WO2023274202A1 - Energy-resistant, corrosion-resistant and abrasion-resistant heat-generating substrate of thermal print head - Google Patents
Energy-resistant, corrosion-resistant and abrasion-resistant heat-generating substrate of thermal print head Download PDFInfo
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- WO2023274202A1 WO2023274202A1 PCT/CN2022/101782 CN2022101782W WO2023274202A1 WO 2023274202 A1 WO2023274202 A1 WO 2023274202A1 CN 2022101782 W CN2022101782 W CN 2022101782W WO 2023274202 A1 WO2023274202 A1 WO 2023274202A1
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- 239000000758 substrate Substances 0.000 title claims abstract description 58
- 230000007797 corrosion Effects 0.000 title claims abstract description 35
- 238000005260 corrosion Methods 0.000 title claims abstract description 35
- 238000005299 abrasion Methods 0.000 title abstract 3
- 239000011241 protective layer Substances 0.000 claims abstract description 98
- 239000011521 glass Substances 0.000 claims abstract description 91
- 239000010410 layer Substances 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 72
- 239000010409 thin film Substances 0.000 claims description 22
- 239000000919 ceramic Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 15
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 14
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 14
- 238000007651 thermal printing Methods 0.000 claims description 13
- 210000003298 dental enamel Anatomy 0.000 claims description 8
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- -1 sialon Chemical compound 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 3
- 229910052593 corundum Inorganic materials 0.000 claims 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 3
- 229910052681 coesite Inorganic materials 0.000 claims 2
- 229910052906 cristobalite Inorganic materials 0.000 claims 2
- 239000000377 silicon dioxide Substances 0.000 claims 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 2
- 229910052682 stishovite Inorganic materials 0.000 claims 2
- 229910052905 tridymite Inorganic materials 0.000 claims 2
- 238000003763 carbonization Methods 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 17
- 230000007704 transition Effects 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- 241000985905 Candidatus Phytoplasma solani Species 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
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- 229920005989 resin Polymers 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/315—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by selective application of heat to a heat sensitive printing or impression-transfer material
- B41J2/32—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by selective application of heat to a heat sensitive printing or impression-transfer material using thermal heads
- B41J2/335—Structure of thermal heads
- B41J2/33505—Constructional details
- B41J2/33535—Substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/315—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by selective application of heat to a heat sensitive printing or impression-transfer material
- B41J2/32—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by selective application of heat to a heat sensitive printing or impression-transfer material using thermal heads
- B41J2/335—Structure of thermal heads
- B41J2/33505—Constructional details
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/315—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by selective application of heat to a heat sensitive printing or impression-transfer material
- B41J2/32—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by selective application of heat to a heat sensitive printing or impression-transfer material using thermal heads
- B41J2/335—Structure of thermal heads
- B41J2/33505—Constructional details
- B41J2/3353—Protective layers
Definitions
- the embodiment of the present application relates to the technical field of thermal printhead manufacturing, for example, a thermal printhead heating substrate that can significantly improve the energy resistance characteristics of the heating resistor in the thermal printhead and effectively improve the wear resistance and corrosion resistance of the heating substrate .
- the thermal print head in the related art includes an insulating substrate, an underglaze layer is provided on the surface of the insulating substrate, a common electrode and an individual electrode are arranged on the surface of the insulating substrate and the underglaze layer, and the heating resistor is arranged between the two electrodes, and the common One end of the electrode is connected to the heating resistor body, and the other end is used to connect to the power supply. One end of individual electrodes is connected to the heating resistor body, and the other end is connected to the pad.
- the surface of the glass enamel protective layer is also provided with a ceramic wear-resistant layer formed in a thin film manner.
- the thermal print head in the related art has low sensitivity to the printing medium and the quality of the printing medium is poor.
- the heating resistor of the thermal printing head needs more Joule heat to make the printing medium develop color, and more Joule heat causes the temperature to exceed that of the heating resistor.
- the resistance value of the heating resistor is prone to rise and damage; in a high temperature and high humidity environment, the corrosion resistance of the protective layer is insufficient and the metal electrode is corroded and disconnected; in addition, the quality of the printing medium is poor.
- the wear resistance of the protective layer is insufficient, and the resistor body or metal electrode is scratched by the medium or foreign particles, which will lead to product damage.
- the embodiment of the present application proposes a heating substrate of a thermal printing head that can significantly improve the energy resistance characteristics of the heating resistor in the thermal printing head, and effectively improve the wear resistance and corrosion resistance of the heating substrate.
- An energy-resistant, corrosion-resistant, and wear-resistant thermal printing head heating substrate is provided with an insulating substrate, and an underglaze layer composed of an amorphous glass material is arranged on the surface of the insulating substrate. There are common electrodes and individual electrodes on the surface, and the heating resistor is arranged between the common electrode and the individual electrodes.
- One end of the common electrode is connected to the heating resistor, and the other end is used to connect to the power supply; One end is connected to the pad; the surface of the heating resistor, the individual electrodes and the common electrode are provided with a protective layer, and the protective layer includes a first protective layer covering the surface of the heating resistor, and the temperature range of the transfer point of the first protective layer is A glass glaze layer at 600-725°C, or a glass glaze layer with a softening point temperature range of 700-870°C.
- the components in the first protective layer described in the examples of this application are based on the oxide state, and the content is as follows: SiO 2 content 49.4mol%-56.8mol%, Al 2 O 3 content 13.7mol%-26.7mol%, CaO content 3.5mol%-13.8mol%, BaO content 1.5mol%-5.9mol%, PbO content 4.8mol%-17.7mol%, ZrO 2 content 1.2mol%-5.0mol%.
- the upper side of the first protective layer is compounded with a second protective layer, the second protective layer adopts an insulating glass glaze layer or a conductive glass glaze layer, and further, the transfer point of the second protective layer Or the softening point is lower than the transition point or softening point of the first protective layer; further, when the second protective layer is a conductive glass glaze layer, the resistivity range is 0.01 ⁇ m-10k ⁇ m.
- the protective layer in the embodiment of the present application is also provided with a thin-film ceramic wear-resistant protective layer above the glass glaze layer, and the thin-film ceramic wear-resistant protective layer is composed of one of silicon carbide, sialon or silicon nitride or is made of Composite thin-film ceramic layer composed of any two of silicon carbide, sialon, and silicon nitride; the thin-film ceramic wear-resistant layer is used to contact the external environment and printing media to improve the wear-resistant characteristics of the product.
- the beneficial effect of the embodiment of the present application is that the insulating glass glaze with a high transition point (greater than 600°C) or a high softening point (greater than 700°C) is used as the first protective layer, and it partially diffuses into the heating resistor during sintering.
- the transfer point or softening point of the glass composition inside the heating resistor is improved, thereby improving the energy resistance of the heating resistor and reducing the resistance value increase of the heating resistor when printing at higher energy;
- the high transfer point or high softening point Insulating glass glaze is made by high-temperature melting and needs to be sintered at a higher temperature. It has good chemical stability and significantly enhances the corrosion resistance of the product.
- the surface of the glass glaze protective layer is equipped with a thin-film ceramic wear protection formed by a thin-film process.
- the heat-generating substrate for the thermal print head of this application has the characteristics of simple production method and low cost, which can greatly reduce the damage of the heat-generating resistor caused by high printing energy, and improve the high-temperature and high-humidity environment of the print head. High corrosion resistance and wear resistance in harsh environments significantly improve product reliability.
- an energy-resistant, corrosion-resistant, and wear-resistant heat-generating substrate for thermal print heads including an insulating substrate, and an amorphous substrate is arranged on the surface of the insulating substrate.
- the bottom glaze layer made of high-quality glass material is provided with a common electrode and individual electrodes on the surface of the bottom glaze layer.
- the heating resistor is arranged between the common electrode and the individual electrodes.
- One end of the common electrode is connected to the heating resistor, and the other end is It is connected to the power supply; one end of individual electrodes is connected to the heating resistor body, and the other end is connected to the pad; the surface of the heating resistor body, individual electrodes and common electrodes is provided with a glass glaze layer and a ceramic wear-resistant layer formed by thin film technology.
