CN104972780A - Thermosensitive recording material - Google Patents
Thermosensitive recording material Download PDFInfo
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- CN104972780A CN104972780A CN201510277560.6A CN201510277560A CN104972780A CN 104972780 A CN104972780 A CN 104972780A CN 201510277560 A CN201510277560 A CN 201510277560A CN 104972780 A CN104972780 A CN 104972780A
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- phenol
- benzenesulfonyl
- recording medium
- thermal recording
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Abstract
The invention discloses a thermosensitive recording material. The thermosensitive recording material comprises base paper. The base paper is coated with a bottom coating, the bottom coating is coated with a thermosensitive developing layer, the thermosensitive developing layer comprises dye and a developing agent, and the developing agent is composed of 2,4-diphenyl sulfonyl phenol, 4-benzenesulfonyl phenol and 2,4,6-triphenyl sulfonyl phenol. The 2,4-diphenyl sulfonyl phenol, the 4-benzenesulfonyl phenol and the 2,4,6-triphenyl sulfonyl phenol are used in cooperation in the developing agent, production cost is reduced, thermosensitivity is greatly enhanced, background decoloration is lower, and image storage stability is better.
Description
Technical field
The present invention relates to a kind of thermal recording medium.
Background technology
Up to now, many thermal recording mediums are proposed, its heat-sensitive color layer (color developing layer) mainly comprises leuco dye and developer (developer), and by one or both heating and meltings in dyestuff or developer and make both contact produce chemical reaction, thus obtain develop the color recording materials.These thermal recording mediums have the following advantages: (1) need not carry out the process as image developing or fixing complexity, makes it possible to the record being carried out the short time by better simply device; (2) level producing noise is low; (3) machine is relatively more cheap, and cost is low etc., is widely used in the logger field, automatic machine field, thermal photography type TAG field etc. of the printer field in facsimile machine field, computer export, electronic calculator etc., medical science mensuration.
As thermal recording medium, need such material, this material can carry out high density colour developing fast, and can give the image and background that have developed the color with fastness.In the last few years, such thermal recording medium was by through being usually used in recording the very important field of fidelity of image, as label; Especially, need such thermal recording medium, this thermal recording medium provides the high stability to the plasticizer in the organic polymer material be contained in for packing and oils.
EP0706997A1 and JP8269000A is to the synthesis of 2,4-dibenzenesulfonyl phenol with should be used as a little explanation, but synthesis cost is high and thermo-responsive sensitivity is low, and the shortcoming of background decolouring easily produces.
Summary of the invention
Technical problem to be solved by this invention is to provide the thermal recording medium that the decolouring of a kind of background is little, image storage is stable.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A kind of thermal recording medium, comprises base paper, base paper is coated with priming coat; priming coat is coated with heat-sensitive color layer, and heat-sensitive color layer comprises dyestuff and developer, and developer is by 2; 4-dibenzenesulfonyl phenol, 4-benzenesulfonyl phenol and 2,4,6-tri-benzenesulfonyl phenol form.
Described developer is made up of 2,4,6-tri-benzenesulfonyl phenol of 2,4-dibenzenesulfonyl phenol of 65-95 mass parts, the 4-benzenesulfonyl phenol of 2-25 mass parts and 0.1-10 mass parts.
As preferably, described developer is made up of 2,4,6-tri-benzenesulfonyl phenol of 2,4-dibenzenesulfonyl phenol of 80-95 mass parts, the 4-benzenesulfonyl phenol of 3-15 mass parts and 0.5-5 mass parts.
Described dyestuff is fluorane compounds or spiro-pyrans compounds.
Compared with prior art; advantage of the present invention is: the present invention adopts 2; 4-dibenzenesulfonyl phenol, 4-benzenesulfonyl phenol and 2; 4; 6-tri-benzenesulfonyl phenol three kinds of developers with the use of, reduce production cost, simultaneously thermo-responsive sensitivity strengthens greatly; background decolouring is less, and image storage stability is better.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Fig. 1 is the thermo-responsive Sensitivity comparison curve map of the embodiment of the present invention 2 to 5.
Detailed description of the invention:
A kind of thermal recording medium, comprises base paper, base paper is coated with priming coat; priming coat is coated with heat-sensitive color layer, and heat-sensitive color layer comprises dyestuff and developer, and developer is by 2; 4-dibenzenesulfonyl phenol, 4-benzenesulfonyl phenol and 2,4,6-tri-benzenesulfonyl phenol form.
