CN104972780B - A kind of thermal recording medium - Google Patents
A kind of thermal recording medium Download PDFInfo
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- CN104972780B CN104972780B CN201510277560.6A CN201510277560A CN104972780B CN 104972780 B CN104972780 B CN 104972780B CN 201510277560 A CN201510277560 A CN 201510277560A CN 104972780 B CN104972780 B CN 104972780B
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- phenol
- color developing
- recording medium
- thermal recording
- benzenesulfonyl
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Abstract
The invention discloses a kind of thermal recording medium, including base paper, priming coat is coated in base paper; heat-sensitive color layer is coated on priming coat, heat-sensitive color layer includes dyestuff and color developing agent, and color developing agent is by 2; 4 dibenzenesulfonyl phenol, 4 benzenesulfonyl phenol and 2,4,6 three benzenesulfonyl phenol composition.The present invention is used cooperatively using 2,4 dibenzenesulfonyl phenol, 4 benzenesulfonyl phenol and 2,4,6 three three kinds of benzenesulfonyl phenol color developing agents, reduces production cost, while thermo-responsive sensitivity greatly enhances, background decoloration smaller, and image storage stability is more preferable.
Description
Technical field
The present invention relates to a kind of thermal recording mediums.
Background technology
So far, it has been proposed that many thermal recording mediums, heat-sensitive color layer（color developing
layer）Include mainly leuco dye and color developing agent（developer）, and one or both of dyestuff or color developing agent are heated
It melts and both contact is made to generate chemical reaction, the recording materials to be developed the color.These thermal recording mediums have as follows
Advantage：（1）It need not carry out the complicated process such as image developing or fixing so that can be carried out in short-term by better simply device
Between record；（2）The level for generating noise is low；（3）Machine is relatively cheap, at low cost etc., is widely used in facsimile machine field, meter
The printer field of the output of calculation machine, electronic calculator etc., the logger field of medicine measurement, automatic machine field, heat
Quick recordable type TAG field etc..
As thermal recording medium, such material is needed, which can carry out quick high density colour developing, and energy
The image to have developed the color and background are enough assigned with fastness.In recent years, such thermal recording medium has been often used in recording
The very important field of fidelity of image, such as label；Especially, such thermal recording medium is needed, the thermal photography material
Material provides the high stability to being contained in plasticizer and oils in the organic polymer material for packaging.
A little explanations have been done in the EP0706997A1 and JP8269000A synthesis to 2,4- dibenzenesulfonyl phenol and application,
But the shortcomings that synthesis cost is high and thermo-responsive sensitivity is low, and background decolourizes easy tos produce.
Invention content
A kind of thermal photography material for small image storage stabilization of decolourizing technical problem to be solved by the invention is to provide background
Material.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of thermal recording medium, including base paper are coated with priming coat in base paper, thermosensitive color development are coated on priming coat
Layer, heat-sensitive color layer include dyestuff and color developing agent, and color developing agent is by 2,4- dibenzenesulfonyls phenol, 4- benzenesulfonyls phenol and 2, and 4,
Tri- benzenesulfonyl phenol of 6- forms.
The color developing agent is by the 2,4- dibenzenesulfonyls phenol of 65-95 mass parts, the 4- benzenesulfonyl benzene of 2-25 mass parts
Phenol and tri- benzenesulfonyl phenol of the 2,4,6- of 0.1-10 mass parts composition.
Preferably, the color developing agent is by 2, the 4- dibenzenesulfonyls phenol of 80-95 mass parts, the 4- of 3-15 mass parts
Benzenesulfonyl phenol and tri- benzenesulfonyl phenol of the 2,4,6- of 0.5-5 mass parts composition.
The dyestuff is fluorane compounds or spiro-pyrans class compound.
Compared with prior art, it is an advantage of the invention that：The present invention is using 2,4- dibenzenesulfonyls phenol, 4- benzenesulfonyls
Phenol and 2,4,6- tri- three kinds of benzenesulfonyl phenol color developing agents are used cooperatively, and reduce production cost, while thermo-responsive sensitivity
It greatly enhances, background decoloration smaller, image storage stability is more preferable.
Description of the drawings
Present invention is further described in detail with reference to the accompanying drawings and detailed description.
Fig. 1 is the thermo-responsive Sensitivity comparison curve graph of the embodiment of the present invention 2 to 5.
Specific implementation mode：
A kind of thermal recording medium, including base paper are coated with priming coat in base paper, thermosensitive color development are coated on priming coat
Layer, heat-sensitive color layer include dyestuff and color developing agent, and color developing agent is by 2,4- dibenzenesulfonyls phenol, 4- benzenesulfonyls phenol and 2, and 4,
Tri- benzenesulfonyl phenol of 6- forms.
Dyestuff in the present invention is selected from fluorane compounds or spiro-pyrans class compound, the former have from yellow, orange, it is red to
The different form and aspect such as green, black have the characteristics that light resistance, water resistance of tone etc. are good, mainly there is 2- anilino- -3- methyl -
6- dibutylamino fluoranes etc.；The latter in addition to color developing, also due to photoinduction generate hydrocarbon control be broken cause it is photochromic
Phenomenon, such as 3- methylspiros dinaphthopyran, the bis- dimethylaminophenyl benzhydryl benzylic ethers of 4,4- etc..