- the glass glaze protective layer at least includes a first protective layer 5a made of insulating glass glaze with a high transfer point or high softening point; the transfer point or softening point of the glass composition constituting the first protective layer 5a is higher than that of the heating resistor
- the transition point or softening point temperature of the glass composition in the body, the first protective layer 5a is subsequently called a high transition point or high softening point insulating glass glaze protective layer, and its transition point is 600-725 ° C or its softening point is 700-870 °C.
- the insulating glass glaze whose transition point temperature is 600-725°C or softening point temperature is 700-870°C has a composition based on oxide state, SiO 2 content of 49.4mol%-56.8mol%, Al 2 O 3 content 13.7mol%-26.7mol%, CaO content 3.5mol%-13.8mol%, BaO content 1.5-5.9mol%, PbO content 4.8mol%-17.7mol%, ZrO 2 content 1.2mol %-5.0mol%.
- the insulating glass glaze whose transition point temperature is 600-725°C or softening point temperature is 700-870°C has a composition based on oxide state, SiO 2 content of 49.4mol%-54.5mol%, Al 2 O 3 content 17.7mol%-26.7mol%, CaO content 3.5mol%-10.5mol%, BaO content 1.5mol%-5.0mol%, PbO content 8.5mol%-17.7mol%, ZrO 2 content 1.2mol%-3.8mol%.
- the insulating glass glaze whose transition point temperature is 600-725°C or softening point temperature is 700-870°C has a composition based on oxide state, SiO 2 content of 52.0mol%-54.5mol%, Al 2 O 3 content 17.7mol%-22.5mol%, CaO content 6.5mol%-10.5mol%, BaO content 2.5mol%-5.0mol%, PbO content 8.5mol%-13.5mol%, ZrO 2 content 2.5mol%-3.8mol%.
- the first protective layer can be used independently as an insulating glass enamel protective layer, or together with other glass enamel protective layers to form a glass enamel protective layer; the other glass enamel protective layers are insulating glass enamel, or conductive glass Glaze; the resistivity of the conductive glass glaze protective layer is 0.01 ⁇ m-10K ⁇ m.
- the transition point or softening point of the insulating glass glaze protective layer other than the first protective layer is lower than the transition point or softening point of the composition of the first protective layer, which is subsequently referred to as low transition point or low softening point insulating glass Glaze protection layer.
- the surface of the protective layer is provided with a thin-film ceramic wear-resistant protective layer 5d formed by a thin-film process, and the thin-film ceramic wear-resistant protective layer 5d is composed of one of silicon carbide, sialon or silicon nitride, or is made of silicon carbide A composite thin-film ceramic layer composed of any two of , sialon, and silicon nitride.
- the insulating glass glaze protective layer composition involved in this application its form does not exist in various single oxides, usually in the state of composite oxides or compounds.
- the components of the glass composition in this application are converted in accordance with the usual practice.
- Single oxides are used for marking.
- the insulating glass glaze may contain forms such as PbSiO 3 , and single oxides are marked as PbO and SiO 2 respectively.
- the energy-resistant thermal printing head heating substrate and its manufacturing method are provided below, and a comparative example is provided:
- Firing appearance (1) Use a surface roughness tester to measure the surface roughness, take 10 samples of each composition of the glass glaze for measurement, and calculate the average value; (2) Observe the surface of the glass glaze with a stereo microscope Condition: Surface leveling and defects.
- Tg glass transition point temperature
- Ts glass softening point temperature
- STOL energy resistance test: Apply 1.5-2 times the rated heating energy to the resistor, measure the resistance value change rate of the heating resistor, measure 192 heating resistors for each glass glaze protective layer sample, and calculate its average.
- Corrosion resistance test Under the conditions of fixed temperature and fixed humidity, the thermal print head is powered on and standby in the actual working state, and the time for corrosion damage of the insulating glass glaze protective layer is measured.
- the insulating glass glaze protective layer slurry prepared above is printed on the surface of the substrate on which the electrode and the ruthenium dioxide heating resistor have been prepared, and sintered to form the first insulating glass glaze protective layer, which is made into a thermal print head substrate , to carry out the power resistance test and the corrosion resistance test, and the results are recorded in Table 2.
- sample 3-sample 7 insulating glass glaze protective layer paste with STOL ⁇ -3% print on the surface of the substrate that has already prepared electrodes and ruthenium dioxide heating resistors, and sinter to make a high transfer point or softening point
- the first glass glaze protective layer sample, and then a part of the sample surface is formed with a silicon carbide wear-resistant layer by thin film technology to make a thermal print head substrate; the other part of the sample surface is printed and sintered with the second glass glaze protective layer slurry to make the second glass Glaze protective layer, and then use thin film technology to form a silicon carbide wear-resistant layer on the surface of the second glass glaze protective layer to make a thermal print head substrate, and further conduct energy resistance and corrosion resistance tests.
- the dot insulating glass protective layer with other glass glaze protective layers the energy resistance and corrosion resistance of the thermal print head of the present application are significantly improved compared with the prior art, and the results are recorded in Table 3.
- the energy-resistant and corrosion-resistant heat-generating substrate for a thermal print head involved in this example includes an insulating substrate 1, and an underglaze made of an amorphous glass material is provided on the surface portion of the insulating substrate 1.
- Layer 2; a common electrode and an individual electrode 3 are provided on the surface of the bottom glaze layer 2, and a heating resistor 4 is arranged between the common electrode and the individual electrode 3 along the main printing direction as a heating element that generates Joule heat.
- One end of the common electrode is connected to the heating resistor 4 along the secondary printing direction, and the other end is used to connect to the power supply; one end of the individual electrode is connected to the heating resistor 4 along the secondary printing direction, for protection
- the heating substrate is covered with a protective layer 5 on the surface of the heating resistor 4, the common electrode and the individual electrodes 3.
- the protective layer 5, as shown in Table 3, selects sample 3 with a transfer point of 600 ° C and a softening point of 700 ° C.
- Insulating glass glaze 5a constitutes the first protective layer and the silicon carbide ceramic protective layer formed by thin film technology.
- the high softening point or transition point glass glaze 5a partly diffuses into the heating resistor body during sintering, which increases the glass softening point temperature of the heating resistor body and enhances the power resistance characteristics of the heating resistor body; the high softening point or transfer point insulating glass glaze 5a, has a certain fluidity during sintering, and has good surface smoothness after sintering.
- the surface of 5a has very few defects, which improves the corrosion resistance of the product.
- the silicon carbide ceramic layer strengthens the wear resistance of the thermal print head substrate and obtains energy resistance. , Corrosion-resistant, wear-resistant thermal print head substrate.
- the energy-resistant and corrosion-resistant heat-generating substrate for a thermal print head involved in this example includes an insulating substrate 1, and an underglaze made of an amorphous glass material is provided on the surface portion of the insulating substrate 1.
- Layer 2. A common electrode and an individual electrode 3 are arranged on the surface of the underglaze layer 2, and a heating resistor 4 is disposed between the common electrode and the individual electrode 3 along the main printing direction, as a heating element generating Joule heat, and the common electrode
- One end is connected to the heating resistor 4 along the secondary printing direction, and the other end is used to connect to the power supply; one end of the individual electrode is connected to the heating resistor 4 along the secondary printing direction, in order to protect the heating substrate,
- the protective layer 5 is covered on the surface of the heating resistor 4, the common electrode and the individual electrodes 3.
- the protective layer 5, as shown in Table 3, uses sample 5, which is made of insulating glass glaze with a transfer point of 683°C and a softening point of 812°C. 5a constitutes the first protective layer, the insulating glass glaze 5b constitutes the second protective layer and the silicon carbide ceramic protective layer formed by thin film technology;
- the high softening point glass glaze 5a partially diffuses into the heating resistor body during sintering, which increases the glass softening point temperature of the heating resistor body and enhances the energy resistance characteristics of the heating resistor body.
- the glass protective layer 5b has good fluidity during sintering, After sintering, the insulating glass glaze 5 has good surface smoothness, improves the compactness of the surface of the high softening point glass glaze 5a, and further improves the corrosion resistance of the product.
- the silicon carbide ceramic layer strengthens the wear resistance of the substrate of the thermal print head to obtain energy resistance , Corrosion-resistant, wear-resistant thermal print head substrate.