Dyestuff in the present invention is selected from fluorane compounds or spiro-pyrans compounds, the former has from yellow, orange, red in the different form and aspect such as green, black, have the advantages that the light resistance of tone, resistance to water etc. are all good, mainly contain 2-anilino--3-methyl-6-dibutylamino fluorane etc.; The latter, except color developing, causes photochromism because photoinduction produces hydrocarbon control fracture in addition, as 3-methylspiro dinaphthopyran, 4,4-two dimethylaminophenyl benzhydryl benzylic ethers etc.
For sensitizer, itself have lower fusing point and melting heat, therefore it is the fusing point depressant of heat sensitive dye and colour developing chaste tree mixture.It and dyestuff, developer form eutectic mixture, have eutectic point, thus when striking, thermal effect record-paper color development temperature are reduced, and improve color development sensitivity, mainly contain beta naphthal benzylic ether etc.
For filler, such as name kind china clay, calcium carbonate, magnesia, aluminium oxide, magnesium hydroxide and aluminium, silicate etc.
For antioxidant and stabilizing agent, can be used in combination with general developer, can prevent picture and text from occurring ghost image, improve fast light, water-fast, resistance to plasticizer, the resistance to wet goods character of quality picture, improve the background color of heat-sensitive paper and the keeping quality of picture and text, mainly contain hindered phenol, zinc acrylate resin, zinc stearate, epoxide, terephalic acid dibenzoyl etc.
For lubricant, prevent sticking together phenomenon and improving printability of electrothermal sensitive recording paper and heating head during in order to record, the coefficient of friction of heat-sensitive paper must reduce, and lubricant made by main use lead stearate and metallic soap.
For pressure color-former preventing agent, the flatness of heat-sensitive paper has a significant impact color development sensitivity, in order to obtain high sensitivity, needs to carry out press polish process to heat-sensitive paper, improves smoothness.But background color color development may be made due to pressure dependence during press polish.Because being employed herein pressure color-former preventing agent, particularly during highly sensitive heat-sensitive paper press polish, line pressure needs height.So pressure color-former preventing agent is essential.The large material of crystallization energy when press polish process can effectively absorption pressure light time heating.Wax class is representational pressure color-former preventing agent, and the paraffin good with the compatibility such as leuco dye, developer is effective especially.When manufacturing record-paper in order to improve production capacity, can add the additive of surfactant, dispersant defoamer and so on, they also play important effect respectively.
Embodiment 1
Prepared by developer:
Phenol 200 kg is added reactor, adds the FeCl of 2-8 kg simultaneously
3, be slowly warmed up to 50-100 DEG C, add benzene sulfonyl chloride 450 kg, slowly drip, 2.5 hours used times, add insulation 1 hour; Slowly be warmed up to 150 DEG C, be incubated 8 hours, be cooled to 100 DEG C; Slow dropping 10% sodium hydroxide solution 1110kg, after adding liquid caustic soda, temperature slowly drops to 95 DEG C, press filtration after 2 hours, and mother liquor is put into acid out still, and filtrate, at 90 DEG C, drips the sulfuric acid of 10%, and rate of addition wants slow, after crystallize out, is incubated 30 minutes; Acid adding, PH controls at 5-6, temperature about 50 DEG C centrifugal, washing 3 times, dry to obtain 700 kg developer finished products.
Get 100kg product and carry out HPLC analysis, HPLC analysis condition is:
Analytical column: Diamonsil II chromatographic column (4.6mm*20cm)
Mobile phase: 50% acetonitrile/water+10 acetic acid
Flow velocity: 0.8ml/min
Column temperature: 35 DEG C
Detector: UV 254nm
In the above conditions, what within about 4.95 minutes, go out peak is 2,4-dibenzenesulfonyl phenol, and what within about 3.98 minutes, go out peak is 4-benzenesulfonyl phenol, and what within about 6.22 minutes, go out peak is 2,4,6-tri-benzenesulfonyl phenol.
HPLC analysis result shows: 2,4-dibenzenesulfonyl phenol contains 91.1kg, and 4-benzenesulfonyl phenol contains 3.83kg, and 2,4,6-tri-benzenesulfonyl phenol contains 2.1kg.
Embodiment 2
Prepared by priming coat:
By mixing component below, being applied over Substance is 60g/m
2base paper on, for 5g/m after making drying
2, and carry out drying, obtain the base paper imposing priming coat:
Calcined kaolin 80 kg;
Plasticity small hollow bead 20 kg;
Aqueous sodium polyacrylate 1 kg of 40%;
Phenylethylene/butadiene latex 15 kg of 50%;
Polyvinyl alcohol water solution 50 kg of 10%;
Water 200 kg.
