, perhaps paper is by paper feeding circuitously, and the perhaps paper ground stack that staggers mutually behind lettering, perhaps original good paper of stack are extruded and become the ground stack that staggers.
(9) measurement of contact angle
The distilled water that drips on the surface (recording surface) of the heat sensitive recording layer of each thermal recording medium uses FIBRO system (DAT1100, ab corporate system) to measure through the contact angle after 0.1 second then.This numerical value is big more, and for effective, this relation can be utilized more.
(10) ion (Na +, K +) mensuration of concentration
With each thermal recording medium of hot water extracting, with the Na of this extraction water of ion determination of quantitative analysis that utilizes the atom light absorption method +Ion and K +The mass of ion of ion.Ion concentration in the table 1 is represented Na +And K +Total ion concentration, with total ppm value representation with respect to the thermal recording medium gross mass.
Table 1
Thermal recording medium Image color (sensitivity) The image keeping quality Background fog concentration Resistance to chemical reagents The thermal head breakage Ink-jet adaptability Height of flange [mm] Operability Contact angle [°] Ion concentration [ppm]
Printing ink patience Ink mist recording adaptability
Embodiment 1 ????(1) ??1.28 ??95％ ??0.09 ??○ 0 ??90％ ??○ ??1.1 ??○ ??51 ?780
Embodiment 2 ????(2) ??1.27 ??98％ ??0.10 ??○ 0 ??93％ ??○ ??1.3 ??○ ??55 ?800
Embodiment 3 ????(3) ??1.26 ??97％ ??0.10 ??○ 0 ??92％ ??○ ??1.2 ??○ ??53 ?800
Embodiment 4 ????(4) ??1.26 ??93％ ??0.10 ??○ 0 ??88％ ??○ ??1.4 ??○ ??50 ?770
Embodiment 5 ????(5) ??1.27 ??96％ ??0.09 ??○ 0 ??91％ ??○ ??1.1 ??○ ??55 ?790
Embodiment 6 ????(6) ??1.30 ??96％ ??0.08 ??○ 0 ??93％ ??○ ??1.5 ??○ ??50 ?800
Embodiment 7 ????(7) ??1.29 ??97％ ??0.08 ??○ 0 ??92％ ??○ ??1.6 ??○ ??52 ?800
Embodiment 8 ????(8) ??1.28 ??95％ ??0.08 ??○ 0 ??93％ ??○ ??1.4 ??○ ??55 ?790
Embodiment 9 ????(9) ??1.28 ??94％ ??0.09 ??○ 0 ??93％ ??○ ??4.0 ??○ ??60 ?800
Embodiment 10 ????(10) ??1.23 ??98％ ??0.09 ??○ 0 ??98％ ??○ ??3.0 ??○ ??45 ?800
Embodiment 11 ????(11) ??1.22 ??97％ ??0.09 ??○ 0 ??97％ ??○ ??2.8 ??○ ??42 ?800
Embodiment 12 ????(12) ??1.21 ??98％ ??0.10 ??○ 0 ??98％ ??○ ??3.3 ??○ ??48 ?790
Embodiment 13 ????(13) ??1.20 ??96％ ??0.10 ??○ 0 ??92％ ??○ ??3.1 ??○ ??35 ?800
Embodiment 14 ????(14) ??1.27 ??94％ ??0.09 ??○ 0 ??89％ ??○ ??1.1 ??○ ??50 ?790
Embodiment 15 ????(15) ??1.26 ??95％ ??0.10 ??○ 0 ??91％ ??○ ??1.3 ??○ ??51 ?800
Embodiment 16 ????(16) ??1.28 ??94％ ??0.09 ??○ 0 ??92％ ??○ ??0.9 ??○ ??51 ?790
Embodiment 17 ????(17) ??1.24 ??91％ ??0.10 ??○ 0 ??89％ ??○ ??1.5 ??○ ??50 ?800
Embodiment 18 ????(18) ??1.26 ??95％ ??0.10 ??○ 0 ??91％ ??○ ??1.6 ??○ ??52 ?790
Embodiment 19 ????(19) ??1.28 ??93％ ??0.09 ??○ 0 ??89％ ??○ ??1.2 ??○ ??51 ?800
Embodiment 20 ????(20) ??1.25 ??92％ ??0.10 ??○ 0 ??91％ ??○ ??1.3 ??○ ??50 ?790
Embodiment 21 ????(21) ??1.28 ??97％ ??0.10 ??○ 0 ??93％ ??○ ??1.2 ??○ ??55 ?790
Embodiment 22 ????(22) ??1.26 ??95％ ??0.10 ??○ 0 ??88％ ??○ ??1.1 ??○ ??55 ?780
Embodiment 23 ????(23) ??1.26 ??92％ ??0.10 ??○ 0 ??87％ ??○ ??1.0 ??○ ??55 ?790
Embodiment 24 ????(24) ??1.28 ??95％ ??0.10 ??○ 0 ??91％ ??○ ??1.0 ??○ ??51 ?790
Embodiment 25 ????(25) ??1.24 ??88％ ??0.08 ??○ 0 ??85％ ??○ ??1.3 ??○ ??50 ?780
Embodiment 26 ????(26) ??1.26 ??93％ ??0.10 ??○ 0 ??90％ ??○ ??1.3 ??○ ??52 ?780
Embodiment 27 ????(27) ??1.20 ??65％ ??0.09 ??△ 0 ??80％ ??△ ??1.5 ??○ ??55 ?760
Embodiment 28 ????(28) ??1.22 ??98％ ??0.12 ??○ 0 ??92％ ??○ ??1.2 ??○ ??50 ?800
Embodiment 29 ????(29) ??1.26 ??98％ ??0.11 ??○ 0 ??96％ ??○ ??1.2 ??○ ??51 ?790
Comparative example 1 ????(30) ??1.30 ??70％ ??0.08 ??× 0 ??60％ ??× ??1.5 ??○ ??45 ?790
Comparative example 2 ????(31) ??1.15 ??65％ ??0.08 ??× 0 ??65％ ??× ??1.4 ??○ ??42 ?780
Comparative example 3 ????(32) ??1.05 ??50％ ??0.09 ??△ 0 ??55％ ??△ ??1.6 ??○ ??45 ?760
Comparative example 4 ????(33) ??1.28 ??95％ ??0.09 ??○ 0 ??90％ ??○ ??6.0 ??× ??51 ?780
Comparative example 5 ????(34) ??1.28 ??95％ ??0.09 ??○ 0 ??90％ ??○ ??5.5 ??× ??51 ?780
From the result of above-mentioned table 1 as can be seen, in thermal recording medium of the present invention (1)～(29), except the distortion that do not have bead-like, can carry out well lettering, conveying and operability good, particularly can obtain not damage the high color development concentration (high sensitivity) (print adaptability is good) of background white, image keeping quality after the print is also good, follow the contact angle raising and have ink-jet adaptability, also have good resistance to chemical reagents, and thermal head wearing and tearing less, also good aspect the matching of thermal head.That is, can satisfy marketing quality and operability, high sensitivityization and background white, image keeping quality, ink-jet adaptability, resistance to chemical reagents and thermal head matching (mar proof) simultaneously.
In addition; with the contrast of thermal recording medium (1) in; for the thermal recording medium that contains image stabilizing agent (2) and (3); can further improve image keeping quality and oil resistant China ink; for the thermal recording medium (6) that uses preferred adhesive (protecting colloid), can further seek high sensitivityization and reduce background fog.In addition, by containing image stabilizing agent, the adaptability of affixing one's seal and operability are also good especially.In the 1st embodiment of the present invention,, can further improve image keeping quality and oil resistant China ink (resistance to chemical reagents) for the thermal recording medium that is provided with the protective layer that contains suitable specific inorganic pigment (10)～(13).Even if use the sensitizer that uses among the embodiment 14～20, also can obtain and the same good performance of the thermal recording medium (1) of embodiment 1; Even if use the electron donability leuco dye that uses among the embodiment 21～25, also background fog can be remained on low-levelly, can also obtain good color emissivity, image keeping quality simultaneously.As embodiment 1 and 26, adopt curtain stream rubbing method useful aspect high sensitivity.In addition, even in support, contain the occasion (embodiment 9) of old paper stock, various performances are not brought adverse influence yet.
On the other hand, as electronic acceptance compound, under the situation that is used for the thermal recording medium of comparison (30)～(34), can not satisfy simultaneously thermal recording medium the various performances that should have, even can improve aspect crimping degree, the operability and can realize high sensitivityization, but variation often all aspect image keeping quality, resistance to chemical reagents and ink-jet adaptability if consider image keeping quality etc., then can't improved aspect crimping degree, the operability.In addition, when the coating back coating liquid, it is effective that coating weight is suited to be adjusted into optimised quantity.
[embodiment of the 2nd embodiment]
Below by embodiment the 2nd embodiment of the present invention is described, but the present invention is not subjected to the qualification of these embodiment." part " in following embodiment and " % " represent " mass parts " and " quality % " respectively.
(embodiment 30)
According to the following order of following composition formation, coating process etc., prepare the thermal recording medium of the 2nd embodiment of the present invention, when carrying out this preparation, be 15.2mJ/mm at the energy that applies by thermal head 2The time color development concentration be more than 1.2.
＜heat sensitive recording layer the preparation of coating fluid 〉
The preparation of-dispersion liquid A (containing the electron donability leuco dye)-
According to the embodiment 1 of the 1st embodiment in same composition and the method for dispersion liquid A, preparation dispersion liquid A.
The preparation of-dispersion liquid B (containing electronic acceptance compound)-
According to the embodiment 1 of the 1st embodiment in same composition and the method for dispersion liquid B, preparation dispersion liquid B.
The preparation of-dispersion liquid C (containing sensitizer)-
According to the embodiment 1 of the 1st embodiment in same composition and the method for dispersion liquid C, preparation dispersion liquid C.
The preparation of-dispersion liquid D-2 (containing pigment)-
Dispersion liquid D in the embodiment 1 of use and the 1st embodiment and use distilled water are as the water, according to same composition and method preparation dispersion liquid D-2.
The preparation of-heat sensitive recording layer usefulness coating fluid-
Following composition is mixed, obtained the heat sensitive recording layer coating fluid.
[the heat sensitive recording layer composition of coating fluid]
Dispersion liquid A ... 60 parts
Dispersion liquid B ... 120 parts
Dispersion liquid C ... 120 parts
Dispersion liquid D-2 ... 101 parts
Zinc stearate 30% dispersion liquid ... 15 parts
Paraffin (30%) ... 15 parts
Neopelex (25%) ... 4 parts
The preparation of＜support coating liquid for undercoat layer 〉
According to composition and the method same with the embodiment 1 of the 1st embodiment, preparation support coating liquid for undercoat layer.