- the energy-resistant and corrosion-resistant heat-generating substrate for a thermal print head involved in this example includes an insulating substrate 1, and an underglaze made of an amorphous glass material is provided on the surface portion of the insulating substrate 1.
- a common electrode and an individual electrode 3 are arranged on the surface of the underglaze layer 2, and a heating resistor 4 is disposed between the common electrode and the individual electrode 3 along the main printing direction, as a heating element generating Joule heat, and the common electrode
- One end is connected to the heating resistor 4 along the secondary printing direction, and the other end is used to connect to the power supply; one end of the individual electrode is connected to the heating resistor 4 along the secondary printing direction, in order to protect the heating substrate,
- the protective layer 5 is covered on the surface of the heating resistor 4, the common electrode and the individual electrodes 3.
- the protective layer 5, as shown in Table 3, uses sample 5, which is made of insulating glass glaze with a transfer point of 683°C and a softening point of 812°C. 5a constitutes the first protective layer, the second protective layer composed of conductive glass glaze 5b with a resistivity of 10 ⁇ m, and a silicon carbide ceramic protective layer formed by thin film technology;
- the high softening point glass glaze 5a partly diffuses into the heating resistor body during sintering, which increases the glass softening point temperature of the heating resistor body and enhances the energy resistance characteristics of the heating resistor body.
- the conductive glass glaze protective layer 5b reduces the surface potential of the substrate , reduce the electrochemical corrosion of the wear-resistant protective layer under high temperature and high humidity, reduce the corrosion effect of the electrode on the high temperature and high humidity environment, and improve the corrosion resistance of the product.
- the silicon carbide ceramic layer strengthens the wear resistance of the thermal print head substrate and obtains energy resistance , Corrosion-resistant, wear-resistant thermal print head substrate.
- the present application can also adopt other combinations, such as adopting high softening point or high transfer point glass glaze as the first protective layer, adopting low softening point or low transfer point glass glaze as the second protective layer and the third protective layer, and using thin film
- the silicon carbide ceramic protective layer formed by the process together constitutes the protective layer, and a thermal print head substrate with energy resistance, corrosion resistance and wear resistance is obtained.
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Abstract
An energy-resistant, corrosion-resistant and abrasion-resistant heat-generating substrate of a thermal print head. The heat-generating substrate is provided with an insulating substrate (1), wherein a ground glaze layer (2), which is made of an amorphous glass material, is arranged on a surface portion of the insulating substrate (1); a common electrode and an individual electrode (3) are arranged on the surface of the ground glaze layer (2); a heat-generating resistor body (4) is configured between the common electrode and the individual electrode (3); the surface of the heat-generating resistor body (4), the surface of the common electrode and the surface of the individual electrode (3) are provided with a protective layer (5); and the protective layer (5) includes a first protective layer (5a) that covers the surface of the heat-generating resistor body (4), the first protective layer (5a) being a glass glaze layer having a transition point temperature ranging from 600°C to 725°C or a glass glaze layer having a softening point temperature ranging from 700°C to 870°C. The heat-generating substrate of a thermal print head has the characteristics of requiring a simple production method and being low cost, can greatly reduce the amount of damage to a heat-generating resistor body that is caused by high word-printing energy, and can improve the corrosion resistance capability of the print head in a high-temperature and high-humidity environment and the abrasion resistance performance thereof in a harsh environment, thereby significantly improving the product reliability.
Description
本申请实施例涉及热敏打印头制造技术领域,例如一种能够显著改善热敏打印头中发热电阻体的耐能量特性,并有效提高发热基板耐磨、耐腐蚀性能的热敏打印头发热基板。The embodiment of the present application relates to the technical field of thermal printhead manufacturing, for example, a thermal printhead heating substrate that can significantly improve the energy resistance characteristics of the heating resistor in the thermal printhead and effectively improve the wear resistance and corrosion resistance of the heating substrate .
相关技术中的热敏打印头包括绝缘基板,绝缘基板表面设有底釉层,在所述绝缘基板与底釉层表面设有共通电极和个别电极,发热电阻体配置在两电极之间,共通电极一端与发热电阻体相连,另一端用于与电源相连,个别电极一端与发热电阻体相连,其另一端与焊盘相连,发热电阻体、个别电极与共通电极表面设有玻璃釉保护层以及玻璃釉保护层表面还设有的采用薄膜方式形成的陶瓷耐磨层。The thermal print head in the related art includes an insulating substrate, an underglaze layer is provided on the surface of the insulating substrate, a common electrode and an individual electrode are arranged on the surface of the insulating substrate and the underglaze layer, and the heating resistor is arranged between the two electrodes, and the common One end of the electrode is connected to the heating resistor body, and the other end is used to connect to the power supply. One end of individual electrodes is connected to the heating resistor body, and the other end is connected to the pad. The surface of the glass enamel protective layer is also provided with a ceramic wear-resistant layer formed in a thin film manner.
相关技术中的热敏打印头在印字介质感度较低以及印字介质质量差,热敏打印头发热电阻体需要更多的焦耳热使印字介质发色,更多的焦耳热导致温度超过发热电阻体内部玻璃软化点或转移点温度时,发热电阻体容易发生电阻值升高破坏;在高温高湿度环境下,保护层耐腐蚀性不足破坏使金属电极被腐蚀断线;另外,在印字介质质量差、室外等环境下,保护层耐磨性能不足,电阻体或金属电极被介质或异物颗粒划伤,均导致产品损坏。The thermal print head in the related art has low sensitivity to the printing medium and the quality of the printing medium is poor. The heating resistor of the thermal printing head needs more Joule heat to make the printing medium develop color, and more Joule heat causes the temperature to exceed that of the heating resistor. When the temperature of the internal glass softening point or transition point is reached, the resistance value of the heating resistor is prone to rise and damage; in a high temperature and high humidity environment, the corrosion resistance of the protective layer is insufficient and the metal electrode is corroded and disconnected; in addition, the quality of the printing medium is poor. In , outdoor and other environments, the wear resistance of the protective layer is insufficient, and the resistor body or metal electrode is scratched by the medium or foreign particles, which will lead to product damage.
发明内容Contents of the invention
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。The following is an overview of the topics described in detail in this article. This summary is not intended to limit the scope of the claims.
本申请实施例提出了一种能够显著改善热敏打印头中发热电阻体的耐能量特性,并有效提高发热基板耐磨、耐腐蚀性能的热敏打印头发热基板。The embodiment of the present application proposes a heating substrate of a thermal printing head that can significantly improve the energy resistance characteristics of the heating resistor in the thermal printing head, and effectively improve the wear resistance and corrosion resistance of the heating substrate.
本申请实施例通过以下措施达到:The embodiment of the present application achieves through the following measures:
一种耐能量耐腐蚀耐磨损的热敏打印头发热基板,设有绝缘基板,在所述绝缘基板的表面部分的设有非晶质玻璃材料构成的底釉层,在所述底釉层的表面设有共通电极和个别电极,发热电阻体配置在共通电极和个别电极之间,共通电极一端与发热电阻体相连,另一端用于与电源相连;个别电极一端与发热 电阻体相连,另一端与焊盘相连;发热电阻体、个别电极与共通电极表面设有保护层,所述保护层包含覆盖在发热电阻体表面的第一保护层,所述第一保护层为转移点温度范围为600-725℃的玻璃釉层,或为软化点温度范围为700-870℃的玻璃釉层。An energy-resistant, corrosion-resistant, and wear-resistant thermal printing head heating substrate is provided with an insulating substrate, and an underglaze layer composed of an amorphous glass material is arranged on the surface of the insulating substrate. There are common electrodes and individual electrodes on the surface, and the heating resistor is arranged between the common electrode and the individual electrodes. One end of the common electrode is connected to the heating resistor, and the other end is used to connect to the power supply; One end is connected to the pad; the surface of the heating resistor, the individual electrodes and the common electrode are provided with a protective layer, and the protective layer includes a first protective layer covering the surface of the heating resistor, and the temperature range of the transfer point of the first protective layer is A glass glaze layer at 600-725°C, or a glass glaze layer with a softening point temperature range of 700-870°C.