Prepared by heat-sensitive color layer:
(1) dispersion A: the composition disperseing below by sand mill, until average grain diameter is 0.5 μm:
2-anilino--3-methyl-6-dibutylamino fluorane (OBD-2) 20 kg;
10% polyvinyl alcohol water solution 30 kg;
Water 50 kg.
(2) dispersion B: the composition disperseing below by sand mill, until average grain diameter is 1.0 μm:
Developer finished product 30 kg that embodiment 1 obtains;
10% polyvinyl alcohol water solution 30 kg;
Water 40 kg.
(3) dispersion C: the composition disperseing below by sand mill, until average grain diameter is 1.0 μm.
Beta naphthal benzylic ether 30 kg;
10% polyvinyl alcohol water solution 30 kg;
Water 40 kg.
(4) by mixing composition below, be applied on priming coat, 4.5g/m after making drying
2, and carry out drying, obtain thermal recording medium of the present invention:
Dispersion A:15 kg;
Dispersion B:25 kg;
Dispersion C:20 kg;
50% calcined kaolin 20 kg;
10% polyvinyl alcohol water solution 20 kg.
Embodiment 3
Prepare thermal recording medium according to the mode identical with embodiment 2, the developer finished product just embodiment 1 obtained changes 2,4-dibenzenesulfonyl phenol into.
Embodiment 4
Prepare the thermal recording medium of embodiment 4 according to the mode identical with embodiment 2, the developer finished product just embodiment 1 obtained changes 4 hydroxyls-4 into '-isopropoxy diphenyl sulphone (DPS).
Embodiment 5
Prepare the thermal recording medium of embodiment 5 according to the mode identical with embodiment 2, just change the reagent composition that embodiment 1 obtains into 4,4 '-dihydroxydiphenylsulisomer.
To thermal recording medium obtained in embodiment 2 to embodiment 5, measure its physical property, as shown in table 1 below:
Table 1
Wherein, oil preventing performance uses thermal response tester, with 0.42mj/dot energy printed drawings picture, image drips edible vegetable oil, blot unnecessary vegetable oil after 10s, place after 24 hours at 20 DEG C of temperature, by the optical density of X-Rite light splitting Density Measuring Instrument test pattern part;
Water resistance uses thermal response tester, with 0.42mj/dot energy printed drawings picture, is flooded after 24 hours by image air-dry in the water of 20 DEG C, by the optical density of X-Rite light splitting Density Measuring Instrument test pattern part;
Anti-alcohol performance uses thermal response tester, with 0.42mj/dot energy printed drawings picture, is that the ethanolic solution of 25% drips one and drops on image, dries air-dry, by the optical density of X-Rite light splitting Density Measuring Instrument test pattern part after 5 hours by volume fraction;
Plasticizer resistance uses thermal response tester, and with 0.42mj/dot energy printed drawings picture, on image, obtain three layers contains the vinyl chloride film of plasticizer, places 24 hours, by the optical density of X-Rite light splitting Density Measuring Instrument test pattern part under 20 DEG C of conditions;
Heat resistance uses thermal response tester, with 0.42mj/dot energy printed drawings picture, is placed 24 hours by image at 60 DEG C of temperature, by the optical density of X-Rite light splitting Density Measuring Instrument test pattern part and blank sheet of paper part;
Moisture resistance properties uses thermal response tester, with 0.42mj/dot energy printed drawings picture, is placed 24 hours by image under 40 DEG C of temperature, 90%RH humidity, by the optical density of X-Rite light splitting Density Measuring Instrument test pattern part and blank sheet of paper part;
Light fastness uses thermal response tester, with 0.42mj/dot energy printed drawings picture, is placed 100 hours by image under 5000lx, by the optical density of X-Rite light splitting Density Measuring Instrument test pattern part and blank sheet of paper part.
Thermo-responsive sensitivity uses thermosensitive response tester (model: TH-M2/N1, OKURA DENKI manufactures), printed drawings picture on thermal recording medium, by X-Rite light splitting Density Measuring Instrument (500 series, manufactured by X-Rite company of the U.S.) density of measurement image part, as shown in Figure 1.
As can be seen from above-mentioned chart, thermal recording medium of the present invention comparatively embodiment 3-5, speed is higher, and oil preventing performance, water resistance, anti-alcohol performance, plasticizer resistance, heat resistance, moisture resistance properties and the performance of light fastness aspect are more outstanding.