The manufacturing of＜thermal recording medium 〉
The good quality paper of preparing a kind of smoothness by JIS-P8119 regulation and be 150 seconds is as support, the support coating liquid for undercoat layer that on the surface of this good quality paper, obtains as stated above with the coating of scraper plate coating machine, and controlling dried coating weight is 8g/m 2Thereby, formed priming coat.By being coated with this priming coat, make the JIS-P8119 smoothness of support become 350 seconds.
Then, the heat sensitive recording layer coating fluid that on above-mentioned priming coat, obtains as stated above with the coating of curtain flow coater, controlling dried coating weight is 4g/m 2, be dried, thereby formed heat sensitive recording layer.Then, the surface that forms heat sensitive recording layer is applied calender process, thereby obtained thermal recording medium of the present invention (35).
According to following (evaluation) same condition and method the thermal recording medium (35) that is obtained being measured, the result records, and is 15.2mJ/mm at the energy that applies of thermal head 2The time color development concentration (use Macbeath reflection of the concentration RD-918) be 1.28.
(embodiment 31)
The preparation of-dispersion liquid E-
According to composition and the method same with the embodiment 2 of the 1st embodiment, preparation dispersion liquid E.
The preparation of-heat sensitive recording layer usefulness coating fluid-
Prepare dispersion liquid A, B, C and D-2 similarly to Example 30, the dispersion liquid E that obtains is as stated above mixed to prepare the heat sensitive recording layer coating fluid with following composition, and then operation similarly to Example 30, obtained thermal recording medium of the present invention (36).
[the temperature-sensitive chromonic layer composition of coating fluid]
Dispersion liquid A ... 60 parts
Dispersion liquid B ... 120 parts
Dispersion liquid C ... 120 parts
Dispersion liquid E ... 30 parts
Dispersion liquid D-2 ... 101 parts
Zinc stearate 30% dispersion liquid ... 15 parts
Paraffin (30%) ... 15 parts
Neopelex (25%) ... 4 parts
(embodiment 32)
Except using 1,1,3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane replace when preparation dispersion liquid E, using among the embodiment 31 1,1, butane (image stabilizing agent) in addition for 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl), all the other and embodiment 31 similarly prepare dispersion liquid E, and then similarly operate with embodiment 31, have obtained thermal recording medium of the present invention (37).
(embodiment 33～34)
Except using amorphous silica (ミ ズ カ ミ Le P832 respectively, marshy land chemical industry (strain) system) 20 part, or calcite class precipitated calcium carbonate (the ユ ニ バ-70 that when preparation dispersion liquid D-2, uses among 40 parts of replacement embodiment 30 of aluminium hydroxide (Ha イ ジ ラ イ ト H42, clear and electrician's (strain) system); Inorganic pigment) beyond 40 parts, all the other are operated similarly to Example 30, have obtained thermal recording medium of the present invention (38)～(39).
(embodiment 35)
Except using sulfo group modified polyvinylalcohol (go-セ ラ Application L3266, Japan's synthetic chemistry (strain) system) polyvinyl alcohol 2.5% aqueous solution (adhesive) that uses when preparation dispersion liquid A, B and C among 2.5% aqueous solution replacement embodiment 30 in addition, all the other are operated similarly to Example 30, have obtained thermal recording medium of the present invention (40).
(embodiment 36)
Except polyvinyl alcohol 2.5% aqueous solution (adhesive) that uses when preparing dispersion liquid A, B and C among the embodiment 30 is changed into diacetone modified polyvinylalcohol (D500, ユ ニ チ カ society system) 2.5% aqueous solution, and dispersion liquid A, B and the C that will so change the back acquisition mix similarly to Example 30, obtain the heat sensitive recording layer coating fluid, and then in this coating fluid, add beyond 13 parts of adipic dihydrazide 5% aqueous solution (crosslinking agent), all the other are operated similarly to Example 30, have obtained thermal recording medium of the present invention (41).
(embodiment 37)
Except polyvinyl alcohol 2.5% aqueous solution (adhesive) that uses when preparing dispersion liquid A, B and C among the embodiment 30 is changed into acetoacetyl modified polyvinylalcohol (go-セ Off ア イ マ-Z210; Japan's synthetic chemistry (strain) system) 2.5% aqueous solution; and dispersion liquid A, B and the C that will so change the back acquisition mix similarly to Example 30; obtain the heat sensitive recording layer coating fluid; and then in this coating fluid, add beyond 13 parts of glyoxal 5% aqueous solution (crosslinking agent); all the other are operated similarly to Example 30, have obtained thermal recording medium of the present invention (42).
(embodiment 38)
A kind of by old paper stock 70% except using, LBKP 30% formation and JIS-P8119 smoothness are 170 seconds recycled writing paper (50g/m 2) beyond the good quality paper that replaces using as support among the embodiment 30, all the other are operated similarly to Example 30, have obtained thermal recording medium of the present invention (43).
(embodiment 39)
Embodiment 30＜manufacturing of thermal recording medium in; after forming priming coat on the support; do not carry out coating, drying and the calender process of heat sensitive recording layer with coating fluid; replace and after forming priming coat, use the curtain flow coater that the heat sensitive recording layer that obtains in embodiment 30 is carried out lamination coating simultaneously, drying, carries out calender process on the surface of the protective layer of lamination with coating fluid with by the following protective layer used coating fluid that constitutes; in addition; operation has obtained thermal recording medium of the present invention (44) similarly to Example 30.Should illustrate that the drying coated amount of protective layer is 2.0g/m 2
The preparation of-protective layer used coating fluid-
According to the embodiment 10 of the 1st embodiment in same composition and the method for protective layer used coating fluid, prepare protective layer used coating fluid.
(embodiment 40～42)
Use aluminium hydroxide (Ha イ ジ ラ イ ト H43 respectively, volume average particle size 0.7 μ, clear and electrician's (strain) system) 40 parts, kaolin (カ オ Block ラ イ ト, volume average particle size 2.5 μ, Bai Shigong industry (strain) system) 40 parts or amorphous silica (ミ ズ カ シ Le P707, volume average particle size 2.2 μ, marshy land chemistry (strain) system) 20 parts replace aluminium hydroxide (the Ha イ ジ ラ イ ト H42 that uses among the embodiment 39 when the protective layer used coating fluid of preparation; Inorganic pigment) 40 parts, in addition, similarly operate with embodiment 39, obtained thermal recording medium of the present invention (45)～(47).
(embodiment 43～49)
Use oxalic acid dimethylbenzyl ester (HS3520R-N respectively, big Japanese ink industry (strain) system), a terphenyl, ethylene glycol 4-tolyl ether, to benzylbiphenyl, 1,2-hexichol oxygen ylmethyl benzene, diphenyl sulphone (DPS) or 1, the 2-benzyloxy naphthalene (sensitizer) that when preparation dispersion liquid C, uses among the 2-biphenoxyl ethane replacement embodiment 30, in addition, operation has obtained thermal recording medium of the present invention (48)～(54) similarly to Example 30.
(embodiment 50～54)
Use 2-anilino--3-methyl-6-dibutylamino fluorane respectively, 2-anilino--3-methyl-6-(N-ethyl-N-isoamylamino) fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-third amino) fluorane, 2-anilino--3-methyl-6-two pentylamine base fluoranes, or the 2-anilino--3-methyl-6-lignocaine fluorane (electron donability leuco dye) that when preparation dispersion liquid A, uses among 2-anilino--3-methyl-6-(N-ethyl-N-p-methylphenyl amino) fluorane replacement embodiment 30, in addition, operation has obtained thermal recording medium of the present invention (55)～(59) similarly to Example 30.
(embodiment 55)
The curtain flow coater that uses when being coated with heat sensitive recording layer with coating fluid in using air knife doctor knife coater replacement embodiment 30, all the other are operated similarly to Example 30, have obtained thermal recording medium of the present invention (60).
(embodiment 56～59)
Use N-benzyl-4-hydroxy benzene sulfonamide (=right-N-benzyl sulfonamides phenol), BTUM, 4-hydroxyl-4 '-isopropoxy diphenyl sulphone (DPS) or 2 respectively; the 4-hydroxy benzenes sulfonanilide (electronic acceptance compound) that when preparation dispersion liquid B, uses among two (phenyl sulfonyl) phenol replacement of the 4-embodiment 30; in addition; operation has obtained thermal recording medium of the present invention (60)～(64) similarly to Example 30.
(comparative example 6～7)
Use 2 respectively, 2 '-two (4-hydroxyl phenol) propane (bisphenol-A) or 4, the 4-hydroxy benzenes sulfonanilide (electronic acceptance compound) that when preparation dispersion liquid B, uses among 4 '-dihydroxydiphenylsulisomer replacement embodiment 30, in addition, operate similarly to Example 30, obtained to be used for thermal recording medium (65)～(66) of comparison.
(comparative example 8)
The 4-hydroxy benzenes sulfonanilide (electronic acceptance compound) that uses when preparing dispersion liquid B among the embodiment 30 is changed into 4 parts for 20 parts, in addition, operate similarly to Example 30, obtained to be used for the thermal recording medium (67) of comparison.
(comparative example 9)
Except will in embodiment 30, changing into 10g/m with coating fluid in dried coating weight by heat sensitive recording layer 2In addition, all the other are operated similarly to Example 30, have obtained to be used for the thermal recording medium (68) of comparison.
(evaluation)
Carry out following mensuration and evaluation for thermal recording medium of the present invention (35)～(64) of above-mentioned acquisition and thermal recording medium (65)～(68) that are used for comparison.Should illustrate that measures and estimate the results are shown in the following table 2.
(1) mensuration of sensitivity
According to the embodiment of the 1st embodiment in the same method of evaluation, the mensuration of carrying out sensitivity.
(2) evaluation of background whiteness
Measure the background part on each thermal recording medium surface with Macbeath reflection of the concentration (RD-918, Macbeath society system).
(3) evaluation of background fog
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out the evaluation of background fog.
(4) the conservatory evaluation of image
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out the conservatory evaluation of image.
(5) evaluation of resistance to chemical reagents
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out the evaluation of resistance to chemical reagents.
(6) evaluation of thermal head breakage
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out the evaluation of thermal head breakage.
(7) the adaptive evaluation of ink-jet
1. oil resistant China ink
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out the evaluation of oil resistant China ink.
