CN101784495B - Low-heat diffusible phosphate glass and thermal head using the low-heat diffusible phosphate glass - Google Patents

Low-heat diffusible phosphate glass and thermal head using the low-heat diffusible phosphate glass Download PDF

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Publication number
CN101784495B
CN101784495B CN200880102887.8A CN200880102887A CN101784495B CN 101784495 B CN101784495 B CN 101784495B CN 200880102887 A CN200880102887 A CN 200880102887A CN 101784495 B CN101784495 B CN 101784495B
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phosphate
glass
mole
based glass
substrate
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CN101784495A (en
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沼田大志
花田成
道又融
中谷寿文
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Alps Alpine Co Ltd
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Alps Electric Co Ltd
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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
    • B41J2/33525—Passivation layers
    • 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
    • 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
    • B41J2/33555—Structure of thermal heads characterised by type
    • B41J2/3356—Corner type resistors
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)
  • Electronic Switches (AREA)

Abstract

To solve a problem of a conventional silicate glass that the heat diffusion is so large that the power consumption of a thermal head could not have been reduced. [MEANS FOR SOLVING PROBLEMS] A phosphate glass comprising by mole 30 to 75% of P2O5 and 8 to 60% of CeO2 as main components. The phosphoate glass has a low thermal diffusivity which is in the range of 0.27 to 0.39 (mm2/sec). By virtue of this property, the phosphate glass, when used in a substrate in a thermal head, can realize lowered power consumption. A phosphate glass having a thermal diffusivity of not more than 0.31 (mm2/sec) is particularly suitable for use in the substrate in the thermal head. Further, the phosphate glass has a low coefficient of thermal expansion and, thus, when used in the substrate, is less likely to be deformed. Furthermore, the glass transition temperature is so high that a thermal head having excellent heat resistance can be realized.

Description

The phosphate-based glass of low thermal diffusivity and use the thermal head of the phosphate-based glass of above-mentioned low thermal diffusivity
Technical field
The present invention relates to a kind of phosphate-based glass, particularly the phosphate-based glass of a kind of low thermal diffusivity and use the thermal head (Thermal head) of the phosphate-based glass of above-mentioned low thermal diffusivity.
Background technology
At present, as low melting glass, use leaded glass, from the viewpoint of the impact on environment always, exist and avoid consciously plumbous trend, as unleaded low melting glass, as described in following patent documentation 1～3, carrying out energetically phosphoric acid-aluminum oxide (P 2o 5-Al 2o 3) be glass, phosphoric acid-tin-zinc (P 2o 5-SnO-ZnO) be the exploitation of glass.
Fig. 2 represents an example of the sectional view of the printhead for thermal printer (thermal head) 1 of use at present.
Thermal head for example comprises following structure, that is, and and by aluminum oxide (Al 2o 3) etc. be formed with the stepped construction of glaze (glaze) layer 12, heating resistor layer 13, conductor layer 14 and protective layer 15 on the substrate 11 that forms of pottery.The heat producing when electric current is flow through to above-mentioned heating resistor layer 13 passes to the media such as temperature-sensitive paper or ink ribbon and prints.
The heat being produced by heating resistor layer 13 passes to medium by protective layer 15, and a part passes to glaze layer 12.Above-mentioned glaze layer 12 makes heat go to substrate 11, and self has and accumulate produced hot recuperation layer and the function of thermal insulation layer.And, by changing height and the shape of glaze layer 12, can manufacture the thermal head that can print on various uses or starting material.
Glaze layer surface on substrate exists when concavo-convex, produces and records density unevenness, therefore, requires above-mentioned glaze layer surface smoothing.Following patent documentation 4 discloses a kind of technology, and it,, by adopting the glass material of surface smoothness excellence to form substrate, even if do not form glaze layer, also can obtain level and smooth surface.
Patent documentation 1: Japanese Patent Publication 6-39337 communique
Patent documentation 2: TOHKEMY 2001-139344 communique
Patent documentation 3: TOHKEMY 2001-302279 communique
Patent documentation 4: Japanese kokai publication hei 4-214368 communique
Along with the high speed of thermal printer, require thermal head to there is thermotolerance, in recent years, pursuing the stable on heating while, pursue the power reducing of thermal head.
Originally, comparatively ideal was that the heat being produced by heating resistor layer passes to medium completely, but the thermal diffusivity of glaze layer is when high, and heat passes to glaze layer 12 and substrate 11 fast, and therefore, enough heat does not pass to medium.Therefore,, in order to print, must make heating resistor layer produce a large amount of heat.Therefore,, for the power reducing of thermal head, need to form glaze layer with the low material of thermal diffusivity.