For sensitizer, itself there is lower fusing point and heat of fusion, therefore it is heat sensitive dye and colour developing chaste tree mixing
The fusing point depressant of object.It forms eutectic mixture with dyestuff, color developing agent, has eutectic point, thus in striking,
Make the reduction of thermal effect recording sheet color development temperature, improves color development sensitivity, mainly there is beta naphthal benzylic ether etc..
For filler, name kind china clay, calcium carbonate, magnesia, aluminium oxide, magnesium hydroxide and aluminium, silicate etc..
For antioxidant, that is, stabilizer, it can be used in mixed way with general color developing agent, can prevent picture and text from ghost image occur, improved
The properties such as fast light, water-fast, the resistance to plasticizer of quality picture, oil resistant, improve the background color of heat-sensitive paper and the keeping quality of picture and text, mainly have
Hindered phenol, zinc acrylate resin, zinc stearate, epoxide, terephalic acid dibenzoyl etc..
The sticking together phenomenon of electrothermal sensitive recording paper and heating head is prevented for lubricant, when in order to record and improves printability, heat
The friction coefficient of quick paper must reduce, and mainly make lubricant using lead stearate and metallic soap.
For pressure color-former preventing agent, the flatness of heat-sensitive paper has a significant impact to color development sensitivity, in order to obtain Gao Ling
Sensitivity needs to carry out press polish processing to heat-sensitive paper, improves smoothness.But background color may be made to send out due to pressure dependence when press polish
Color.When therefore having used pressure color-former preventing agent, the especially heat-sensitive paper press polish of high sensitivity, line pressure needs height.So pressure
Color development preventing agent is essential.Fever when the big substance of crystallization energy can effectively absorb press polish when press polish is handled.Wax class
It is representative pressure color-former preventing agent, it is especially effective with the good paraffin of compatibilities such as leuco dye, color developing agent.It is recorded in manufacture
In order to improve production capacity when paper, the additive of surfactant, dispersion Antifoam Agent etc can be added, they also rise respectively
To important role.
Embodiment 1
It is prepared by color developing agent：
Reaction kettle is added in 200 kg of phenol, while the FeCl of 2-8 kg is added3, it is slowly warming up to 50-100 DEG C, adds benzene
450 kg of sulfonic acid chloride, is slowly added dropwise, 2.5 hours used times, adds heat preservation 1 hour；150 DEG C are slowly warming up to, keeps the temperature 8 hours, drop
Temperature is to 100 DEG C；10% sodium hydroxide solution 1110kg is slowly added dropwise, after adding liquid caustic soda, temperature slowly drops to 95 DEG C, is pressed after 2 hours
Filter, mother liquor are put into acid out kettle, and 10% sulfuric acid is added dropwise at 90 DEG C in filtrate, and rate of addition is slow, after precipitating crystal, keeps the temperature 30 points
Clock；Acid adding, PH are controlled in 5-6, and temperature is centrifuged at 50 DEG C or so, washed 3 times, dries to obtain 700 kg developer finished products.
100kg products are taken to carry out HPLC analyses, HPLC analysis conditions are：
Analytical column：Diamonsil II chromatographic columns（4.6mm*20cm）
Mobile phase：50% acetonitrile/water+10 drips acetic acid
Flow velocity：0.8ml/min
Column temperature：35℃
Detector：UV 254nm
In the above conditions, about 4.95 minutes appearances is 2,4- dibenzenesulfonyl phenol, and about 3.98 minutes appearances are
4- benzenesulfonyl phenol, about 6.22 minutes appearances are 2,4,6- tri- benzenesulfonyl phenol.
HPLC analysis results are shown：2,4- dibenzenesulfonyl phenol contain 91.1kg, and 4- benzenesulfonyl phenol contains
3.83kg, 2,4,6- tri- benzenesulfonyl phenol contain 2.1kg.
Embodiment 2
It is prepared by priming coat：
By mixing following component, it is 60g/m to be applied to Substance2Base paper on so that be after dry
5g/m2, and be dried, obtain the base paper for imposing priming coat：
80 kg of calcined kaolin；
Small 20 kg of hollow bead of plasticity；
40% 1 kg of aqueous sodium polyacrylate；
50% 15 kg of phenylethylene/butadiene latex；
10% 50 kg of polyvinyl alcohol water solution；
200 kg of water.
It is prepared by heat-sensitive color layer：
（1）Dispersion A：Disperse following ingredient by sand mill, until average grain diameter is 0.5 μm：
2- anilino- -3- methyl -6- dibutylamino fluoranes（OBD-2） 20 kg；
10% polyvinyl alcohol water solution, 30 kg；
50 kg of water.
（2）Dispersion B:Disperse following ingredient by sand mill, until average grain diameter is 1.0 μm：
30 kg of color developing agent finished product that embodiment 1 obtains；
10% polyvinyl alcohol water solution, 30 kg；
40 kg of water.