2. ink mist recording adaptability
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out the adaptive evaluation of ink mist recording.
(8) measurement of contact angle
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out measurement of contact angle.
(9) ion (Na +, K +) mensuration of concentration
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out the mensuration of ion concentration.
Table 2
Thermal recording medium Image color (sensitivity) The background whiteness The image keeping quality Background fog concentration Resistance to chemical reagents The thermal head breakage Ink-jet adaptability Contact angle [°] Ion concentration [ppm]
Printing ink patience Ink mist recording adaptability
Embodiment 30 ????(35) ??1.28 ??0.07 ??95％ ??0.09 ??○ 0 ??90％ ??○ ??51 ??780
Embodiment 31 ????(36) ??1.27 ??0.08 ??98％ ??0.10 ??○ 0 ??93％ ??○ ??55 ??800
Embodiment 32 ????(37) ??1.26 ??0.08 ??97％ ??0.10 ??○ 0 ??92％ ??○ ??53 ??800
Embodiment 33 ????(38) ??1.26 ??0.08 ??93％ ??0.10 ??○ 0 ??88％ ??○ ??50 ??770
Embodiment 34 ????(39) ??1.27 ??0.07 ??96％ ??0.09 ??○ 0 ??91％ ??○ ??55 ??790
Embodiment 35 ????(40) ??1.30 ??0.06 ??96％ ??0.08 ??○ 0 ??93％ ??○ ??50 ??800
Embodiment 36 ????(41) ??1.29 ??0.06 ??97％ ??0.08 ??○ 0 ??92％ ??○ ??52 ??800
Embodiment 37 ????(42) ??1.28 ??0.07 ??95％ ??0.08 ??○ 0 ??93％ ??○ ??55 ??790
Embodiment 38 ????(43) ??1.28 ??0.07 ??94％ ??0.09 ??○ 0 ??93％ ??○ ??60 ??800
Embodiment 39 ????(44) ??1.23 ??0.07 ??98％ ??0.09 ??○ 0 ??98％ ??○ ??45 ??800
Embodiment 40 ????(45) ??1.22 ??0.07 ??97％ ??0.09 ??○ 0 ??97％ ??○ ??42 ??800
Embodiment 41 ????(46) ??1.21 ??0.08 ??98％ ??0.10 ??○ 0 ??98％ ??○ ??48 ??790
Embodiment 42 ????(47) ??1.20 ??0.08 ??96％ ??0.10 ??○ 0 ??92％ ??○ ??35 ??800
Embodiment 43 ????(48) ??1.27 ??0.07 ??94％ ??0.09 ??○ 0 ??89％ ??○ ??50 ??790
Embodiment 44 ????(49) ??1.26 ??0.08 ??95％ ??0.10 ??○ 0 ??91％ ??○ ??51 ??800
Embodiment 45 ????(50) ??1.28 ??0.07 ??94％ ??0.09 ??○ 0 ??92％ ??○ ??51 ??790
Embodiment 46 ????(51) ??1.24 ??0.07 ??91％ ??0.10 ??○ 0 ??89％ ??○ ??50 ??800
Embodiment 47 ????(52) ??1.26 ??0.08 ??95％ ??0.10 ??○ 0 ??91％ ??○ ??52 ??790
Embodiment 48 ????(53) ??1.28 ??0.07 ??93％ ??0.09 ??○ 0 ??89％ ??○ ??51 ??800
Embodiment 49 ????(54) ??1.25 ??0.07 ??92％ ??0.10 ??○ 0 ??91％ ??○ ??50 ??790
Embodiment 50 ????(55) ??1.28 ??0.08 ??97％ ??0.10 ??○ 0 ??93％ ??○ ??55 ??790
Embodiment 51 ????(56) ??1.26 ??0.08 ??95％ ??0.10 ??○ 0 ??88％ ??○ ??55 ??780
Embodiment 52 ????(57) ??1.26 ??0.08 ??92％ ??0.10 ??○ 0 ??87％ ??○ ??55 ??790
Embodiment 53 ????(58) ??1.28 ??0.08 ??95％ ??0.10 ??○ 0 ??91％ ??○ ??51 ??790
Embodiment 54 ????(59) ??1.24 ??0.06 ??88％ ??0.08 ??○ 0 ??85％ ??○ ??50 ??780
Embodiment 55 ????(60) ??1.26 ??0.09 ??93％ ??0.10 ??○ 0 ??90％ ??○ ??52 ??780
Embodiment 56 ????(61) ??1.20 ??0.10 ??65％ ??0.09 ??△ 0 ??80％ ??△ ??55 ??760
Embodiment 57 ????(62) ??1.22 ??0.10 ??98％ ??0.12 ??○ 0 ??92％ ??○ ??50 ??800
Embodiment 58 ????(63) ??1.26 ??0.07 ??91％ ??0.07 ??○ 0 ??93％ ??○ ??52 ??780
Embodiment 59 ????(64) ??1.30 ??0.09 ??98％ ??0.11 ??○ 0 ??96％ ??○ ??51 ??790
Comparative example 6 ????(65) ??1.15 ??0.07 ??70％ ??0.08 ??× 0 ??60％ ??× ??45 ??790
Comparative example 7 ????(66) ??1.05 ??0.07 ??65％ ??0.08 ??× 0 ??65％ ??× ??42 ??780
Comparative example 8 ????(67) ??1.28 ??0.07 ??50％ ??0.09 ??△ 0 ??55％ ??△ ??45 ??760
Comparative example 9 ????(68) ??1.28 ??0.12 ??85％ ??0.15 ??○ 0 ??80％ ??○ ??55 ??1100
From the result of above-mentioned table 2 as can be seen, for containing the electron donability leuco dye simultaneously and being 15.2mJ/mm by the electronic acceptance compound of general formula (1) expression and when applying energy 2The time color development concentration be thermal recording medium of the present invention (35)～(64) more than 1.20, particularly can when keeping background fog, obtain high color development concentration (high sensitivity) (print adaptability is good), image keeping quality after print is also good, follow the raising of contact angle and have ink-jet adaptability, also have good resistance to chemical reagents, and thermal head wearing and tearing less, also good aspect the matching of thermal head.That is, can satisfy high sensitivityization and background white, image keeping quality, ink-jet adaptability, resistance to chemical reagents and thermal head matching (mar proof) simultaneously.
In addition, with the contrast of thermal recording medium (35) in, for the thermal recording medium that contains image stabilizing agent (36) and (37), can further improve image keeping quality and oil resistant China ink; For the thermal recording medium (40) that uses preferred adhesive (protecting colloid), can seek the reduction of further high sensitivityization and background fog.In addition, by containing image stabilizing agent, make affix one's seal adaptability and operability also good especially.In the 2nd embodiment of the present invention,, can further improve image keeping quality and oil resistant China ink (resistance to chemical reagents) for the thermal recording medium that is provided with the protective layer that contains suitable specific inorganic pigment (44)～(47).Even if use the sensitizer that in embodiment 43～49, uses, also can obtain and the same good performance of the thermal recording medium (35) of embodiment 30; Even if use the electron donability leuco dye that in embodiment 50～54, uses, also background fog can be remained on low-levelly, can also obtain good color emissivity and image keeping quality simultaneously.As embodiment 30 and 55, adopt curtain stream rubbing method useful aspect high sensitivityization.In addition, even in support, contain the occasion (embodiment 38) of old paper stock, various performances are not brought adverse effect yet.
On the other hand, relatively use thermal recording medium (65)～(68) for not using as electronic acceptance compound by the compound of general formula (1) expression, particularly not only can not seek high sensitivityization, and all inferior aspect image keeping quality, resistance to chemical reagents and ink-jet adaptability, can not satisfy simultaneously thermal recording medium the various performances that should have.In addition, for the thermal recording medium that increases coating weight (68), except increasing the raw material use amount, increasing the influence of environment and must increase the energy consumption when the drying, also must be set at higher temperature to baking temperature, its result, also can cause the whiteness of this bottom to reduce, and the image keeping quality also have the tendency of reduction.
[embodiment of the 3rd embodiment]
Below by embodiment the 3rd embodiment of the present invention is described, but the present invention is not subjected to the qualification of these embodiment." part " in following embodiment and " % " represent " mass parts " and " quality % " respectively.
(embodiment 60)
According to the following order of following composition formation, coating process etc., prepare the thermal recording medium of the 3rd embodiment of the present invention, when carrying out this preparation, be 15.2mJ/mm at the energy that applies by thermal head 2The time color development concentration be more than 1.20.
＜heat sensitive recording layer the preparation of coating fluid 〉
The preparation of-dispersion liquid A (containing the electron donability leuco dye)-
According to the embodiment 1 of the 1st embodiment in same composition and the method for dispersion liquid A, preparation dispersion liquid A.
The preparation of-dispersion liquid B (containing electronic acceptance compound)-
According to the embodiment 1 of the 1st embodiment in same composition and the method for dispersion liquid B, preparation dispersion liquid B.
The preparation of-dispersion liquid C (containing sensitizer)-
According to the embodiment 1 of the 1st embodiment in same composition and the method for dispersion liquid C, preparation dispersion liquid C.
The preparation of-dispersion liquid D (containing pigment)-
According to the embodiment 1 of the 1st embodiment in same composition and the method for dispersion liquid D, preparation dispersion liquid D.
The preparation of-heat sensitive recording layer usefulness coating fluid-
Following composition is mixed, obtained the heat sensitive recording layer coating fluid.
[the heat sensitive recording layer composition of coating fluid]
Dispersion liquid A ... 60 parts
Dispersion liquid B ... 120 parts
Dispersion liquid C ... 120 parts
Dispersion liquid D ... 101 parts
Zinc stearate 30% dispersion liquid ... 15 parts
Paraffin (30%) ... 15 parts
Neopelex (25%) ... 4 parts
The preparation of＜support coating liquid for undercoat layer 〉
According to composition and the method same with the embodiment 1 of the 1st embodiment, preparation support coating liquid for undercoat layer.
The manufacturing of＜thermal recording medium 〉
The good quality paper of preparing a kind of smoothness by JIS-P8119 regulation and be 150 seconds is as support, the support coating liquid for undercoat layer that on the surface of this good quality paper, obtains as stated above with the coating of scraper plate coating machine, controlling dried coating weight is 8g/m2, thereby has formed priming coat.By being coated with this priming coat, make the JIS-P8119 smoothness of support become 350 seconds.