In addition, when the coefficient of thermal expansion of the substrate consisting of pottery and glaze layer is different, due to heating and cooling repeatedly, glaze layer can be from strippable substrate, therefore, requires the coefficient of thermal expansion of the material that both use roughly the same.
In above-mentioned patent documentation 4, owing to forming substrate with glass materials such as barium borosilicic acid, manosil AS, soda-lime, therefore, do not need to form glaze layer, can solve the problem that glaze layer is peeled off from ceramic substrate, but because these silicate Glass thermal diffusivities are high, therefore, the heat that should pass to medium often passes to glass substrate one side, so, there is the high problem of power consumption.
In above-mentioned patent documentation 1～3, recorded following technology, it discloses a kind of phosphate-based glass, by regulating added ingredients, can obtain glass or the large glass of thermal conductivity of electrical insulating property excellence.But, the phosphate-based glass that thermal conductivity is low is not recorded entirely.
Summary of the invention
Therefore, the present invention is for solving the invention of above-mentioned prior art problem, and its object is, provides especially a kind of and existing and compares, the phosphate-based glass that thermal diffusivity is low.Its object is also, a kind of thermal head is provided, and it forms substrate and glaze layer with the low phosphate-based glass of thermal diffusivity, thereby power consumption is low.
The invention is characterized in, it is with P 2o 5and CeO 2for the phosphate-based glass of low thermal diffusivity of main component, wherein, contain 30～75 (% by mole) P 2o 5, contain 8～60 (% by mole) CeO 2.
By with P 2o 5and CeO 2both are as the main component of glass, by P 2o 5be set as 30～75 (% by mole) scope, by CeO 2be set as 8～60 (% by mole) scope, can obtain the glass that thermal diffusivity is low.Therefore, phosphate-based glass of the present invention can be preferred for the substrate of thermal head.In addition, to containing 50～67 (% by mole) P 2o 5, contain 9～39 (% by mole) CeO 2phosphate-based glass, its thermal diffusivity is at 0.27～0.39 (mm 2/ second) scope, can be aptly for the substrate of thermal head.And thermal diffusivity is 0.31 (mm 2/ second) the following phosphate-based glass of low thermal diffusivity, as thermal head substrate, be particularly suitable for.
In addition, the phosphate-based glass of low thermal diffusivity of the present invention also can contain other trace ingredients.For example, preferably contain 0～2.2 (% by mole) Pr 6o 11or 0～10 (% by mole) Cr 2o 3.
Thermal head of the present invention is formed with heating resistor layer and protective layer on substrate, it is characterized in that, utilize and to contain 30～75 (% by mole) P 2o 5, contain 8～60 (% by mole) CeO 2the phosphate-based glass of low thermal diffusivity form described substrate.
In above-mentioned thermal head, also can on above-mentioned heating resistor layer, form conductor layer.
Compare with existing, the phosphate-based glass of low thermal diffusivity of the present invention can reduce thermal diffusivity.Therefore,, by utilizing for example substrate of phosphate-based glass formation thermal head of the present invention, the power consumption of thermal head can realize than existing low power consumption.In addition, the phosphate-based glass of low thermal diffusivity of the present invention is because second-order transition temperature is high, excellent heat resistance, therefore, can be used in particular for the substrate of the thermal head that high speed thermal printer uses.In addition, the phosphate-based glass of low thermal diffusivity of the present invention also can be for the glaze layer of thermal head.
Accompanying drawing explanation
Fig. 1 is the sectional view of the thermal head of embodiments of the present invention;
Fig. 2 is the sectional view of existing thermal head.
The explanation of symbol
1 thermal head
11 substrates
12 glaze layers
13 heating resistor layers
14 conductor layers
15 protective layers
Embodiment
The phosphate-based glass of low thermal diffusivity of present embodiment is with phosphoric acid (P 2o 5) and cerium oxide (CeO 2) be main component, 30～75 (% by mole) scope contain P 2o 5, 8～60 (% by mole) scope contain CeO 2.In addition, phosphate-based glass contain 50～67 (% by mole) P 2o 5, contain 9～39 (% by mole) CeO 2time, can reduce thermal diffusivity.Now, P 2o 5as the 1st principal constituent (ratio of components is maximum), preferably in phosphate-based glass, content compares CeO 2many, can be by CeO 2as the 2nd principal constituent (ratio of components the 2nd is large), contain.Phosphate-based glass can contain other trace ingredients, for example Praseodymium trioxide (Pr 6o 11) or chromic oxide (Cr 2o 3) etc. oxide compound.