Claims (4)
1. a thermal recording medium; comprise base paper; described base paper is coated with priming coat; described priming coat is coated with heat-sensitive color layer; it is characterized in that: described heat-sensitive color layer comprises dyestuff and developer, described developer is by 2,4-dibenzenesulfonyl phenol, 4-benzenesulfonyl phenol and 2; 4,6-tri-benzenesulfonyl phenol forms.
2. a kind of thermal recording medium according to claim 1; it is characterized in that: described developer is by 2 of 65-95 mass parts; the 4-benzenesulfonyl phenol of 4-dibenzenesulfonyl phenol, 2-25 mass parts and 2,4,6-tri-benzenesulfonyl phenol compositions of 0.1-10 mass parts.
3. a kind of thermal recording medium according to claim 2; it is characterized in that: described developer is by 2 of 80-95 mass parts; the 4-benzenesulfonyl phenol of 4-dibenzenesulfonyl phenol, 3-15 mass parts and 2,4,6-tri-benzenesulfonyl phenol compositions of 0.5-5 mass parts.
4. a kind of thermal recording medium according to claim 1, is characterized in that: described dyestuff is fluorane compounds or spiro-pyrans compounds.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283489A (en) * | 2019-06-06 | 2019-09-27 | 山西大学 | A kind of thermosensitive color development water suction coaster and preparation method thereof |
| CN110497709A (en) * | 2019-08-28 | 2019-11-26 | 江苏傲伦达科技实业股份有限公司 | A kind of novel thermosensitive recording materials and preparation method thereof |
| CN111619258A (en) * | 2020-05-29 | 2020-09-04 | 乐凯医疗科技有限公司 | Thermosensitive recording material and preparation method thereof |
| CN112239963A (en) * | 2019-07-17 | 2021-01-19 | 金华盛纸业（苏州工业园区）有限公司 | Thermosensitive coating and preparation method thereof, thermosensitive paper and preparation method thereof |
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| CN1297166A (en) * | 1999-11-18 | 2001-05-30 | 富士胶片株式会社 | Silver halide color photographic sensitive material and color picture forming method |
| JP2002002120A (en) * | 2000-06-23 | 2002-01-08 | Harima Chem Inc | Developer composition for heat sensitive recording paper and heat sensitive recording material |
| CN1464843A (en) * | 2001-06-01 | 2003-12-31 | 株式会社Api | Developers for thermal recording materials and thermal recording materials |
| CN101992620A (en) * | 2009-08-05 | 2011-03-30 | 株式会社理光 | Thermosensitive recording material |
| CN102433798A (en) * | 2011-09-29 | 2012-05-02 | 河南省江河纸业有限责任公司 | Method for manufacturing thermal paper capable of preventing fading of thermal paper containing organic pulp/chemical-organic pulp |
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2015
- 2015-05-27 CN CN201510277560.6A patent/CN104972780B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297166A (en) * | 1999-11-18 | 2001-05-30 | 富士胶片株式会社 | Silver halide color photographic sensitive material and color picture forming method |
| JP2002002120A (en) * | 2000-06-23 | 2002-01-08 | Harima Chem Inc | Developer composition for heat sensitive recording paper and heat sensitive recording material |
| CN1464843A (en) * | 2001-06-01 | 2003-12-31 | 株式会社Api | Developers for thermal recording materials and thermal recording materials |
| CN101992620A (en) * | 2009-08-05 | 2011-03-30 | 株式会社理光 | Thermosensitive recording material |
| CN102433798A (en) * | 2011-09-29 | 2012-05-02 | 河南省江河纸业有限责任公司 | Method for manufacturing thermal paper capable of preventing fading of thermal paper containing organic pulp/chemical-organic pulp |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283489A (en) * | 2019-06-06 | 2019-09-27 | 山西大学 | A kind of thermosensitive color development water suction coaster and preparation method thereof |
| CN112239963A (en) * | 2019-07-17 | 2021-01-19 | 金华盛纸业（苏州工业园区）有限公司 | Thermosensitive coating and preparation method thereof, thermosensitive paper and preparation method thereof |
| CN110497709A (en) * | 2019-08-28 | 2019-11-26 | 江苏傲伦达科技实业股份有限公司 | A kind of novel thermosensitive recording materials and preparation method thereof |
| CN111619258A (en) * | 2020-05-29 | 2020-09-04 | 乐凯医疗科技有限公司 | Thermosensitive recording material and preparation method thereof |
| CN111619258B (en) * | 2020-05-29 | 2021-10-19 | 乐凯医疗科技有限公司 | Thermosensitive recording material and preparation method thereof |
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| CN104972780B (en) | 2018-09-28 |
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