Then, the heat sensitive recording layer coating fluid that on above-mentioned priming coat, obtains as stated above with the coating of curtain flow coater, controlling dried coating weight is 4g/m 2, be dried, thereby formed heat sensitive recording layer.Then, the surface that forms heat sensitive recording layer is applied calender process, thereby obtained thermal recording medium of the present invention (69).
According to following (evaluation) same condition and method the thermal recording medium (69) that is obtained being measured, the result records, and is 15.2mJ/mm at the energy that applies of thermal head 2The time color development concentration (use Macbeath reflection of the concentration RD-918) be 1.28.
(embodiment 61)
The preparation of-dispersion liquid E-
According to composition and the method same with the embodiment 2 of the 1st embodiment, preparation dispersion liquid E.
The preparation of-heat sensitive recording layer usefulness coating fluid-
Similarly prepare dispersion liquid A, B, C and D with embodiment 60, the dispersion liquid E that obtains is as stated above mixed to prepare the heat sensitive recording layer coating fluid with following composition, and then similarly operate with embodiment 60, obtained thermal recording medium of the present invention (70).
[the temperature-sensitive chromonic layer composition of coating fluid]
Dispersion liquid A ... 60 parts
Dispersion liquid B ... 120 parts
Dispersion liquid C ... 120 parts
Dispersion liquid E ... 30 parts
Dispersion liquid D ... 101 parts
Zinc stearate 30% dispersion liquid ... 20 parts
Paraffin (30%) ... 20 parts
Neopelex (25%) ... 4 parts
(embodiment 62)
Except using 1,1,3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane replace when preparation dispersion liquid E, using among the embodiment 61 1,1, butane (image stabilizing agent) in addition for 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl), all the other and embodiment 61 similarly prepare dispersion liquid E, and then similarly operate with embodiment 61, have obtained thermal recording medium of the present invention (71).
(embodiment 63～64)
Except using amorphous silica (ミ ズ カ ミ Le P832 respectively, marshy land chemical industry (strain) system) 20 part, or calcite class precipitated calcium carbonate (the ユ ニ バ-70 that when preparation dispersion liquid D, uses among 40 parts of replacement embodiment 60 of aluminium hydroxide (Ha イ ジ ラ イ ト H42, clear and electrician's (strain) system); Inorganic pigment) beyond 40 parts, all the other and embodiment 60 similarly operate, and have obtained thermal recording medium of the present invention (72)～(73).
(embodiment 65)
Except using sulfo group modified polyvinylalcohol (go-セ ラ Application L3266, Japan's synthetic chemistry (strain) system) polyvinyl alcohol 2.5% aqueous solution (adhesive) that uses when preparation dispersion liquid A, B and C among 2.5% aqueous solution replacement embodiment 60 in addition, all the other and embodiment 60 similarly operate, and have obtained thermal recording medium of the present invention (74).
(embodiment 66)
Except polyvinyl alcohol 2.5% aqueous solution (adhesive) that uses when preparing dispersion liquid A, B and C among the embodiment 60 is changed into diacetone modified polyvinylalcohol (D500, ユ ニ チ カ society system) 2.5% aqueous solution, and dispersion liquid A, B and the C that will so change the back acquisition similarly mix with embodiment 60, obtain the heat sensitive recording layer coating fluid, and then in this coating fluid, add beyond 13 parts of adipic dihydrazide 5% aqueous solution (crosslinking agent), all the other and embodiment 60 similarly operate, and have obtained thermal recording medium of the present invention (75).
(embodiment 67)
Except polyvinyl alcohol 2.5% aqueous solution (adhesive) that uses when preparing dispersion liquid A, B and C among the embodiment 60 is changed into acetoacetyl modified polyvinylalcohol (go-セ Off ア イ マ-Z210; Japan's synthetic chemistry (strain) system) 2.5% aqueous solution; and dispersion liquid A, B and the C that will so change the back acquisition similarly mix with embodiment 60; obtain the heat sensitive recording layer coating fluid; and then in this coating fluid, add beyond 13 parts of glyoxal 5% aqueous solution (crosslinking agent); all the other and embodiment 60 similarly operate, and have obtained thermal recording medium of the present invention (76).
(embodiment 68)
A kind of by old paper stock 70% except using, LBKP 30% formation and JIS-P8119 smoothness are 170 seconds recycled writing paper (50g/m 2) beyond the good quality paper that replaces using as support among the embodiment 60, all the other and embodiment 60 similarly operate, and have obtained thermal recording medium of the present invention (77).
(embodiment 69)
Embodiment 60＜manufacturing of thermal recording medium in; after forming priming coat on the support; do not carry out coating, drying and the calender process of heat sensitive recording layer with coating fluid; replace and after forming priming coat, use the curtain flow coater that the heat sensitive recording layer that obtains in embodiment 60 is carried out lamination coating simultaneously, drying, carries out calender process on the surface of the protective layer of lamination with coating fluid with by the following protective layer used coating fluid that constitutes; in addition; similarly operate with embodiment 60, obtained thermal recording medium of the present invention (78).Should illustrate that the drying coated amount of protective layer is 2.0g/m 2
The preparation of-protective layer used coating fluid-
According to the embodiment 10 of the 1st embodiment in same composition and the method for protective layer used coating fluid, prepare protective layer used coating fluid.
(embodiment 70～72)
Use aluminium hydroxide (Ha イ ジ ラ イ ト H43 respectively, volume average particle size 0.7 μ m, clear and electrician's (strain) system) 40 parts, kaolin (カ オ Block ラ イ ト, volume average particle size 2.5 μ m, Bai Shigong industry (strain) system) 40 parts or amorphous silica (ミ ズ カ シ Le P707, volume average particle size 2.2 μ m, marshy land chemistry (strain) system) 20 parts replace aluminium hydroxide (the Ha イ ジ ラ イ ト H42 that uses among the embodiment 69 when the protective layer used coating fluid of preparation; Inorganic pigment) 40 parts, in addition, similarly operate with embodiment 69, obtained thermal recording medium of the present invention (79)～(81).
(embodiment 73～79)
Use oxalic acid dimethylbenzyl ester (HS3520R-N respectively, big Japanese ink industry (strain) system), a terphenyl, ethylene glycol 4-tolyl ether, to benzylbiphenyl, 1,2-hexichol oxygen ylmethyl benzene, diphenyl sulphone (DPS) or 1, the 2-benzyloxy naphthalene (sensitizer) that when preparation dispersion liquid C, uses among the 2-biphenoxyl ethane replacement embodiment 60, in addition, similarly operate with embodiment 60, obtained thermal recording medium of the present invention (82)～(88).
(embodiment 80～84)
Use 2-anilino--3-methyl-6-dibutylamino fluorane respectively, 2-anilino--3-methyl-6-(N-ethyl-N-isoamylamino) fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-third amino) fluorane, 2-anilino--3-methyl-6-two pentylamine base fluoranes, or the 2-anilino--3-methyl-6-lignocaine fluorane (electron donability leuco dye) that when preparation dispersion liquid A, uses among 2-anilino--3-methyl-6-(N-ethyl-N-p-methylphenyl amino) fluorane replacement embodiment 60, in addition, similarly operate with embodiment 60, obtained thermal recording medium of the present invention (89)～(93).
(embodiment 85)
The curtain flow coater that uses when being coated with heat sensitive recording layer with coating fluid in using air knife doctor knife coater replacement embodiment 60, all the other and embodiment 60 similarly operate, and have obtained thermal recording medium of the present invention (94).
(embodiment 86～89)
Use N-benzyl-4-hydroxy benzene sulfonamide (=right-N-benzyl sulfonamides phenol), BTUM, 4-hydroxyl-4 '-isopropoxy diphenyl sulphone (DPS) or 2 respectively; the 4-hydroxy benzenes sulfonanilide (electronic acceptance compound) that when preparation dispersion liquid B, uses among two (phenyl sulfonyl) phenol replacement of the 4-embodiment 60; in addition; similarly operate with embodiment 60, obtained thermal recording medium of the present invention (95)～(98).
(comparative example 10)
Except using 4, the 4-hydroxy benzenes sulfonanilide (electronic acceptance compound) that uses when preparation dispersion liquid B among 4 '-dihydroxydiphenylsulisomer replacement embodiment 60 in addition, all the other and embodiment 60 similarly operate, and have obtained to be used for the thermal recording medium (99) of comparison.
(comparative example 11)
Except the 4-hydroxy benzenes sulfonanilide (electronic acceptance compound) that uses when preparing dispersion liquid B among the embodiment 60 is changed into 4 parts for 20 parts, all the other and embodiment 60 similarly operate, and have obtained to be used for the thermal recording medium (100) of comparison.
(comparative example 12)
Be used as among the embodiment 60 support, be that to change into above-mentioned smoothness be 30 seconds good quality paper for 150 seconds good quality paper by the smoothness of JIS-P8119 regulation, and then do not use zinc stearate 30% dispersion liquid and paraffin in coating fluid at heat sensitive recording layer, in addition, similarly operate with embodiment 60, obtained to be used for the thermal recording medium (101) of comparison.
(comparative example 13)
Be used as among the embodiment 60 support, be that to change into above-mentioned smoothness be 1000 seconds coated paper for 150 seconds good quality paper by the smoothness of JIS-P8119 regulation, and then heat sensitive recording layer changed into 45 parts for 15 parts with zinc stearate 30% dispersion liquid that uses in the coating fluid, and 15 parts in paraffin changed into 45 parts, in addition, similarly operate with embodiment 60, obtained to be used for the thermal recording medium (102) of comparison.
(evaluation)
Carry out following mensuration and evaluation for thermal recording medium of the present invention (69)～(98) of above-mentioned acquisition and thermal recording medium (99)～(102) that are used for comparison.Should illustrate that measures and estimate the results are shown in the following table 3.
(1) mensuration of sensitivity
According to the embodiment of the 1st embodiment in the same method of evaluation, the mensuration of carrying out sensitivity.
(2) mensuration of the confficient of static friction coefficient of kinetic friction
The confficient of static friction and the coefficient of kinetic friction have been measured according to ASTM D1894-73.That is, thermal recording medium is cut into the size (thermal recording medium sheet A) of wide 100mm, long 200mm in 23 ℃ thermostatic chamber, thermal photography is assemblied on the flat runner faceup.Similarly, the thermal recording medium sheet B that is cut into wide 60mm, long 120mm size as load weight (W °=1.96N (200gf); Hereinafter referred to as " sled "), reel as the mode of inboard by its thermal photography face, fix with adhesive tape.Then, sled is connected on the load cell with monofilament, the sled that forms of being reeled by the thermal recording medium sheet is placed on the thermal photography face of the thermal recording medium sheet that is assemblied on the flat runner lightly, flat runner is moved by the test speed that 600mm/ divides, measure the confficient of static friction and the coefficient of kinetic friction.