Above-mentioned content is the content with respect to phosphate-based bulk glass, as described below, and when making phosphate-based glass, the mode that reaches the above-mentioned content being calculated by mol% according to each composition in the glass making after making is carried out weighing, the allotment of raw material.
Phosphate-based glass contain 30～75 (% by mole) P 2o 5as main component.Further preferably contain 50～67 (% by mole) P 2o 5.With P 2o 5and CeO 2for the phosphate-based glass of main component, P 2o 5fewer, water tolerance is higher, easily causes but then and is difficult to form glass by crystallization.
P 2o 5content be less than 30 (% by mole) time, glass generation crystallization, it is unstable that vitreousness becomes.In addition, when containing 50 (% by mole) more than P 2o 5time, can obtain the phosphate-based glass that thermal diffusivity is low especially.In addition, P 2o 5be greater than 75 (% by mole) time, weathering resistance can worsen, therefore not preferred.Due to P 2o 5the water tolerance reduction of many times, therefore, further preferred P 2o 5content be 67 (% by mole) below.
CeO 2with P 2o 5be similarly main component, in phosphate-based glass, contain 8～60 (% by mole).Further preferably contain 9～39 (% by mole) CeO 2.CeO 2be less than 8 (% by mole) time, weathering resistance and poor water resistance, therefore not preferred.And then, in order to obtain the phosphate-based glass that thermal diffusivity is lower, preferably contain 9 (% by mole) above CeO 2.
In addition, contain CeO 2more, glass is more unstable, easily causes crystallization, therefore, and preferred CeO 2be 60 (% by mole) below.In addition, CeO 2be 39 (% by mole) when following, can obtain the phosphate-based glass that thermal diffusivity is low.Now, preferably phosphate is that glass is with P 2o 5be the 1st main component, and content compare CeO 2many.
The phosphate-based glass of low thermal diffusivity of the present invention is except containing the P as main component 2o 5, CeO 2oxide compound outside, as other trace ingredients, can contain Pr 6o 11, Cr 2o 3, titanium oxide (TiO 2), barium oxide (BaO), boron oxide (B 2o 3), aluminum oxide (Al 2o 3), zinc oxide (ZnO), strontium oxide (SrO), ferric oxide (Fe 2o 3), lanthanum trioxide (La 2o 3), Neodymium trioxide (Nd 2o 3), Cs2O (Cs 2o), yttrium oxide (Y 2o 3), niobium oxides (Nb 2o 3), manganese oxide (MnO), ytterbium oxide (Yb 2o 3), tantalum oxide (Ta 2o 5), silicon-dioxide (SiO 2), stannic oxide (SnO 2), Lithium Oxide 98min (Li 2o), calcium oxide (CaO), magnesium oxide (MgO), sodium oxide (Na 2o), potassium oxide (K 2o), Calcium Fluoride (Fluorspan) (CaF 2) at least a kind.These oxide compounds are crystallizations in order to suppress glass, adjust second-order transition temperature etc. and add.
The main component of phosphate-based glass is P 2o 5and CeO 2, in the low glass of thermal diffusivity, the 1st main component (ratio of components is maximum) is P 2o 5, while adding other trace ingredients, the 2nd main component (ratio of components the 2nd is large) is CeO 2, but be not limited to this, for example, also can be greater than CeO 2the composition of ratio of components.But, in order to obtain the phosphate-based glass that thermal diffusivity is low, more preferably P 2o 5be the 1st main component, CeO 2it is the 2nd main component.
Phosphate-based glass preferably contain 0～2.2 (% by mole) Pr 6o 11, more preferably contain 0.1～2 (% by mole).P 2o 5while being reduced, becoming gasiform metal phosphorus (P) and evaporate Pr 6o 11there is the P of preventing 2o 5the effect of reduction.Therefore, with P 2o 5, CeO 2for the phosphate-based glass of main component contains Pr 6o 11time, showing the above-mentioned evaporation effect that prevents phosphorus, water tolerance improves.Even if do not contain Pr 6o 11, also can obtain the phosphate-based glass that thermal diffusivity is low, but contain 0.1 (% by mole) above Pr 6o 11time, utilize the above-mentioned evaporation effect that prevents phosphorus, can obtain the glass that water tolerance is high.In addition, Pr 6o 11there is the effect that reduces thermal diffusivity, therefore, in order to obtain the glass that thermal diffusivity is low, preferably in phosphate-based glass, contain.If Pr 6o 11be greater than 2.2 (% by mole), can promote the crystallization of phosphate glass, therefore not preferred.And then, Pr 6o 11even if trace also can obtain the above-mentioned evaporation effect that prevents phosphorus, therefore, more preferably contain 2 (% by mole) following Pr 6o 11.