本申请实施例所述第一保护层中组分以氧化物状态计,含量如下:SiO
2含有量49.4mol%-56.8mol%、Al
2O
3含有量13.7mol%-26.7mol%、CaO含有量3.5mol%-13.8mol%、BaO含有量1.5mol%-5.9mol%、PbO含有量4.8mol%-17.7mol%、ZrO
2含有量1.2mol%-5.0mol%。
The components in the first protective layer described in the examples of this application are based on the oxide state, and the content is as follows: SiO 2 content 49.4mol%-56.8mol%, Al 2 O 3 content 13.7mol%-26.7mol%, CaO content 3.5mol%-13.8mol%, BaO content 1.5mol%-5.9mol%, PbO content 4.8mol%-17.7mol%, ZrO 2 content 1.2mol%-5.0mol%.
本申请实施例所述保护层中第一保护层的上侧复合第二保护层,所述第二保护层采用绝缘玻璃釉层或导电玻璃釉层,进一步,所述第二保护层的转移点或软化点低于第一保护层的转移点或软化点;进一步,所述第二保护层为导电玻璃釉层时,电阻率范围为0.01Ω·m-10kΩ·m。In the protective layer described in the embodiment of the present application, the upper side of the first protective layer is compounded with a second protective layer, the second protective layer adopts an insulating glass glaze layer or a conductive glass glaze layer, and further, the transfer point of the second protective layer Or the softening point is lower than the transition point or softening point of the first protective layer; further, when the second protective layer is a conductive glass glaze layer, the resistivity range is 0.01Ω·m-10kΩ·m.
本申请实施例所述保护层还设有位于玻璃釉层上方的薄膜陶瓷耐磨保护层,所述薄膜陶瓷耐磨保护层由碳化硅、赛隆或者氮化硅中的一种组成或者是由碳化硅、赛隆、氮化硅中的任意2种组成的复合薄膜陶瓷层;薄膜陶瓷耐磨层用于与外部环境及打印介质接触,提高产品的耐磨特性。The protective layer in the embodiment of the present application is also provided with a thin-film ceramic wear-resistant protective layer above the glass glaze layer, and the thin-film ceramic wear-resistant protective layer is composed of one of silicon carbide, sialon or silicon nitride or is made of Composite thin-film ceramic layer composed of any two of silicon carbide, sialon, and silicon nitride; the thin-film ceramic wear-resistant layer is used to contact the external environment and printing media to improve the wear-resistant characteristics of the product.
本申请实施例的有益效果在于,采用高转移点(大于600℃)或高软化点(大于700℃)的绝缘玻璃釉作为第一保护层,在烧结时,部分地扩散入发热电阻体内部,提高了发热电阻体内部玻璃组合物的转移点或软化点,进而提高发热电阻体耐能量特性,减少发热电阻体在较高能量打印时的电阻值升高;所述高转移点或高软化点绝缘玻璃釉,采用高温熔融制得,并且需要采用较高温度烧结,具有良好的化学稳定性,显著增强产品耐腐蚀性能,玻璃釉保护层表面设有的采用薄膜工艺形成的薄膜陶瓷耐磨保护层进一步强化耐磨性能,本申请的热敏打印头用发热基板,具有生产方法简单、成本低的特点,能极大地减少高印字能量导致的发热电阻体破坏、提高打印头高温、高湿度环境下的耐腐蚀能力以及恶劣环境下耐磨损性能,显著提高了产品可靠性。The beneficial effect of the embodiment of the present application is that the insulating glass glaze with a high transition point (greater than 600°C) or a high softening point (greater than 700°C) is used as the first protective layer, and it partially diffuses into the heating resistor during sintering. The transfer point or softening point of the glass composition inside the heating resistor is improved, thereby improving the energy resistance of the heating resistor and reducing the resistance value increase of the heating resistor when printing at higher energy; the high transfer point or high softening point Insulating glass glaze is made by high-temperature melting and needs to be sintered at a higher temperature. It has good chemical stability and significantly enhances the corrosion resistance of the product. The surface of the glass glaze protective layer is equipped with a thin-film ceramic wear protection formed by a thin-film process. layer to further strengthen the wear resistance, the heat-generating substrate for the thermal print head of this application has the characteristics of simple production method and low cost, which can greatly reduce the damage of the heat-generating resistor caused by high printing energy, and improve the high-temperature and high-humidity environment of the print head. High corrosion resistance and wear resistance in harsh environments significantly improve product reliability.
在阅读并理解了附图和详细描述后,可以明白其他方面。Other aspects will be apparent to others upon reading and understanding the drawings and detailed description.
附图用来提供对本文技术方案的进一步理解,并且构成说明书的一部分, 与本申请的实施例一起用于解释本文的技术方案,并不构成对本文技术方案的限制。The accompanying drawings are used to provide a further understanding of the technical solutions herein, and constitute a part of the description, and are used together with the embodiments of the application to explain the technical solutions herein, and do not constitute limitations to the technical solutions herein.
附图1是本申请实施例1的结构示意图。Accompanying drawing 1 is the schematic structural diagram of embodiment 1 of the present application.
附图2是本申请实施例2的结构示意图。Accompanying drawing 2 is the schematic structural diagram of embodiment 2 of the present application.
附图3是本申请实施例3的结构示意图。Accompanying drawing 3 is the schematic structural diagram of embodiment 3 of the present application.
附图标记:绝缘基板1、底釉层2、共通电极与个别电极3、发热电阻体4、保护层5、第一保护层(高转移点或高软化点绝缘玻璃釉层)5a、第二保护层(低转移点或低软化点绝缘玻璃釉层)5b、第三保护层(低转移点或低软化点绝缘玻璃釉层)5c、薄膜陶瓷耐磨保护层5d。Reference signs: insulating substrate 1, bottom glaze layer 2, common electrode and individual electrode 3, heating resistor 4, protective layer 5, first protective layer (insulating glass glaze layer with high transfer point or high softening point) 5a, second Protective layer (low transition point or low softening point insulating glass glaze layer) 5b, third protective layer (low transition point or low softening point insulating glass glaze layer) 5c, thin-film ceramic wear-resistant protective layer 5d.
下面结合附图和实施例,对本申请作进一步说明。The application will be further described below in conjunction with the accompanying drawings and embodiments.
本申请针对现有技术的缺陷和不足,提出了一种耐能量、耐腐蚀、耐磨损的热敏打印头用发热基板,包括绝缘基板,在所述绝缘基板的表面部分的设有非晶质玻璃材料构成的底釉层,在所述底釉层的表面设有共通电极和个别电极,发热电阻体配置在共通电极和个别电极之间,共通电极一端与发热电阻体相连,另一端用于与电源相连;个别电极一端与发热电阻体相连,其另一端与焊盘相连;发热电阻体、个别电极与共通电极表面设有由玻璃釉层以及由薄膜工艺形成的陶瓷耐磨层组成的复合保护层,所述玻璃釉保护层至少包含有高转移点或高软化点绝缘玻璃釉构成的第一保护层5a;构成第一保护层5a的玻璃组合物转移点或软化点高于发热电阻体中玻璃组合物的转移点或软化点温度,第一保护层5a后续称为高转移点或高软化点绝缘玻璃釉保护层,其转移点为600-725℃或者其软化点为700-870℃。Aiming at the defects and deficiencies of the prior art, the present application proposes an energy-resistant, corrosion-resistant, and wear-resistant heat-generating substrate for thermal print heads, including an insulating substrate, and an amorphous substrate is arranged on the surface of the insulating substrate. The bottom glaze layer made of high-quality glass material is provided with a common electrode and individual electrodes on the surface of the bottom glaze layer. The heating resistor is arranged between the common electrode and the individual electrodes. One end of the common electrode is connected to the heating resistor, and the other end is It is connected to the power supply; one end of individual electrodes is connected to the heating resistor body, and the other end is connected to the pad; the surface of the heating resistor body, individual electrodes and common electrodes is provided with a glass glaze layer and a ceramic wear-resistant layer formed by thin film technology. Composite protective layer, the glass glaze protective layer at least includes a first protective layer 5a made of insulating glass glaze with a high transfer point or high softening point; the transfer point or softening point of the glass composition constituting the first protective layer 5a is higher than that of the heating resistor The transition point or softening point temperature of the glass composition in the body, the first protective layer 5a is subsequently called a high transition point or high softening point insulating glass glaze protective layer, and its transition point is 600-725 ° C or its softening point is 700-870 ℃.