(3) the conservatory evaluation of image
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out the conservatory evaluation of image.
(4) evaluation of background fog
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out the evaluation of background fog.
(5) evaluation of resistance to chemical reagents
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out the evaluation of resistance to chemical reagents.
(6) evaluation of thermal head breakage
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out the evaluation of thermal head breakage.
(7) conveying property
Use word processor (Le Port 95JV, (strain) Toshiba system), on its sheet feeding section, place 30 pages on A4 paper, carry out lettering, according to the conveying of following benchmark evaluation paper.
Zero: can 1 page of 1 page of normal paper feeding.
*: can not paper feeding, perhaps with multipage paper paper feeding simultaneously.
(8) the adaptive evaluation of ink-jet
1. oil resistant China ink
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out the evaluation of oil resistant China ink.
2. ink mist recording adaptability
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out the adaptive evaluation of ink mist recording.
(9) measurement of contact angle
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out measurement of contact angle.
(10) ion (Na +, K +) mensuration of concentration
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out the mensuration of ion concentration.
Table 3
Thermal recording medium Image color (sensitivity) Confficient of static friction The coefficient of kinetic friction The image keeping quality Background fog concentration Resistance to chemical reagents The thermal head breakage Conveying property Ink-jet adaptability Contact angle [°] Ion concentration [ppm]
Printing ink patience Ink mist recording adaptability
Embodiment 60 ????(69) ??1.28 ??0.40 ??0.35 ??95％ ??0.09 ??○ 0 ??○ ??90％ ??○ ??51 ??780
Embodiment 61 ????(70) ??1.27 ??0.40 ??0.36 ??98％ ??0.10 ??○ 0 ??○ ??93％ ??○ ??55 ??800
Embodiment 62 ????(71) ??1.26 ??0.40 ??0.35 ??97％ ??0.10 ??○ 0 ??○ ??92％ ??○ ??53 ??800
Embodiment 63 ????(72) ??1.26 ??0.39 ??0.35 ??93％ ??0.10 ??○ 0 ??○ ??88％ ??○ ??50 ??770
Embodiment 64 ????(73) ??1.27 ??0.42 ??0.39 ??96％ ??0.09 ??○ 0 ??○ ??91％ ??○ ??55 ??790
Embodiment 65 ????(74) ??1.30 ??0.40 ??0.35 ??96％ ??0.08 ??○ 0 ??○ ??93％ ??○ ??50 ??800
Embodiment 66 ????(75) ??1.29 ??0.40 ??0.36 ??97％ ??0.08 ??○ 0 ??○ ??92％ ??○ ??52 ??800
Embodiment 67 ????(76) ??1.28 ??0.40 ??0.35 ??95％ ??0.08 ??○ 0 ??○ ??93％ ??○ ??55 ??790
Embodiment 68 ????(77) ??1.28 ??0.47 ??0.44 ??94％ ??0.09 ??○ 0 ??○ ??93％ ??○ ??60 ??800
Embodiment 69 ????(78) ??1.23 ??0.35 ??0.30 ??98％ ??0.09 ??○ 0 ??○ ??98％ ??○ ??45 ??800
Embodiment 70 ????(79) ??1.22 ??0.30 ??0.27 ??97％ ??0.09 ??○ 0 ??○ ??97％ ??○ ??42 ??800
Embodiment 71 ????(80) ??1.21 ??0.36 ??0.28 ??98％ ??0.10 ??○ 0 ??○ ??98％ ??○ ??48 ??790
Embodiment 72 ????(81) ??1.20 ??0.35 ??0.29 ??96％ ??0.10 ??○ 0 ??○ ??92％ ??○ ??35 ??800
Embodiment 73 ????(82) ??1.27 ??0.40 ??0.35 ??94％ ??0.09 ??○ 0 ??○ ??89％ ??○ ??50 ??790
Embodiment 74 ????(83) ??1.26 ??0.40 ??0.36 ??95％ ??0.10 ??○ 0 ??○ ??91％ ??○ ??51 ??800
Embodiment 75 ????(84) ??1.28 ??0.41 ??0.35 ??94％ ??0.09 ??○ 0 ??○ ??92％ ??○ ??51 ??790
Embodiment 76 ????(85) ??1.24 ??0.40 ??0.35 ??91％ ??0.10 ??○ 0 ??○ ??89％ ??○ ??50 ??800
Embodiment 77 ????(86) ??1.26 ??0.41 ??0.36 ??95％ ??0.10 ??○ 0 ??○ ??91％ ??○ ??52 ??790
Embodiment 78 ????(87) ??1.28 ??0.40 ??0.35 ??93％ ??0.09 ??○ 0 ??○ ??89％ ??○ ??51 ??800
Embodiment 79 ????(88) ??1.25 ??0.41 ??0.36 ??92％ ??0.10 ??○ 0 ??○ ??91％ ??○ ??50 ??790
Embodiment 80 ????(89) ??1.28 ??0.41 ??0.35 ??97％ ??0.10 ??○ 0 ??○ ??93％ ??○ ??55 ??790
Embodiment 81 ????(90) ??1.26 ??0.40 ??0.36 ??95％ ??0.10 ??○ 0 ??○ ??88％ ??○ ??55 ??780
Embodiment 82 ????(91) ??1.26 ??0.40 ??0.35 ??92％ ??0.10 ??○ 0 ??○ ??87％ ??○ ??55 ??790
Embodiment 83 ????(92) ??1.28 ??0.40 ??0.36 ??95％ ??0.10 ??○ 0 ??○ ??91％ ??○ ??51 ??790
Embodiment 84 ????(93) ??1.24 ??0.41 ??0.35 ??88％ ??0.08 ??○ 0 ??○ ??85％ ??○ ??50 ??780
Embodiment 85 ????(94) ??1.26 ??0.34 ??0.31 ??93％ ??0.10 ??○ 0 ??○ ??90％ ??○ ??52 ??780
Embodiment 86 ????(95) ??1.20 ??0.40 ??0.35 ??65％ ??0.09 ??△ 0 ??○ ??80％ ??△ ??55 ??760
Embodiment 87 ????(96) ??1.22 ??0.40 ??0.36 ??98％ ??0.12 ??○ 0 ??○ ??92％ ??○ ??50 ??800
Embodiment 88 ????(97) ??1.26 ??0.41 ??0.36 ??91％ ??0.07 ??○ 0 ??○ ??93％ ??○ ??52 ??780
Embodiment 89 ????(98) ??1.26 ??0.40 ??0.35 ??98％ ??0.11 ??○ 0 ??○ ??96％ ??○ ??51 ??790
Comparative example 10 ????(99) ??1.15 ??0.41 ??0.36 ??65％ ??0.08 ??× 0 ??○ ??65％ ??× ??42 ??780
Comparative example 11 ????(100) ??1.05 ??0.40 ??0.35 ??50％ ??0.09 ??△ 0 ??○ ??55％ ??△ ??45 ??760
Comparative example 12 ????(101) ??1.1 ??0.65 ??0.60 ????92％ ??0.09 ??× 0 ??× ??88％ ??○ ??35 ??720
Comparative example 13 ????(102) ??1.16 ??0.17 ??0.15 ??88％ ??0.10 ??× ??× ??84％ ??○ ??60 ??820
From the result of above-mentioned table 3 as can be seen, thermal recording medium of the present invention (69)～(98) are owing to be 15.2mJ/mm applying energy 2The time color development concentration more than 1.20, and in the confficient of static friction and the scope of the coefficient of kinetic friction when the mantle friction of the most surperficial and dorsal part that makes thermal recording medium table side 0.2～0.5, therefore, particularly can be when keeping low background fog, obtain high color development concentration (high sensitivity) (print adaptability is good), image keeping quality after print is also good, follow the raising of contact angle and have ink-jet adaptability, also has good resistance to chemical reagents, and the thermal head wearing and tearing are few, and are also good aspect the matching of thermal head.That is, can satisfy high sensitivityization and background white, image keeping quality, ink-jet adaptability, resistance to chemical reagents and thermal head matching (mar proof) simultaneously.And then the 3rd embodiment of thermal recording medium of the present invention is also good aspect conveying property.
In addition, with the contrast of thermal recording medium (69) in, for the thermal recording medium that contains image stabilizing agent (70) and (71), can further improve image keeping quality and oil resistant China ink; For the thermal recording medium (74) that uses preferred adhesive (protecting colloid), can seek the reduction of further high sensitivityization and background fog.In addition, by containing image stabilizing agent, make affix one's seal adaptability and operability also good especially.In the 3rd embodiment of the present invention,, can further improve image keeping quality and oil resistant China ink (resistance to chemical reagents) for the thermal recording medium that is provided with the protective layer that contains suitable specific inorganic pigment (78)～(81).Even if use the sensitizer that in embodiment 73～79, uses, also can obtain and the same good performance of the thermal recording medium (69) of embodiment 60; Even if use the electron donability leuco dye that in embodiment 80～84, uses, also background fog can be kept low level, can also obtain good color emissivity and image keeping quality simultaneously.As embodiment 60 and 85, adopt curtain stream rubbing method useful aspect high sensitivityization, in addition,, various performances are not brought adverse effect even in support, contain the occasion (embodiment 68) of old paper stock yet.
On the other hand, for not using compound by general formula (1) expression, and utilize thermal head to apply 15.2mJ/mm as electronic acceptance compound 2The image color less than 1.20 that obtains when coming print of energy relatively use thermal recording medium (99)～(102), particularly not only can not seek high sensitivityization, and all inferior aspect image keeping quality, resistance to chemical reagents and ink-jet adaptability, can not satisfy simultaneously thermal recording medium the various performances that should have.
[embodiment of the 4th embodiment]
Below by embodiment the 4th embodiment of the present invention is described, but the present invention is not subjected to the qualification of these embodiment." part " in following embodiment and " % " represent " mass parts " and " quality % " respectively.
(embodiment 90)
＜heat sensitive recording layer the preparation of coating fluid 〉
The preparation of-dispersion liquid A (containing the electron donability leuco dye)-
According to the embodiment 1 of the 1st embodiment in same composition and the method for dispersion liquid A, preparation dispersion liquid A.
The preparation of-dispersion liquid B (containing electronic acceptance compound)-
According to the embodiment 1 of the 1st embodiment in same composition and the method for dispersion liquid B, preparation dispersion liquid B.