Phosphate-based glass preferably contain 0～10 (% by mole) Cr 2o 3.Cr 2o 3there is the effect that reduces thermal diffusivity, therefore, more preferably contain 0.2 (% by mole) above Cr 2o 3.In addition, Cr 2o 3be greater than 10 (% by mole) time, can there is the crystallization of glass, therefore not preferred.
Phosphate-based glass preferably contain 0～20 (% by mole) B 2o 3.B 2o 3have and prevent with P 2o 5, CeO 2for the crystallization of the phosphate-based glass of main component, make the effect of stabilization.In the situation that contain other composition that prevents crystallization, even if do not contain B 2o 3, also can prevent the crystallization of phosphate-based glass, due to B 2o 3crystallization inhibition is high, therefore, preferably contain 2 (% by mole) more than.In addition, B 2o 3be greater than 20 (% by mole) time, the weathering resistance of the phosphate-based glass obtaining is poor, therefore not preferred.B 2o 3be 8 (% by mole) when following, can obtain the phosphate-based glass that thermal diffusivity is low.
Phosphate-based glass preferably contain 0～10 (% by mole) Al 2o 3.Al 2o 3be greater than 10 (% by mole) time, promote the crystallization of glass, therefore not preferred.In addition, due to Al 2o 3there is the effect that improves second-order transition temperature, therefore, even 0～10 (% by mole) scope in Al 2o 3content when high, also can make the phosphate-based glass that thermotolerance is high.
Phosphate-based glass preferably contain 0～20 (% by mole) TiO 2.In addition, can contain BaO:0～17 (% by mole), ZnO:0～13.4 (% by mole), SrO:0～16 (% by mole), Fe 2o 3: 0～2.5 (% by mole), La 2o 3: 0～5 (% by mole), Nd 2o 3: 0～2 (% by mole), Cs 2o:0～4 (% by mole), Y 2o 3: 0～4 (% by mole), Nb 2o 3: 0～4 (% by mole), MnO:0～4 (% by mole), Yb 2o 3: 0～2 (% by mole), Ta 2o 5: 0～5 (% by mole), SiO:0～10 (% by mole), SnO 2: 0～10 (% by mole), Li 2o:0～4 (% by mole), CaO:0～4 (% by mole), MgO:0～4 (% by mole), Na 2o:0～1.5 (% by mole), K 2o:0～1.5 (% by mole), CaF 2: 0～1 (% by mole).These compositions add in order to suppress crystallization, the adjustment second-order transition temperature of glass, and each composition, when above-mentioned scope, can obtain the phosphate-based glass that thermal diffusivity is low.In addition, the content of each composition, than in the many situations of above-mentioned scope, causes phosphate-based glass crystallization sometimes, therefore not preferred.
With P 2o 5and CeO 2for contained composition in the phosphate-based glass of main component is not limited to these oxide compounds, for example, also can contain ferric oxide (II) (FeO), cerium oxide (II) (CeO), bismuth oxide (Bi 2o 3), cupric oxide (CuO), vanadium oxide (V 2o 5), cobalt oxide (CoO), nickel oxide (NiO), zirconium white (ZrO 2) etc. oxide compound.
The assembly that forms above-mentioned phosphate-based glass is divided while amounting to, be 100 (% by mole).
After composition as above is measured in accordance with regulations and weighed and mix, heat, thereby make glass.For example, as phosphoric acid, use the former phosphoric acid dewatered, with reach specified amount % by mole mode weigh, and similarly weigh CeO 2, other Pr 6o 11, Cr 2o 3, Al 2o 3, BaO etc., then use mortar that these compositions are pulverized, fully mix, to reach even simultaneously.The powdered glass material composition being uniformly mixed into is put into for example crucible of platinum system, and use electric furnace is in atmosphere, with the temperature heating specified times of approximately 1000～1500 ℃ and make its melting.Now, heat-up rate is not particularly limited, and can carry out rapid heating with the heat-up rate of 10 ℃/min.