优选的是,所述转移点温度为600-725℃或软化点温度为700-870℃的绝缘玻璃釉,其组合物以氧化物状态计,SiO
2含有量49.4mol%-56.8mol%、Al
2O
3含有量13.7mol%-26.7mol%、CaO含有量3.5mol%-13.8mol%、BaO含有量1.5-5.9mol%、PbO含有量4.8mol%-17.7mol%、ZrO
2含有量1.2mol%-5.0mol%。
Preferably, the insulating glass glaze whose transition point temperature is 600-725°C or softening point temperature is 700-870°C has a composition based on oxide state, SiO 2 content of 49.4mol%-56.8mol%, Al 2 O 3 content 13.7mol%-26.7mol%, CaO content 3.5mol%-13.8mol%, BaO content 1.5-5.9mol%, PbO content 4.8mol%-17.7mol%, ZrO 2 content 1.2mol %-5.0mol%.
优选的是,所述转移点温度为600-725℃或软化点温度为700-870℃的绝缘玻璃釉,其组合物以氧化物状态计,SiO
2含有量49.4mol%-54.5mol%、Al
2O
3含有量17.7mol%-26.7mol%、CaO含有量3.5mol%-10.5mol%、BaO含有量 1.5mol%-5.0mol%、PbO含有量8.5mol%-17.7mol%、ZrO
2含有量1.2mol%-3.8mol%。
Preferably, the insulating glass glaze whose transition point temperature is 600-725°C or softening point temperature is 700-870°C has a composition based on oxide state, SiO 2 content of 49.4mol%-54.5mol%, Al 2 O 3 content 17.7mol%-26.7mol%, CaO content 3.5mol%-10.5mol%, BaO content 1.5mol%-5.0mol%, PbO content 8.5mol%-17.7mol%, ZrO 2 content 1.2mol%-3.8mol%.
优选的是,所述转移点温度为600-725℃或软化点温度为700-870℃的绝缘玻璃釉,其组合物以氧化物状态计,SiO
2含有量52.0mol%-54.5mol%、Al
2O
3含有量17.7mol%-22.5mol%、CaO含有量6.5mol%-10.5mol%、BaO含有量2.5mol%-5.0mol%、PbO含有量8.5mol%-13.5mol%、ZrO
2含有量2.5mol%-3.8mol%。
Preferably, the insulating glass glaze whose transition point temperature is 600-725°C or softening point temperature is 700-870°C has a composition based on oxide state, SiO 2 content of 52.0mol%-54.5mol%, Al 2 O 3 content 17.7mol%-22.5mol%, CaO content 6.5mol%-10.5mol%, BaO content 2.5mol%-5.0mol%, PbO content 8.5mol%-13.5mol%, ZrO 2 content 2.5mol%-3.8mol%.
优选的是,第一保护层既可以独立作为绝缘玻璃釉保护层,也可以与其它玻璃釉保护层共同构成玻璃釉保护层;所述其它玻璃釉保护层是绝缘玻璃釉,也可以是导电玻璃釉;所述导电玻璃釉保护层的电阻率是0.01Ω·m-10KΩ·m。Preferably, the first protective layer can be used independently as an insulating glass enamel protective layer, or together with other glass enamel protective layers to form a glass enamel protective layer; the other glass enamel protective layers are insulating glass enamel, or conductive glass Glaze; the resistivity of the conductive glass glaze protective layer is 0.01Ω·m-10KΩ·m.
优选的是,除第一保护层以外的其它绝缘玻璃釉保护层的转移点或软化点低于第一保护层组合物的转移点或软化点,后续称为低转移点或低软化点绝缘玻璃釉保护层。Preferably, the transition point or softening point of the insulating glass glaze protective layer other than the first protective layer is lower than the transition point or softening point of the composition of the first protective layer, which is subsequently referred to as low transition point or low softening point insulating glass Glaze protection layer.
优选的是,所述保护层表面设置薄膜工艺形成的薄膜陶瓷耐磨保护层5d,薄膜陶瓷耐磨保护层5d由碳化硅、赛隆或者氮化硅中的一种组成,或者是由碳化硅、赛隆、氮化硅中的任意2种组成的复合薄膜陶瓷层。Preferably, the surface of the protective layer is provided with a thin-film ceramic wear-resistant protective layer 5d formed by a thin-film process, and the thin-film ceramic wear-resistant protective layer 5d is composed of one of silicon carbide, sialon or silicon nitride, or is made of silicon carbide A composite thin-film ceramic layer composed of any two of , sialon, and silicon nitride.
本申请涉及的绝缘玻璃釉保护层组合物中,其形态并不是以各种单一氧化物存在,通常以复合氧化物或者化合物的状态,本申请中玻璃组合物的成分按照通常惯例,以换算为单一氧化物进行标记,例如,绝缘玻璃釉中可能含有PbSiO
3等形态,以单一氧化物分别标记为PbO、SiO
2。
In the insulating glass glaze protective layer composition involved in this application, its form does not exist in various single oxides, usually in the state of composite oxides or compounds. The components of the glass composition in this application are converted in accordance with the usual practice. Single oxides are used for marking. For example, the insulating glass glaze may contain forms such as PbSiO 3 , and single oxides are marked as PbO and SiO 2 respectively.
下面提供耐能量热敏打印头发热基板及其制造方法,并提供对比例:The energy-resistant thermal printing head heating substrate and its manufacturing method are provided below, and a comparative example is provided:
其中以下叙述中所提到的各参数含义如下:The meanings of the parameters mentioned in the following description are as follows:
烧成外观:(1)使用表面粗糙度测试仪测量表面粗糙度,对每个组成的玻璃釉料取10个样品进行测定,并求取其平均值;(2)体视显微镜观察玻璃釉表面状态:表面流平以及缺陷。Firing appearance: (1) Use a surface roughness tester to measure the surface roughness, take 10 samples of each composition of the glass glaze for measurement, and calculate the average value; (2) Observe the surface of the glass glaze with a stereo microscope Condition: Surface leveling and defects.
Tg(玻璃转移点温度)、Ts(玻璃软化点温度):采用差热分析DTA,对每个组成的玻璃釉料取10个样品进行测定,并求取其平均值。Tg (glass transition point temperature), Ts (glass softening point temperature): Differential thermal analysis (DTA) was used to measure 10 samples of glass frits of each composition, and the average value was calculated.
STOL(耐能量测试):对电阻体施加1.5-2倍额定发热能量,测定发热电阻体的电阻值变化率,对每个组成的玻璃釉料保护层样品测定192个发热电阻体,并求取其平均值。STOL (energy resistance test): Apply 1.5-2 times the rated heating energy to the resistor, measure the resistance value change rate of the heating resistor, measure 192 heating resistors for each glass glaze protective layer sample, and calculate its average.
耐腐蚀测试:固定温度、固定湿度条件下,热敏打印头实际工作状态时通电待机,测定绝缘玻璃釉保护层发生腐蚀破坏的时间。Corrosion resistance test: Under the conditions of fixed temperature and fixed humidity, the thermal print head is powered on and standby in the actual working state, and the time for corrosion damage of the insulating glass glaze protective layer is measured.
首先,将各种氧化物,按照计量比进行混合,高温熔融制得玻璃料,取各个样品进行Tg、Ts测定;取适量玻璃料粉碎后制得玻璃釉粉,添加填料、有机溶剂以及树脂,混合后制得高转移点或高软化点绝缘玻璃釉保护层浆料。First, mix various oxides according to the metering ratio, and melt at high temperature to obtain glass frit, take each sample for Tg and Ts measurement; take an appropriate amount of glass frit and pulverize to obtain glass glaze powder, add fillers, organic solvents and resins, After mixing, a high transfer point or high softening point insulating glass glaze protective layer slurry is prepared.