The preparation of-dispersion liquid C (containing sensitizer)-
According to the embodiment 1 of the 1st embodiment in same composition and the method for dispersion liquid C, preparation dispersion liquid C.
The preparation of-dispersion liquid D-4 (containing pigment)-
Each following composition is mixed, disperses with puddle mixer, and having obtained volume average particle size is the dispersion liquid D-4 of 2.0 μ m.Volume average particle size is according to similarly measuring with the occasion of dispersion liquid A.
[composition of dispersion liquid D-4]
Calcite class precipitated calcium carbonate (pigment) ... 40 parts
(ユ ニ バ-70, white lapicide's industry (strain) system,
Boil the oil absorption of Linseed oil: 55ml/100g)
Calgon 40% aqueous solution ... 1 part
Distilled water ... 60 parts
The preparation of-heat sensitive recording layer usefulness coating fluid-
Following composition is mixed, obtained the heat sensitive recording layer coating fluid.
[the heat sensitive recording layer composition of coating fluid]
Dispersion liquid A ... 60 parts
Dispersion liquid B ... 120 parts
Dispersion liquid C ... 120 parts
Dispersion liquid D-4 ... 101 parts
Zinc stearate 30% dispersion liquid ... 15 parts
Paraffin (30%) ... 15 parts
Neopelex (25%) ... 4 parts
The preparation of＜support coating liquid for undercoat layer 〉
Except using distilled water as the water, according to the embodiment 1 of the 1st embodiment beyond same composition and method, preparation support coating liquid for undercoat layer.
The manufacturing of＜thermal recording medium 〉
The good quality paper of preparing a kind of smoothness by JIS-P8119 regulation and be 150 seconds is as support, the support coating liquid for undercoat layer that on the surface of this good quality paper, obtains as stated above with the coating of scraper plate coating machine, and controlling dried coating weight is 8g/m 2Thereby, formed priming coat.By being coated with this priming coat, make the JIS-P8119 smoothness of support become 350 seconds.
Then, the heat sensitive recording layer coating fluid that on above-mentioned priming coat, obtains as stated above with the coating of curtain flow coater, controlling dried coating weight is 4g/m 2, be dried, thereby formed heat sensitive recording layer.Then, the surface that forms heat sensitive recording layer is applied calender process, thereby obtained thermal recording medium of the present invention (103).
(embodiment 91)
The preparation of-dispersion liquid E-
According to composition and the method same with the embodiment 2 of the 1st embodiment, preparation dispersion liquid E.
The preparation of-heat sensitive recording layer usefulness coating fluid-
Similarly prepare dispersion liquid A, B, C and D-4 with embodiment 90, the dispersion liquid E that obtains is as stated above mixed to prepare the heat sensitive recording layer coating fluid with following composition, and then similarly operate with embodiment 90, obtained thermal recording medium of the present invention (104).
[the temperature-sensitive chromonic layer composition of coating fluid]
Dispersion liquid A ... 60 parts
Dispersion liquid B ... 120 parts
Dispersion liquid C ... 120 parts
Dispersion liquid E ... 30 parts
Dispersion liquid D-4 ... 101 parts
Zinc stearate 30% dispersion liquid ... 15 parts
Paraffin (30%) ... 15 parts
Neopelex (25%) ... 4 parts
(embodiment 92)
Except using 1,1,3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane replace when preparation dispersion liquid E, using among the embodiment 91 1,1, butane (image stabilizing agent) in addition for 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl), all the other and embodiment 91 similarly prepare dispersion liquid E, and then similarly operate with embodiment 91, have obtained thermal recording medium of the present invention (105).
(embodiment 93)
Except using amorphous silica (ミ ズ カ ミ Le P832, marshy land chemical industry (strain) system, boil the Linseed oil oil absorption: 145ml/100g) 20 parts replace calcite class precipitated calcium carbonate (the ユ ニ バ-70 that uses among the embodiment 90 when preparation dispersion liquid D-4; Inorganic pigment) beyond 40 parts, all the other and embodiment 90 similarly operate, and have obtained thermal recording medium of the present invention (106).Should illustrate that the volume average particle size of the dispersible pigment dispersion D of present embodiment is 2.5 μ m.
(embodiment 94)
(Ha イ ジ ラ イ ト H42, clear and electrician's (strain) system are boiled the Linseed oil oil absorption: 43ml/100g) 40 parts replace calcite class precipitated calcium carbonate (the ユ ニ バ-70 that uses among the embodiment 90 when preparing dispersion liquid D-4 except using aluminium hydroxide; Inorganic pigment) beyond 40 parts, all the other and embodiment 90 similarly operate, and have obtained thermal recording medium of the present invention (107).Should illustrate that the volume average particle size of the dispersible pigment dispersion D-4 of present embodiment is 0.8 μ m.
(embodiment 95)
Except using sulfo group modified polyvinylalcohol (go-セ ラ Application L3266, Japan's synthetic chemistry (strain) system) polyvinyl alcohol 2.5% aqueous solution (adhesive) that uses when preparation dispersion liquid A, B and C among 2.5% aqueous solution replacement embodiment 90 in addition, all the other and embodiment 90 similarly operate, and have obtained thermal recording medium of the present invention (108).
(embodiment 96)
Except polyvinyl alcohol 2.5% aqueous solution (adhesive) that uses when preparing dispersion liquid A, B and C among the embodiment 90 is changed into diacetone modified polyvinylalcohol (D500, ユ ニ チ カ society system) 2.5% aqueous solution, and dispersion liquid A, B and the C that will so change the back acquisition similarly mix with embodiment 90, obtain the heat sensitive recording layer coating fluid, and then in this coating fluid, add beyond 13 parts of adipic dihydrazide 5% aqueous solution (crosslinking agent), all the other and embodiment 90 similarly operate, and have obtained thermal recording medium of the present invention (109).
(embodiment 97)
Except polyvinyl alcohol 2.5% aqueous solution (adhesive) that uses when preparing dispersion liquid A, B and C among the embodiment 90 is changed into acetoacetyl modified polyvinylalcohol (go-セ Off ア イ マ-Z210; Japan's synthetic chemistry (strain) system) 2.5% aqueous solution; and dispersion liquid A, B and the C that will so change the back acquisition mix similarly to Example 30; obtain the heat sensitive recording layer coating fluid; and then in this coating fluid, add beyond 13 parts of glyoxal 5% aqueous solution (crosslinking agent); all the other and embodiment 90 similarly operate, and have obtained thermal recording medium of the present invention (110).
(embodiment 98)
A kind of by old paper stock 70% except using, LBKP 30% formation and JIS-P8119 smoothness are 170 seconds recycled writing paper (50g/m 2) beyond the good quality paper that replaces using as support among the embodiment 90, all the other and embodiment 90 similarly operate, and have obtained thermal recording medium of the present invention (111).
(embodiment 99)
Embodiment 90＜manufacturing of thermal recording medium in; after forming priming coat on the support; do not carry out coating, drying and the calender process of heat sensitive recording layer with coating fluid; replace and after forming priming coat, use the curtain flow coater that the heat sensitive recording layer that obtains in embodiment 90 is carried out lamination coating simultaneously, drying, carries out calender process on the surface of the protective layer of lamination with coating fluid with by the following protective layer used coating fluid that constitutes; in addition; similarly operate with embodiment 90, obtained thermal recording medium of the present invention (112).Should illustrate that the drying coated amount of protective layer is 2.0g/m 2
The preparation of-protective layer used coating fluid-
According to the embodiment 10 of the 1st embodiment in same composition and the method for protective layer used coating fluid, prepare protective layer used coating fluid.
(embodiment 100～102)
Use aluminium hydroxide (Ha イ ジ ラ イ ト H43 respectively, volume average particle size 0.7 μ m, clear and electrician's (strain) system) 40 parts, kaolin (カ オ Block ラ イ ト, volume average particle size 2.5 μ m, Bai Shigong industry (strain) system) 40 parts or amorphous silica (ミ ズ カ シ Le P707, volume average particle size 2.2 μ m, marshy land chemistry (strain) system) 20 parts replace aluminium hydroxide (the Ha イ ジ ラ イ ト H42 that uses among the embodiment 99 when the protective layer used coating fluid of preparation; Inorganic pigment) 40 parts, in addition, similarly operate with embodiment 99, obtained thermal recording medium of the present invention (113)～(115).
(embodiment 103～109)
Use oxalic acid dimethylbenzyl ester (HS3520R-N respectively, big Japanese ink industry (strain) system), a terphenyl, ethylene glycol 4-tolyl ether, to benzylbiphenyl, 1,2-hexichol oxygen ylmethyl benzene, diphenyl sulphone (DPS) or 1, the 2-benzyloxy naphthalene (sensitizer) that when preparation dispersion liquid C, uses among the 2-biphenoxyl ethane replacement embodiment 90, in addition, similarly operate with embodiment 90, obtained thermal recording medium of the present invention (116)～(122).
(embodiment 110～114)
Use 2-anilino--3-methyl-6-dibutylamino fluorane respectively, 2-anilino--3-methyl-6-(N-ethyl-N-isoamylamino) fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-third amino) fluorane, 2-anilino--3-methyl-6-two pentylamine base fluoranes, or the 2-anilino--3-methyl-6-lignocaine fluorane (electron donability leuco dye) that when preparation dispersion liquid A, uses among 2-anilino--3-methyl-6-(N-ethyl-N-p-methylphenyl amino) fluorane replacement embodiment 90, in addition, similarly operate with embodiment 90, obtained thermal recording medium of the present invention (123)～(127).
(embodiment 115)
The curtain flow coater that uses when being coated with heat sensitive recording layer with coating fluid in using air knife doctor knife coater replacement embodiment 90, all the other and embodiment 90 similarly operate, and have obtained thermal recording medium of the present invention (128).
(embodiment 116～119)
Use N-benzyl-4-hydroxy benzene sulfonamide (=right-N-benzyl sulfonamides phenol), BTUM, 4-hydroxyl-4 '-isopropoxy diphenyl sulphone (DPS) or 2 respectively; the 4-hydroxy benzenes sulfonanilide (electronic acceptance compound) that when preparation dispersion liquid B, uses among two (phenyl sulfonyl) phenol replacement of the 4-embodiment 90; in addition; similarly operate with embodiment 90, obtained thermal recording medium of the present invention (128)～(132).