, be configured as tabular or bar-shaped, carry out coolingly simultaneously, more tabular or bar-shaped phosphate-based glass is pulverized, make pulverous phosphate-based glass thereafter.It should be noted that, preferably, before hybrid glass raw material, the component of glass raw material of powdery is sieved, make particle diameter be tending towards certain size when following, glass is more even.
The phosphate-based glass being obtained by the present invention is transparent, presents the colors such as yellow, yellow-green colour, green, brown or black according to the trace ingredients being added.
It should be noted that, because phosphate-based glass of the present invention keeps stable vitreousness, therefore, and even the glass of for example vitreousness is heated and cooling again, can crystallization yet, can again return to vitreousness.
The phosphate-based glass of of the present invention low thermal diffusivity obtaining according to above-mentioned composition, diffusivity can be set in 0.27～0.39 (mm 2/ second) in scope.In the past, high for the thermal diffusivity of the silicate Glass of various uses, for example fused quartz was 0.88 (mm 2/ second).Therefore,, even if silicate Glass is used for to substrate or the glaze layer of thermal head, can not make the low thermal head of power consumption.In addition, the glass using in the glaze layer of existing thermal head is presumed to borosilicate (silicate Glass), while measuring the thermal diffusivity of this glass, is 0.53 (mm 2/ second).Therefore, in existing thermal head, there are the following problems: due in the situation that the thermal diffusivity of glaze layer or do not form glaze layer and form the thermal diffusivity of substrate of substrate with glass high, so need a large amount of electric power during heating, electrical efficiency is low.
The phosphate-based glass of low thermal diffusivity of the present invention is compared with existing silicate Glass, and thermal diffusivity is little.The glass of the present invention that thermal diffusivity is especially little is existing silicate Glass approximately 1/2, even if the larger glass of the thermal diffusivity in the present invention is compared with existing silicate Glass, also reduces approximately 20%.As mentioned above, because thermal diffusivity is little, therefore, while forming the substrate of thermal head with the phosphate-based glass of low thermal diffusivity of the present invention, the heat producing in heating resistor layer is few to the heat radiation of substrate, can power consumption be suppressed lowlyer.In addition, use the phosphate-based glass of low thermal diffusivity of the present invention to form the glaze layer of thermal head, be also difficult to transfer heat to the substrate below it, therefore, can power consumption be suppressed lowlyer equally.
The thermal diffusivity of phosphate-based glass is 0.31 (mm 2/ second) when following, can more appropriately be used as the substrate of thermal head.Thermal diffusivity is 0.31 (mm 2/ second) following phosphate glass, because thermal diffusivity is low especially, therefore, while being used as the substrate of thermal head, can be accumulated the heat producing in heating resistor layer in substrate.Therefore, the heat being produced by heating resistor layer is few, power consumption can be suppressed to low especially.
The coefficient of thermal expansion coefficient (α) of phosphate-based glass of the present invention can be controlled at 60～108 (* 10 - 7/ ℃) scope in.
While utilizing phosphate-based glass to form the substrate of thermal head, do not need to form glaze layer, therefore, what can not occur that the difference of the coefficient of thermal expansion coefficient (α) of baseplate material and glazing material layer produces peels off.Therefore, do not exist and must form the such restriction of glaze layer by the phosphate-based glass with the coefficient of thermal expansion coefficient (α) roughly the same with the coefficient of thermal expansion coefficient (α) of substrate, can expand the range of choice of the glass material that forms substrate.Therefore, can not consider the value of coefficient of thermal expansion coefficient (α) and with the less phosphate-based glass formation substrate of the value of thermal diffusivity, therefore, can the power consumption of thermal head is suppressed to lower.In this case, if the coefficient of thermal expansion coefficient (α) of substrate is excessive, can there is large distortion in substrate self, and therefore, the coefficient of thermal expansion coefficient (α) of phosphate-based glass that is preferably formed substrate is less.
The coefficient of thermal expansion coefficient (α) of aluminum oxide is 66～76 (* 10 -7/ ℃) scope.Therefore, if the phosphate-based glass roughly the same with coefficient of thermal expansion coefficient (α) and the coefficient of thermal expansion coefficient (α) of this aluminum oxide forms glaze layer, while again substrate being made as to aluminum oxide, can the coefficient of thermal expansion coefficient (α) of substrate and glaze layer be set as roughly the same.Thus, when using thermal head, even if the heat producing in heating resistor layer passes to glaze layer and substrate, between glaze layer and ceramic substrate, be also difficult to occur that difference because of coefficient of thermal expansion causes peels off, thereby, excellent in te pins of durability.