以氧化物计算,高转移点或高软化点绝缘玻璃釉组合物各种成分含量,如表1:Calculated by oxides, the contents of various components of the high transfer point or high softening point insulating glass glaze composition are shown in Table 1:
表1Table 1
其次,将上述制得的绝缘玻璃釉保护层浆料,印刷于已经制备完成电极、二氧化钌发热电阻体的基板表面,烧结制成第一绝缘玻璃釉保护层,制成热敏打印头基板,进行耐功率特性测试、耐腐蚀特性测试,其各项结果记录在表2中。Secondly, the insulating glass glaze protective layer slurry prepared above is printed on the surface of the substrate on which the electrode and the ruthenium dioxide heating resistor have been prepared, and sintered to form the first insulating glass glaze protective layer, which is made into a thermal print head substrate , to carry out the power resistance test and the corrosion resistance test, and the results are recorded in Table 2.
表2:Table 2:
第一绝缘玻璃釉保护层The first protective layer of insulating glass glaze | 烧结表面状态Sintered surface state | STOL(%)STOL(%) | 耐腐蚀特性(Hr)Corrosion Resistance (Hr) |
试样1(现有技术)Sample 1 (Prior Art) | 平滑smooth | -7.5%-7.5% | 264264 |
试样2Sample 2 | 无光泽,粗糙度大dull, rough | -5.0%-5.0% | 24twenty four |
试样3Sample 3 | 平滑、光泽smooth, glossy | -2.5%-2.5% | 168168 |
试样4Sample 4 | 平滑、光泽smooth, glossy | -2.0%-2.0% | 192192 |
试样5Sample 5 | 平滑、光泽smooth, glossy | -1.9%-1.9% | 192192 |
试样6Sample 6 | 无光泽dull | -2.2%-2.2% | 144144 |
试样7Sample 7 | 无光泽dull | -2.3%-2.3% | 144144 |
试样8Sample 8 | 无光泽dull | -1.5%-1.5% | 4848 |
另外,选择STOL<-3%的试样3-试样7绝缘玻璃釉保护层浆料,印刷于已经制备完成电极、二氧化钌发热电阻体的基板表面,烧结制成高转移点或软化点第一玻璃釉保护层样品,然后一部分样品表面采用薄膜工艺形成碳化硅耐磨 层,制成热敏打印头基板;另一部分样品表面印刷、烧结第二玻璃釉保护层浆料制成第二玻璃釉保护层,再在第二玻璃釉保护层表面采用薄膜工艺形成碳化硅耐磨层,制成热敏打印头基板,进一步进行耐能量特性测试、耐腐蚀特性测试,采用高转移点或高软化点绝缘玻璃保护层与其他玻璃釉保护层结合,本申请的热敏打印头耐能量以及耐腐蚀性能比现有技术有明显提升,其各项结果记录在表3中。In addition, select sample 3-sample 7 insulating glass glaze protective layer paste with STOL<-3%, print on the surface of the substrate that has already prepared electrodes and ruthenium dioxide heating resistors, and sinter to make a high transfer point or softening point The first glass glaze protective layer sample, and then a part of the sample surface is formed with a silicon carbide wear-resistant layer by thin film technology to make a thermal print head substrate; the other part of the sample surface is printed and sintered with the second glass glaze protective layer slurry to make the second glass Glaze protective layer, and then use thin film technology to form a silicon carbide wear-resistant layer on the surface of the second glass glaze protective layer to make a thermal print head substrate, and further conduct energy resistance and corrosion resistance tests. Combining the dot insulating glass protective layer with other glass glaze protective layers, the energy resistance and corrosion resistance of the thermal print head of the present application are significantly improved compared with the prior art, and the results are recorded in Table 3.
表3table 3
实施例1:Example 1:
如图1所示,本例所涉及的耐能量耐腐性的热敏打印头用发热基板包括绝缘基板1,在所述绝缘基板1的表面部分的设有非晶质玻璃材料构成的底釉层2;在所述底釉层2的表面设有共通电极与个别电极3,发热电阻体4沿主打印方向配置在共通电极与个别电极3之间,作为产生焦耳热的发热体,所述共通电极的一端沿副打印方向与所述发热电阻体4相连接,其另一端用于与电源相连接;所述个别电极的一端沿副打印方向与所述发热电阻体4相连接,为保护发热基板,在所述发热电阻体4、共通电极与个别电极3的表面覆盖保护层5,所述保护层5,如表3选用试样3由转移点600℃、软化点700℃绝缘玻璃釉5a构成第一保护层以及采用薄膜工艺形成的碳化硅陶瓷保护层组成。As shown in Figure 1, the energy-resistant and corrosion-resistant heat-generating substrate for a thermal print head involved in this example includes an insulating substrate 1, and an underglaze made of an amorphous glass material is provided on the surface portion of the insulating substrate 1. Layer 2; a common electrode and an individual electrode 3 are provided on the surface of the bottom glaze layer 2, and a heating resistor 4 is arranged between the common electrode and the individual electrode 3 along the main printing direction as a heating element that generates Joule heat. One end of the common electrode is connected to the heating resistor 4 along the secondary printing direction, and the other end is used to connect to the power supply; one end of the individual electrode is connected to the heating resistor 4 along the secondary printing direction, for protection The heating substrate is covered with a protective layer 5 on the surface of the heating resistor 4, the common electrode and the individual electrodes 3. The protective layer 5, as shown in Table 3, selects sample 3 with a transfer point of 600 ° C and a softening point of 700 ° C. Insulating glass glaze 5a constitutes the first protective layer and the silicon carbide ceramic protective layer formed by thin film technology.
高软化点或转移点玻璃釉5a烧结时部分地扩散入发热电阻体,提高了发热电阻体的玻璃软化点温度,增强了发热的电阻体的耐功率特性;高软化点或转移点绝缘玻璃釉5a,烧结时具有一定的流动性、烧结后具有良好的表面平滑性, 5a表面的极少缺陷,提高产品耐腐蚀性能,碳化硅陶瓷层强化热敏打印头基板的耐磨性能,得到耐能量、耐腐蚀、耐磨损的热敏打印头基板。The high softening point or transition point glass glaze 5a partly diffuses into the heating resistor body during sintering, which increases the glass softening point temperature of the heating resistor body and enhances the power resistance characteristics of the heating resistor body; the high softening point or transfer point insulating glass glaze 5a, has a certain fluidity during sintering, and has good surface smoothness after sintering. The surface of 5a has very few defects, which improves the corrosion resistance of the product. The silicon carbide ceramic layer strengthens the wear resistance of the thermal print head substrate and obtains energy resistance. , Corrosion-resistant, wear-resistant thermal print head substrate.
实施例2:Example 2:
如图2所示,本例所涉及的耐能量耐腐性的热敏打印头用发热基板包括绝缘基板1,在所述绝缘基板1的表面部分的设有非晶质玻璃材料构成的底釉层2。在所述底釉层2的表面设有共通电极与个别电极3,发热电阻体4沿主打印方向配置在共通电极与个别电极3之间,作为产生焦耳热的发热体,所述共通电极的一端沿副打印方向与所述发热电阻体4相连接,其另一端用于与电源相连接;所述个别电极的一端沿副打印方向与所述发热电阻体4相连接,为保护发热基板,在所述发热电阻体4、共通电极与个别电极3的表面覆盖保护层5,所述保护层5,如表3,选用试样5,由转移点683℃、软化点812℃的绝缘玻璃釉5a构成第一保护层,绝缘玻璃釉5b构成的第二保护层以及采用薄膜工艺形成的碳化硅陶瓷保护层组成;As shown in Figure 2, the energy-resistant and corrosion-resistant heat-generating substrate for a thermal print head involved in this example includes an insulating substrate 1, and an underglaze made of an amorphous glass material is provided on the surface portion of the insulating substrate 1. Layer 2. A common electrode and an individual electrode 3 are arranged on the surface of the underglaze layer 2, and a heating resistor 4 is disposed between the common electrode and the individual electrode 3 along the main printing direction, as a heating element generating Joule heat, and the common electrode One end is connected to the heating resistor 4 along the secondary printing direction, and the other end is used to connect to the power supply; one end of the individual electrode is connected to the heating resistor 4 along the secondary printing direction, in order to protect the heating substrate, The protective layer 5 is covered on the surface of the heating resistor 4, the common electrode and the individual electrodes 3. The protective layer 5, as shown in Table 3, uses sample 5, which is made of insulating glass glaze with a transfer point of 683°C and a softening point of 812°C. 5a constitutes the first protective layer, the insulating glass glaze 5b constitutes the second protective layer and the silicon carbide ceramic protective layer formed by thin film technology;
高软化点玻璃釉5a烧结时部分地扩散入发热电阻体,提高了发热电阻体的玻璃软化点温度,增强了发热电阻体的耐能量特性,玻璃保护层5b,烧结时具有良好的流动性、烧结后绝缘玻璃釉5具有良好的表面平滑性,提高高软化点玻璃釉5a表面的致密性,进一步提升产品耐腐蚀性能,碳化硅陶瓷层强化热敏打印头基板的耐磨性能,得到耐能量、耐腐蚀、耐磨损的热敏打印头基板。The high softening point glass glaze 5a partially diffuses into the heating resistor body during sintering, which increases the glass softening point temperature of the heating resistor body and enhances the energy resistance characteristics of the heating resistor body. The glass protective layer 5b has good fluidity during sintering, After sintering, the insulating glass glaze 5 has good surface smoothness, improves the compactness of the surface of the high softening point glass glaze 5a, and further improves the corrosion resistance of the product. The silicon carbide ceramic layer strengthens the wear resistance of the substrate of the thermal print head to obtain energy resistance , Corrosion-resistant, wear-resistant thermal print head substrate.