(comparative example 14)
40 parts of calcite class precipitated calcium carbonates that uses in the dispersible pigment dispersion D-4 with embodiment 90 are changed into aluminium hydroxide and (are boiled the Linseed oil oil absorption: 22ml/100g) 40 parts, all the other and embodiment 90 similarly operate, and have obtained to be used for the thermal recording medium (133) of comparison.Should illustrate that the volume average particle size of the dispersible pigment dispersion D-4 of this comparative example is 4.0 μ m.
(comparative example 15)
40 parts of calcite class precipitated calcium carbonates that uses in the dispersible pigment dispersion D-4 with embodiment 90 are changed into amorphous silica and (are boiled the Linseed oil oil absorption: 210m1/100g) 40 parts, all the other and embodiment 90 similarly operate, and have obtained to be used for the thermal recording medium (134) of comparison.Should illustrate that the volume average particle size of the dispersible pigment dispersion D-4 of this comparative example is 2.4 μ m.
(evaluation)
Carry out following mensuration and evaluation for thermal recording medium of the present invention (103)～(132) of above-mentioned acquisition and thermal recording medium (133)～(134) that are used for comparison.Should illustrate that measures and estimate the results are shown in the following table 1.
(1) mensuration of sensitivity
According to the embodiment of the 1st embodiment in the same method of evaluation, the mensuration of carrying out sensitivity.
(2) thermal head pollutes
Observe the surface of the thermal head that uses in the above-mentioned sensitivity determination and the recording quality of thermal recording medium, estimate according to following benchmark.
Zero: do not find on the thermal head to pollute the no abnormal sense of recording quality
△: though find a point pollution is arranged a little, the no abnormal sense of recording quality on the thermal head
*: find on the thermal head to pollute, also have pollutant to adhere on the recording materials
(3) plasticizer resistance properties
Make each thermal recording medium and 1 vinyl chloride resin packaging film (the Port リ マ of SHIN-ETSU HANTOTAI one system of lettering under the condition of above-mentioned (1), Port リ マ ラ Star プ 300) state that fits tightly, after under 25 ℃, the environmental condition of 50%RH, placing 24 hours, measure image color (concentration after the placement) with Macbeath reflection of the concentration (RD-918).In addition, be determined at the image color that is next under the condition identical after the lettering with above-mentioned (1).Calculate the ratio (plasticizer storage rate) of the two.Should illustrate that numerical value is high more, the presentation video keeping quality is good more.
Plasticizer storage rate=[(image color after placing under these conditions)/(image color that records immediately behind the lettering)] * 100
(4) evaluation of background fog
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out the evaluation of background fog.
(5) the conservatory evaluation of image
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out the conservatory evaluation of image.
(6) evaluation of resistance to chemical reagents
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out the evaluation of resistance to chemical reagents.
(7) evaluation of thermal head breakage
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out the evaluation of thermal head breakage.
(8) the adaptive evaluation of ink-jet
1. oil resistant China ink
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out the evaluation of oil resistant China ink.
2. ink mist recording adaptability
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out the adaptive evaluation of ink mist recording.
(9) measurement of contact angle
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out measurement of contact angle.
(10) ion (Na +, K +) mensuration of concentration
According to the embodiment of the 1st embodiment in the same method of evaluation, carry out the mensuration of ion concentration.
Table 4
Thermal recording medium Image color (sensitivity) Head pollutes Anti-plasticity The image keeping quality Background fog concentration Resistance to chemical reagents The thermal head breakage Ink-jet adaptability Contact angle [°] Ion concentration [ppm]
Printing ink patience Ink mist recording adaptability
Embodiment 90 ????(103) ??1.28 ??○ ??75％ ??95％ ??0.09 ??○ 0 ??90％ ??○ ??51 ?780
Embodiment 91 ????(104) ??1.27 ??○ ??78％ ??98％ ??0.10 ??○ 0 ??93％ ??○ ??55 ?800
Embodiment 92 ????(105) ??1.26 ??○ ??77％ ??97％ ??0.10 ??○ 0 ??92％ ??○ ??53 ?800
Embodiment 93 ????(106) ??1.26 ??○ ??70％ ??93％ ??0.10 ??○ 0 ??88％ ??○ ??50 ?770
Embodiment 94 ????(107) ??1.27 ??○ ??76％ ??96％ ??0.09 ??○ 0 ??91％ ??○ ??55 ?790
Embodiment 95 ????(108) ??1.30 ??○ ??75％ ??96％ ??0.08 ??○ 0 ??93％ ??○ ??50 ?800
Embodiment 96 ????(109) ??1.29 ??○ ??77％ ??97％ ??0.08 ??○ 0 ??92％ ??○ ??52 ?800
Embodiment 97 ????(110) ??1.28 ??○ ??76％ ??95％ ??0.08 ??○ 0 ??93％ ??○ ??55 ?790
Embodiment 98 ????(111) ??1.28 ??○ ??76％ ??94％ ??0.09 ??○ 0 ??93％ ??○ ??60 ?800
Embodiment 99 ????(112) ??1.23 ??○ ??80％ ??98％ ??0.09 ??○ 0 ??98％ ??○ ??45 ?800
Embodiment 100 ????(113) ??1.22 ??○ ??85％ ??97％ ??0.09 ??○ 0 ??97％ ??○ ??42 ?800
Embodiment 101 ????(114) ??1.21 ??○ ??87％ ??98％ ??0.10 ??○ 0 ??98％ ??○ ??48 ?790
Embodiment 102 ????(115) ??1.20 ??○ ??77％ ??96％ ??0.10 ??○ 0 ??92％ ??○ ??35 ?800
Embodiment 103 ????(116) ??1.27 ??○ ??73％ ??94％ ??0.09 ??○ 0 ??89％ ??○ ??50 ?790
Embodiment 104 ????(117) ??1.26 ??○ ??74％ ??95％ ??0.10 ??○ 0 ??91％ ??○ ??51 ?800
Embodiment 105 ????(118) ??1.28 ??○ ??76％ ??94％ ??0.09 ??○ 0 ??92％ ??○ ??51 ?790
Embodiment 106 ????(119) ??1.24 ??○ ??72％ ??91％ ??0.10 ??○ 0 ??89％ ??○ ??50 ?800
Embodiment 107 ????(120) ??1.26 ??○ ??74％ ??95％ ??0.10 ??○ 0 ??91％ ??○ ??52 ?790
Embodiment 108 ????(121) ??1.28 ??○ ??72％ ??93％ ??0.09 ??○ 0 ??89％ ??○ ??51 ?800
Embodiment 109 ????(122) ??1.25 ??○ ??70％ ??92％ ??0.09 ??○ 0 ??91％ ??○ ??50 ?790
Embodiment 110 ????(123) ??1.28 ??○ ??80％ ??97％ ??0.10 ??○ 0 ??93％ ??○ ??55 ?790
Embodiment 111 ????(124) ??1.26 ??○ ??78％ ??95％ ??0.10 ??○ 0 ??88％ ??○ ??55 ?780
Embodiment 112 ????(125) ??1.26 ??○ ??77％ ??92％ ??0.10 ??○ 0 ??87％ ??○ ??55 ?790
Embodiment 113 ????(126) ??1.28 ??○ ??78％ ??95％ ??0.10 ??○ 0 ??91％ ??○ ??51 ?790
Embodiment 114 ????(127) ??1.24 ??○ ??68％ ??88％ ??0.08 ??○ 0 ??85％ ??○ ??50 ?780
Embodiment 115 ????(128 ??1.26 ??○ ??74％ ??93％ ??0.10 ??○ 0 ??90％ ??○ ??52 ?780
Embodiment 116 ????(129) ??1.20 ??○ ??65％ ??65％ ??0.09 ??△ 0 ??80％ ??△ ??55 ?760
Embodiment 117 ????(130) ??1.22 ??○ ??65％ ??98％ ??0.12 ??○ 0 ??92％ ??○ ??50 ?800
Embodiment 118 ????(131) ??1.26 ??○ ??60％ ??91％ ??0.07 ??○ 0 ??93％ ??○ ??52 ?780
Embodiment 119 ????(132) ??1.26 ??○ ??65％ ??98％ ??0.11 ??○ 0 ??96％ ??○ ??51 ?790
Comparative example 14 ????(133) ??1.15 ??△ ??70％ ??89％ ??0.09 ??○ 0 ??85％ ??○ ??50 ?780
Comparative example 15 ????(134) ??1.03 ??○ ??72％ ??75％ ??0.10 ??○ 0 ??75％ ??○ ??40 ?800
From the result of above-mentioned table 4 as can be seen, thermal recording medium of the present invention (103)～(132) are because the electronic acceptance compound that contains the electron donability leuco dye simultaneously and represented by general formula (1), and be 30～200ml/100g to the oil absorption of boiling Linseed oil, and contain the pigment that volume average particle size is 0.5～3 μ m, therefore, particularly can be when keeping low background fog, obtain high color development concentration (high sensitivity) (print adaptability is good), image keeping quality after print is also good, follow the raising of contact angle and have ink-jet adaptability, also has good resistance to chemical reagents, plasticizer resistance properties, and the wearing and tearing of thermal head are few when the high speed lettering, and are also good aspect the matching of thermal head.That is, can satisfy high sensitivityization and background white, image keeping quality, ink-jet adaptability, resistance to chemical reagents and thermal head matching (mar proof) simultaneously.
In addition, with the contrast of thermal recording medium (103) in, for the thermal recording medium that contains image stabilizing agent (104) and (105), can further improve image keeping quality and oil resistant China ink; For the thermal recording medium (108) that uses preferred adhesive (protecting colloid), can seek the reduction of further high sensitivityization and background fog.In addition, by containing image stabilizing agent, make affix one's seal adaptability and operability also good especially.In the 4th embodiment of the present invention,, can further improve image keeping quality and oil resistant China ink (resistance to chemical reagents) for the thermal recording medium that is provided with the protective layer that contains suitable specific inorganic pigment (112)～(115).Even if use the sensitizer that in embodiment 103～109, uses, also can obtain and the same good performance of the thermal recording medium (103) of embodiment 90; Even if use the electron donability leuco dye that in embodiment 110～114, uses, also background fog can be kept low level, can also obtain good color emissivity and image keeping quality simultaneously.As embodiment 90 and 115, adopt curtain stream rubbing method useful aspect high sensitivityization.In addition, even if in support, contain the occasion (embodiment 98) of old paper stock, various performances are not brought adverse effect yet.
On the other hand, use to the oil absorption of boiling Linseed oil not the pigment in 30～200ml/100g scope relatively use thermal recording medium (133), (134), can not satisfy simultaneously that thermal head pollutes and various performances such as image keeping quality.