（3）Dispersion C:Disperse following ingredient by sand mill, until average grain diameter is 1.0 μm.
30 kg of beta naphthal benzylic ether；
10% polyvinyl alcohol water solution, 30 kg；
40 kg of water.
（4）It by mixing following ingredient, is applied on priming coat so that 4.5g/m after dry2, and done
It is dry, obtain the 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
Thermal recording medium is prepared according to the same manner as in Example 2, the color developing agent finished product for only obtaining embodiment 1
It is changed to 2,4- dibenzenesulfonyl phenol.
Embodiment 4
The thermal recording medium of embodiment 4 is prepared according to the same manner as in Example 2, only obtains embodiment 1
Color developing agent finished product is changed to 4 hydroxyls -4 '-isopropoxy diphenyl sulphone (DPS).
Embodiment 5
The thermal recording medium of embodiment 5 is prepared according to the same manner as in Example 2, only obtains embodiment 1
Reagent composition is changed to 4,4 '-dihydroxydiphenylsulisomers.
To thermal recording medium obtained in embodiment 2 to embodiment 5, its physical property is measured, as shown in table 1 below：
Table 1
Wherein, oil preventing performance is dripped using thermal response tester with 0.42mj/dot energy print images on the image
Edible vegetable oil blots extra vegetable oil after 10s, and after being placed 24 hours at a temperature of 20 DEG C, density is divided with X-Rite
The optical density of instrument test image part；
Water resistance uses thermal response tester, with 0.42mj/dot energy print images, by image in 20 DEG C of water
Dipping air-dries after 24 hours, with the optical density of X-Rite light splitting densimeter test images part；
Anti- alcohol performance uses thermal response tester, with 0.42mj/dot energy print images, the second for being 25% by volume fraction
Alcoholic solution drips on the image, dried after 5 hours it is air-dried, with the optical density of X-Rite light splitting densimeter test image part；
Plasticizer resistance uses thermal response tester, with 0.42mj/dot energy print images, covers 3 layers on the image
Vinyl chloride film containing plasticizer is placed 24 hours under the conditions of 20 DEG C, with X-Rite light splitting densimeter test images part
Optical density；
Heat resistance uses thermal response tester, with 0.42mj/dot energy print images, by image at a temperature of 60 DEG C
It places 24 hours, the optical density of densimeter test image part and blank sheet of paper part is divided with X-Rite；
Moisture resistance properties use thermal response tester, with 0.42mj/dot energy print images, by image 40 DEG C of temperature,
It is placed 24 hours under 90%RH humidity, the optical density of densimeter test image part and blank sheet of paper part is divided with X-Rite；
Light fastness uses thermal response tester, and with 0.42mj/dot energy print images, image is transferred in 5000lx
It sets 100 hours, the optical density of densimeter test image part and blank sheet of paper part is divided with X-Rite.
Thermo-responsive sensitivity uses thermosensitive response tester（Model：TH-M2/N1, OKURA DENKI manufactures）, in temperature-sensitive
Print image on recording materials is divided densimeter with X-Rite（500 series, are manufactured by X-Rite companies of the U.S.）Measure image portion
The density divided, as shown in Figure 1.
The thermal recording medium of the present invention is compared with embodiment 3-5, sensitivity higher, grease proofness it can be seen from above-mentioned chart
Performance is more prominent in terms of energy, water resistance, anti-alcohol performance, plasticizer resistance, heat resistance, moisture resistance properties and light fastness.
Claims (4)
1. a kind of thermal recording medium, including base paper, it is coated with priming coat in the base paper, temperature-sensitive is coated on the priming coat
Color layer, it is characterised in that：The heat-sensitive color layer includes dyestuff and color developing agent, and the color developing agent is by 2,4- dibenzenesulfonyl benzene
Phenol, 4- benzenesulfonyls phenol and tri- benzenesulfonyl phenol of 2,4,6- composition.
2. a kind of thermal recording medium according to claim 1, it is characterised in that：The color developing agent is by 65-95 mass parts
2,4- dibenzenesulfonyls phenol, the 4- benzenesulfonyls phenol of 2-25 mass parts and tri- benzene sulfonyls of 2,4,6- of 0.1-10 mass parts
Base phenol forms.
3. a kind of thermal recording medium according to claim 2, it is characterised in that：The color developing agent is by 80-95 mass parts
2,4- dibenzenesulfonyls phenol, the 4- benzenesulfonyls phenol of 3-15 mass parts and tri- benzene sulfonyls of 2,4,6- of 0.5-5 mass parts
Base phenol forms.
4. a kind of thermal recording medium according to claim 1, it is characterised in that：The dyestuff be fluorane compounds or
Spiro-pyrans class compound.
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| CN104972780B true CN104972780B (en) | 2018-09-28 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
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 | Thermal paper manufacturing method capable of preventing mechanical pulp/ chemical mechanical pulp thermal paper from fading |
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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 | Thermal paper manufacturing method capable of preventing mechanical pulp/ chemical mechanical pulp thermal paper from fading |
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