实施例3:Example 3:
如图3所示,本例所涉及的耐能量耐腐性的热敏打印头用发热基板包括绝缘基板1,在所述绝缘基板1的表面部分的设有非晶质玻璃材料构成的底釉层2。在所述底釉层2的表面设有共通电极与个别电极3,发热电阻体4沿主打印方向配置在共通电极与个别电极3之间,作为产生焦耳热的发热体,所述共通电极的一端沿副打印方向与所述发热电阻体4相连接,其另一端用于与电源相连接;所述个别电极的一端沿副打印方向与所述发热电阻体4相连接,为保护发热基板,在所述发热电阻体4、共通电极与个别电极3的表面覆盖保护层5,所述保护层5,如表3,选用试样5,由转移点683℃、软化点812℃的绝缘玻璃釉5a构成第一保护层、电阻率为10Ω·m的导电玻璃釉5b构成的第二保护层以及采用薄膜工艺形成的碳化硅陶瓷保护层组成;As shown in FIG. 3 , the energy-resistant and corrosion-resistant heat-generating substrate for a thermal print head involved in this example includes an insulating substrate 1, and an underglaze made of an amorphous glass material is provided on the surface portion of the insulating substrate 1. Layer 2. A common electrode and an individual electrode 3 are arranged on the surface of the underglaze layer 2, and a heating resistor 4 is disposed between the common electrode and the individual electrode 3 along the main printing direction, as a heating element generating Joule heat, and the common electrode One end is connected to the heating resistor 4 along the secondary printing direction, and the other end is used to connect to the power supply; one end of the individual electrode is connected to the heating resistor 4 along the secondary printing direction, in order to protect the heating substrate, The protective layer 5 is covered on the surface of the heating resistor 4, the common electrode and the individual electrodes 3. The protective layer 5, as shown in Table 3, uses sample 5, which is made of insulating glass glaze with a transfer point of 683°C and a softening point of 812°C. 5a constitutes the first protective layer, the second protective layer composed of conductive glass glaze 5b with a resistivity of 10Ω·m, and a silicon carbide ceramic protective layer formed by thin film technology;
本例中高软化点玻璃釉5a烧结时部分地扩散入发热电阻体,提高了发热电 阻体的玻璃软化点温度,增强了发热电阻体的耐能量特性,导电玻璃釉保护层5b,降低基板表面电位,减少高温高湿下耐磨保护层的电化学腐蚀,降低高温高湿度环境对电极的腐蚀作用,提升产品耐腐蚀性能,碳化硅陶瓷层强化热敏打印头基板的耐磨性能,得到耐能量、耐腐蚀、耐磨损的热敏打印头基板。In this example, the high softening point glass glaze 5a partly diffuses into the heating resistor body during sintering, which increases the glass softening point temperature of the heating resistor body and enhances the energy resistance characteristics of the heating resistor body. The conductive glass glaze protective layer 5b reduces the surface potential of the substrate , reduce the electrochemical corrosion of the wear-resistant protective layer under high temperature and high humidity, reduce the corrosion effect of the electrode on the high temperature and high humidity environment, and improve the corrosion resistance of the product. The silicon carbide ceramic layer strengthens the wear resistance of the thermal print head substrate and obtains energy resistance , Corrosion-resistant, wear-resistant thermal print head substrate.
本申请还可以采用其它组合方式,例如采用高软化点或高转移点玻璃釉作为第一保护层,采用低软化点或低转移点玻璃釉作为第二保护层和第三保护层,以及采用薄膜工艺形成的碳化硅陶瓷保护层共同构成保护层,得到耐能量、耐腐蚀、耐磨损的热敏打印头基板。The present application can also adopt other combinations, such as adopting high softening point or high transfer point glass glaze as the first protective layer, adopting low softening point or low transfer point glass glaze as the second protective layer and the third protective layer, and using thin film The silicon carbide ceramic protective layer formed by the process together constitutes the protective layer, and a thermal print head substrate with energy resistance, corrosion resistance and wear resistance is obtained.
Claims (8)
- 一种耐能量耐腐蚀耐磨损的热敏打印头发热基板,设有绝缘基板,在所述绝缘基板的表面部分的设有非晶质玻璃材料构成的底釉层,在所述底釉层的表面设有共通电极和个别电极,发热电阻体配置在共通电极和个别电极之间,共通电极一端与发热电阻体相连,另一端用于与电源相连;个别电极一端与发热电阻体相连,另一端与焊盘相连;发热电阻体、个别电极与共通电极表面设有保护层,其中,所述保护层包含覆盖在发热电阻体表面的第一保护层,所述第一保护层为转移点温度范围为600-725℃的玻璃釉层,或为软化点温度范围为700-870℃的玻璃釉层。An energy-resistant, corrosion-resistant, and wear-resistant thermal printing head heating substrate is provided with an insulating substrate, and an underglaze layer composed of an amorphous glass material is arranged on the surface of the insulating substrate. There are common electrodes and individual electrodes on the surface, and the heating resistor is arranged between the common electrode and the individual electrodes. One end of the common electrode is connected to the heating resistor, and the other end is used to connect to the power supply; One end is connected to the pad; the surface of the heating resistor, the individual electrodes and the common electrode are provided with a protective layer, wherein the protective layer includes a first protective layer covering the surface of the heating resistor, and the first protective layer is the transfer point temperature A glass enamel layer in the range of 600-725°C, or a glass enamel layer with a softening point temperature in the range of 700-870°C.
- 根据权利要求1所述的一种耐能量耐腐蚀耐磨损的热敏打印头发热基板,其中,所述第一保护层中组分以氧化物状态计,含量如下:SiO 2含有量49.4mol%-56.8mol%、Al 2O 3含有量13.7mol%-26.7mol%、CaO含有量3.5mol%-13.8mol%、BaO含有量1.5mol%-5.9mol%、PbO含有量4.8mol%-17.7mol%、ZrO 2含有量1.2mol%-5.0mol%。 An energy-resistant, corrosion-resistant and wear-resistant thermal printing head heating substrate according to claim 1, wherein the components in the first protective layer are calculated as oxides, and the content is as follows: SiO 2 content 49.4mol %-56.8mol%, Al2O3 content 13.7mol %-26.7mol%, CaO content 3.5mol%-13.8mol%, BaO content 1.5mol%-5.9mol%, PbO content 4.8mol%-17.7 mol%, ZrO 2 content 1.2mol%-5.0mol%.
- 根据权利要求1所述的一种耐能量耐腐蚀耐磨损的热敏打印头发热基板,其中,所述保护层中第一保护层的外侧复合第二保护层,所述第二保护层采用绝缘玻璃釉层或导电玻璃釉层。An energy-resistant, corrosion-resistant, and wear-resistant thermal printing head heating substrate according to claim 1, wherein the outer side of the first protective layer in the protective layer is compounded with a second protective layer, and the second protective layer adopts Insulating glass glaze layer or conductive glass glaze layer.