                          Industrial applicibility
According to the present invention, a kind of like this thermal recording medium can be provided, this thermal recording medium particularly distortion of its bead-like is little, can record in high quality and carry, can be suppressed to the photographic fog concentration (background fog) of background part low-level, can form high sensitivity and be the image (print adaptability is good) of high concentration, Image Saving, resistance to chemical reagents after the print are good, can not follow the image fade that the color and luster that ink jet image occurs is bad or ooze profit and caused by ink for inking, namely has ink-jet adaptability, and, even if having the occasion of high-performance printer of the thermal head of parts of fine crack structtire being used for high-speed printer or outfit, the matching of thermal head is also good, and the wearing and tearing of thermal head and the pollution of thermal head be less (the thermal head adaptability when the high speed lettering is good) all.
In addition; a kind of like this thermal recording medium can also be provided; this thermal recording medium is on the basis of above-mentioned advantage; can also obtain the image of distinct high image quality; the light resistance that has formed image is good, can be on heat sensitive recording layer or protective layer do not ooze profit printing, affix one's seal etc., can and form at low cost image by few coating weight (environmental suitability); the sensation that also can have as required, the common paper of resembling.

Claims (28)

1. thermal recording medium possesses on support and contains electron donability leuco dye and the heat sensitive recording layer by the electronic acceptance compound of color development with this electron donability leuco dye reaction, it is characterized in that,
Above-mentioned electronic acceptance compound is the compound by following general formula (1) expression, and the maximum of height of flange is below 5.0mm,
R 1-Ph-SO 2R 2General formula (1)
(in the formula, R 1Expression hydroxyl, alkyl.R 2Expression-Ph ,-NH-Ph ,-Ph-OH ,-NH-CO-NH-Ph.Ph represents phenyl, also can be contained-SO 2R 2Substituting group replace).
2. thermal recording medium as claimed in claim 1 wherein, is coated with heat sensitive recording layer, the drying coated quantity not sufficient 6g/cm after the coating 2
3. thermal recording medium as claimed in claim 1 or 2, wherein, the compound of being represented by general formula (1) is a 4-hydroxy benzenes sulfonanilide.
As above-mentioned claim 1～3 in each described thermal recording medium, wherein, Na +Ion and K +The total ion concentration of ion is below 1500ppm.
5. as each the described thermal recording medium in the right 1～4, wherein, after the distilled water that on the surface of heat sensitive recording layer, drips through the contact angle after 0.1 second more than 20 °.
6. as each the described thermal recording medium in the claim 1～5, wherein, heat sensitive recording layer contains sensitizer, and this sensitizer be selected from 2-benzyloxy naphthalene, oxalic acid dimethylbenzyl ester, a terphenyl, ethylene glycol 4-tolyl ether at least, to benzylbiphenyl, 1,2-hexichol oxygen ylmethyl benzene, 1, a kind of in 2-biphenoxyl ethane and the diphenyl sulphone (DPS).
7. as each the described thermal recording medium in the claim 1～6, wherein, the electron donability leuco dye is to be selected from a kind of in 2-anilino--3-methyl-6-lignocaine fluorane, 2-anilino--3-methyl-6-dibutylamino fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-isoamylamino) fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-third amino) fluorane, 2-anilino--3-methyl-6-two pentylamine base fluoranes and 2-anilino--3-methyl-6-(N-ethyl-N-p-methylphenyl amino) fluorane at least.
8. as each the described thermal recording medium in the claim 1～7, wherein, the one deck at least on the support is to form by the coating of curtain stream rubbing method.
9. thermal recording medium possesses on support and contains electron donability leuco dye and the heat sensitive recording layer by the electronic acceptance compound of color development with this electron donability leuco dye reaction, it is characterized in that,
Above-mentioned electronic acceptance compound is the compound by following general formula (1) expression:
R 1-Ph-SO 2R 2General formula (1)
(in the formula, R 1Expression hydroxyl, alkyl.R 2Expression-Ph ,-NH-Ph ,-Ph-OR 3,-NH-CO-NH-Ph.R 3The expression alkyl.Ph represents phenyl, also can be contained-SO 2R 2Substituting group replace),
And, from the side with heat sensitive recording layer of described support by applying 15.2mJ/mm 2Energy carry out image color that the hot stamping phase time obtains more than 1.20.
10. thermal recording medium as claimed in claim 9 wherein, is coated with heat sensitive recording layer, the drying coated quantity not sufficient 6g/cm after the coating 2
11. as claim 9 or 10 described thermal recording mediums, wherein, the compound of being represented by general formula (1) is a 4-hydroxy benzenes sulfonanilide.
12. as each the described thermal recording medium in the claim 9～11, wherein, heat sensitive recording layer contains sensitizer, and this sensitizer be selected from 2-benzyloxy naphthalene, oxalic acid dimethylbenzyl ester, a terphenyl, ethylene glycol 4-tolyl ether at least, to benzylbiphenyl, 1,2-hexichol oxygen ylmethyl benzene, 1, a kind of in 2-biphenoxyl ethane and the diphenyl sulphone (DPS).
13. as each the described thermal recording medium in the claim 9～12, wherein, the electron donability leuco dye is to be selected from a kind of in 2-anilino--3-methyl-6-lignocaine fluorane, 2-anilino--3-methyl-6-dibutylamino fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-isoamylamino) fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-third amino) fluorane, 2-anilino--3-methyl-6-two pentylamine base fluoranes and 2-anilino--3-methyl-6-(N-ethyl-N-p-methylphenyl amino) fluorane at least.
14. as each the described thermal recording medium in the claim 9～13, wherein, the one deck at least on the support is to form by the coating of curtain stream rubbing method.
15. a thermal recording medium possesses on support and contains electron donability leuco dye and the heat sensitive recording layer by the electronic acceptance compound of color development with the reaction of this electron donability leuco dye, it is characterized in that,
Applying 15.2mJ/mm 2The image color that obtains when carrying out print of energy by thermal head more than 1.20,
And in the most surperficial and dorsal part with table side of the above-mentioned heat sensitive recording layer of one deck at least the most surperficial confficient of static friction and the scope of the coefficient of kinetic friction during in friction 0.2～0.5.
16. thermal recording medium as claimed in claim 15, wherein, electronic acceptance compound is the compound by following general formula (1) expression:
R 1-Ph-SO 2R 2General formula (1)
(in the formula, R 1Expression hydroxyl, alkyl, R 2Expression-Ph ,-NH-Ph ,-Ph-OR 3,-NH-CO-NH-Ph, R 3The expression alkyl.Ph represents phenyl, also can be contained-SO 2R 2Substituting group replace).
17. as claim 15 or 16 described thermal recording mediums, wherein, the compound of being represented by general formula (1) is a 4-hydroxy benzenes sulfonanilide.
18. as each the described thermal recording medium in the claim 15～17, wherein, support contains old paper stock.
19. as each the described thermal recording medium in the claim 15～18, wherein, Na +Ion and K +The total ion concentration of ion is below 1500ppm.
20. as each the described thermal recording medium in the claim 15～19, wherein, heat sensitive recording layer contains sensitizer, and this sensitizer be selected from 2-benzyloxy naphthalene, oxalic acid dimethylbenzyl ester, a terphenyl, ethylene glycol 4-tolyl ether at least, to benzylbiphenyl, 1,2-hexichol oxygen ylmethyl benzene, diphenyl sulphone (DPS) and 1, a kind of in the 2-biphenoxyl ethane.
21. as each the described thermal recording medium in the claim 15～20, wherein, the electron donability leuco dye is to be selected from a kind of in 2-anilino--3-methyl-6-lignocaine fluorane, 2-anilino--3-methyl-6-dibutylamino fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-isoamylamino) fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-third amino) fluorane, 2-anilino--3-methyl-6-two pentylamine base fluoranes and 2-anilino--3-methyl-6-(N-ethyl-N-p-methylphenyl amino) fluorane at least.
22. as each the described thermal recording medium in the claim 15～21, wherein, the one deck at least on the support is to form by the coating of curtain stream rubbing method.
23. thermal recording medium, on support, possess contain the electron donability leuco dye, by the electronic acceptance compound of color development and the heat sensitive recording layer of pigment with the reaction of this electron donability leuco dye, it is characterized in that, above-mentioned pigment is 30～200ml/100g to the oil absorption of boiling Linseed oil, volume average particle size is 0.5～3 μ m, and can use in the tape deck that carries out the hot stamping word by the speed more than the per second 10cm.
24. thermal recording medium as claimed in claim 23, wherein, electronic acceptance compound is the compound by following general formula (1) expression:
R 1-Ph-SO 2R 2General formula (1)
(in the formula, R 1Expression hydroxyl, alkyl, R 2Expression-Ph ,-NH-Ph ,-Ph-OR 3,-NH-CO-NH-Ph, R 3The expression alkyl, Ph represents phenyl, also can be contained-SO 2R 2Substituting group replace).
25. thermal recording medium as claimed in claim 24, wherein, the compound of being represented by general formula (1) is a 4-hydroxy benzenes sulfonanilide.
26. as each the described thermal recording medium in the claim 23～25, wherein, above-mentioned pigment is to be selected from a kind of in calcite class (lightweight) calcium carbonate, amorphous silica and the aluminium hydroxide at least.
27. as each the described thermal recording medium in the claim 23～26, wherein, heat sensitive recording layer contains sensitizer, and this sensitizer be selected from 2-benzyloxy naphthalene, oxalic acid dimethylbenzyl ester, a terphenyl, ethylene glycol 4-tolyl ether at least, to benzylbiphenyl, 1,2-hexichol oxygen ylmethyl benzene, diphenyl sulphone (DPS) and 1, a kind of in the 2-biphenoxyl ethane.
28. as each the described thermal recording medium in the claim 23～27, wherein, the electron donability leuco dye is to be selected from a kind of in 2-anilino--3-methyl-6-lignocaine fluorane, 2-anilino--3-methyl-6-dibutylamino fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-isoamylamino) fluorane, 2-anilino--3-methyl-6-(N-ethyl-N-third amino) fluorane, 2-anilino--3-methyl-6-two pentylamine base fluoranes and 2-anilino--3-methyl-6-(N-ethyl-N-p-methylphenyl amino) fluorane at least.
CNA028258002A 2001-12-20 2002-12-20 Heat-sensitive recording material Pending CN1606508A (en)

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JP387597/2001 2001-12-20
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JP2001387677A JP2003182228A (en) 2001-12-20 2001-12-20 Thermal recording method
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