- 根据权利要求3所述的一种耐能量耐腐蚀耐磨损的热敏打印头发热基板,其中,所述第二保护层的转移点或软化点低于第一保护层的转移点或软化点。An energy-resistant, corrosion-resistant and wear-resistant thermal printing head heating substrate according to claim 3, wherein the transfer point or softening point of the second protective layer is lower than the transfer point or softening point of the first protective layer .
- 根据权利要求3所述的一种耐能量耐腐蚀耐磨损的热敏打印头发热基板,其中,所述第二保护层为导电玻璃釉层,电阻率范围为0.01Ω·m-10kΩ·m。An energy-resistant, corrosion-resistant and wear-resistant thermal printing head heating substrate according to claim 3, wherein the second protective layer is a conductive glass glaze layer, and the resistivity range is 0.01Ω·m-10kΩ·m .
- 根据权利要求1所述的一种耐能量耐腐蚀耐磨损的热敏打印头发热基板,其中,所述保护层还设有薄膜陶瓷耐磨保护层,所述薄膜陶瓷耐磨保护层由碳化硅、赛隆或者氮化硅中的一种组成或者是由碳化硅、赛隆、氮化硅中的任意2种组成的复合薄膜陶瓷层。An energy-resistant, corrosion-resistant and wear-resistant thermal printing head heating substrate according to claim 1, wherein the protective layer is also provided with a thin-film ceramic wear-resistant protective layer, and the thin-film ceramic wear-resistant protective layer is formed by carbonization One of silicon, sialon, or silicon nitride, or a composite thin-film ceramic layer composed of any two of silicon carbide, sialon, and silicon nitride.
- 根据权利要求2所述的一种耐能量耐腐蚀耐磨损的热敏打印头发热基板,其中,所述转移点温度为600-725℃或软化点温度为700-870℃的绝缘玻璃釉,其组合物以氧化物状态计,SiO 2含有量49.4mol%-54.5mol%、Al 2O 3含有量17.7mol%-26.7mol%、CaO含有量3.5mol%-10.5mol%、BaO含有量1.5mol%-5.0mol%、PbO含有量8.5mol%-17.7mol%、ZrO 2含有量1.2mol%-3.8mol%。 An energy-resistant, corrosion-resistant and wear-resistant thermal printing head heating substrate according to claim 2, wherein the insulating glass glaze with a transfer point temperature of 600-725°C or a softening point temperature of 700-870°C, Its composition is based on the oxide state, SiO2 content 49.4mol%-54.5mol%, Al2O3 content 17.7mol %-26.7mol%, CaO content 3.5mol%-10.5mol%, BaO content 1.5 mol%-5.0mol%, PbO content 8.5mol%-17.7mol%, ZrO 2 content 1.2mol%-3.8mol%.
- 根据权利要求2所述的一种耐能量耐腐蚀耐磨损的热敏打印头发热基板,其中,所述转移点温度为600-725℃或软化点温度为700-870℃的绝缘玻璃釉,其组合物以氧化物状态计,SiO 2含有量52.5mol%-54.5mol%、Al 2O 3含有量17.7mol%-22.5mol%、CaO含有量6.5mol%-10.5mol%、BaO含有量2.5mol%-5.0mol%、PbO含有量8.5mol%-13.5mol%、ZrO 2含有量2.5mol%-3.8mol%。 An energy-resistant, corrosion-resistant and wear-resistant thermal printing head heating substrate according to claim 2, wherein the insulating glass glaze with a transfer point temperature of 600-725°C or a softening point temperature of 700-870°C, Its composition is based on the oxide state, SiO2 content 52.5mol%-54.5mol%, Al2O3 content 17.7mol %-22.5mol%, CaO content 6.5mol%-10.5mol%, BaO content 2.5 mol%-5.0mol%, PbO content 8.5mol%-13.5mol%, ZrO 2 content 2.5mol%-3.8mol%.
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Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5066960A (en) * | 1989-04-05 | 1991-11-19 | Sharp | Thermal printing head |
CN1163011A (en) * | 1994-09-13 | 1997-10-22 | 株式会社东芝 | Thermal head and its manufacture |
JP2000229435A (en) * | 1999-02-09 | 2000-08-22 | Alps Electric Co Ltd | Production of thermal head |
CN1968820A (en) * | 2004-06-15 | 2007-05-23 | 罗姆股份有限公司 | Thermal head and manufacturing method thereof |
JP2008080786A (en) * | 2006-08-28 | 2008-04-10 | Hideo Taniguchi | Heating head, heating head unit, and heating head module |
CN101784495A (en) * | 2007-10-31 | 2010-07-21 | 阿尔卑斯电气株式会社 | Low-heat diffusible phosphate glass and thermal head using the low-heat diffusible phosphate glass |
CN101934637A (en) * | 2009-06-30 | 2011-01-05 | 山东华菱电子有限公司 | Thermal print head and preparation method thereof |
CN102725145A (en) * | 2010-01-29 | 2012-10-10 | 青井电子株式会社 | Thermal head |
CN206884473U (en) * | 2017-06-20 | 2018-01-16 | 山东华菱电子股份有限公司 | A kind of thermal printing head heating base plate of wear resistant corrosion resistant |
CN114368224A (en) * | 2021-07-02 | 2022-04-19 | 山东华菱电子股份有限公司 | Energy-resistant and corrosion-resistant heating substrate for thermal printing head |
CN114379238A (en) * | 2021-07-02 | 2022-04-22 | 山东华菱电子股份有限公司 | Energy-resistant, corrosion-resistant and wear-resistant thermosensitive printing head heating substrate |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007268970A (en) * | 2006-03-31 | 2007-10-18 | Toshiba Corp | Thermal printer head and method for manufacturing the same |
CN101734020A (en) * | 2008-11-17 | 2010-06-16 | 山东新北洋信息技术股份有限公司 | Hot erasing head for erasing erasable medium and printer thereof |
-
2021
- 2021-07-02 CN CN202110753758.2A patent/CN114379238B/en active Active
-
2022
- 2022-06-28 WO PCT/CN2022/101782 patent/WO2023274202A1/en active Application Filing
- 2022-06-28 JP JP2023562756A patent/JP2024517390A/en active Pending
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5066960A (en) * | 1989-04-05 | 1991-11-19 | Sharp | Thermal printing head |
CN1163011A (en) * | 1994-09-13 | 1997-10-22 | 株式会社东芝 | Thermal head and its manufacture |
JP2000229435A (en) * | 1999-02-09 | 2000-08-22 | Alps Electric Co Ltd | Production of thermal head |
CN1968820A (en) * | 2004-06-15 | 2007-05-23 | 罗姆股份有限公司 | Thermal head and manufacturing method thereof |
JP2008080786A (en) * | 2006-08-28 | 2008-04-10 | Hideo Taniguchi | Heating head, heating head unit, and heating head module |
CN101784495A (en) * | 2007-10-31 | 2010-07-21 | 阿尔卑斯电气株式会社 | Low-heat diffusible phosphate glass and thermal head using the low-heat diffusible phosphate glass |
CN101934637A (en) * | 2009-06-30 | 2011-01-05 | 山东华菱电子有限公司 | Thermal print head and preparation method thereof |
CN102725145A (en) * | 2010-01-29 | 2012-10-10 | 青井电子株式会社 | Thermal head |
CN206884473U (en) * | 2017-06-20 | 2018-01-16 | 山东华菱电子股份有限公司 | A kind of thermal printing head heating base plate of wear resistant corrosion resistant |
CN114368224A (en) * | 2021-07-02 | 2022-04-19 | 山东华菱电子股份有限公司 | Energy-resistant and corrosion-resistant heating substrate for thermal printing head |
CN114379238A (en) * | 2021-07-02 | 2022-04-22 | 山东华菱电子股份有限公司 | Energy-resistant, corrosion-resistant and wear-resistant thermosensitive printing head heating substrate |
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JP2024517390A (en) | 2024-04-22 |
CN114379238A (en) | 2022-04-22 |
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