Because the thermal diffusivity of phosphate-based glass of the present invention is low, therefore, by selecting thermal expansivity (α) in above-mentioned 66～76 (* 10 -7/ ℃) scope in glass, just not can with strippable substrate, and can form the glaze layer of accumulation of heat effect excellence.
Phosphate-based glass of the present invention can be set in the scope of 520～700 ℃ by second-order transition temperature (Tg).As mentioned above, because thermotolerance is high, therefore, be used in the substrate of thermal head, also can not cause and add thermogenetic deformation and metamorphism.Along with the high speed of thermal printer, the heat that is sometimes applied to thermal head also reaches 500 ℃, but the high of the present invention phosphate-based glass of thermotolerance can be compatibly for aforesaid substrate.In addition, due to excellent heat resistance, therefore, can be preferably used as glaze layer.
Use the phosphate-based glass of low thermal diffusivity obtaining in the present invention, by the thermal head 1 shown in following manufacture method shop drawings 1.It should be noted that, the thermal head shown in Fig. 1 is an example, and the shape of the thermal head preferably using in present embodiment etc. is not limited to the shape shown in Fig. 1.A part for substrate shown in Fig. 1 is the shape that bulges into semicylinder shape, but for example, also can make the smooth plane substrate that there is no protrusion.
As mentioned above, the glass that the composition that becomes frit is mixed, heated and makes, then this glass is pulverized, making particle diameter is the powder below 5 μ m.To the temperature more than softening temperature of glass, utilize the methods such as float glass process to be configured as tabular this pulverous glass heats.The part that bulges into the semicylinder shape shown in Fig. 1 can utilize methods such as spraying processing to form.
On the above substrate 11 forming, form heating resistor layer 13, conductor layer 14 and protective layer 15.Heating resistor layer 13 is to utilize for example Ta-SiO of the generals such as sputtering method 2, or Ta 2n is filmed and forms, and conductor layer 14 utilizes sputtering method etc. that for example Al is filmed and is formed, and then protective layer 15 utilizes sputtering method etc. that for example SIALON (mixture consisting of Si, Al, O and N) is filmed and is formed.
In the thermal head 1 of making above, owing to forming substrate with the phosphate-based glass of low thermal diffusivity of the present invention, so the thermal diffusivity of substrate is low, and power consumption is little.In addition, the second-order transition temperature of substrate is high, and therefore, the thermotolerance of thermal head 1 is high.
It should be noted that, also can in the glaze layer shown in Fig. 2, use the phosphate-based glass of low thermal diffusivity of the present invention.In this case, the paste that coating contains phosphate-based glass of the present invention on the ceramic substrate 11 of aluminum oxide, and burn till with electric furnace, thereby form glaze layer 12.The thickness of the glaze layer after burning till is preferably 50～250 μ m.And, if the coefficient of thermal expansion coefficient (α) of use and aluminum oxide phosphate-based glass about equally, the coefficient of thermal expansion coefficient (α) of glaze layer 12 equates with the coefficient of thermal expansion coefficient (α) of aluminum oxide as ceramic substrate 11, therefore, be difficult for causing peeling off between glaze layer 12 and ceramic substrate 11, can make the glaze layer of excellent in te pins of durability.
Embodiment
Making have the ratio of components shown in table 1 (% by mole) phosphate-based glass.Press shown in table 1, weigh each regulation raw material, is mixed after, put into platinum crucible, in the electric furnace of 1000～1500 ℃, heat also melting in 30 minutes, cooling in, be configured as bar-shapedly, obtain phosphate-based glass.Phosphate-based glass shown in table 1 is all at P 2o 5be 30～75 (% by mole), CeO 2be 8～60 (% by mole) scope in so that at P 2o 5be 50～67 (% by mole), CeO 2be 9～39 (% by mole) scope in.
The phosphate-based glass with the moiety of embodiment 1～132 can crystallization, can make good phosphate-based glass.
The phosphate-based glass being obtained by forming shown in each embodiment is carried out to thermal diffusivity (mm 2/ second), the mensuration of coefficient of thermal expansion coefficient (α), second-order transition temperature (Tg), be shown in identical table.
As shown in table 1, the thermal diffusivity of phosphate-based glass of the present invention is 0.27～0.39 (mm 2/ second).The thermal diffusivity of fused quartz is 0.88 (mm 2/ second), for the thermal diffusivity of the glass of the glaze layer of existing thermal head, be 0.53 (mm 2/ second), learn thus: phosphate-based glass of the present invention is compared with existing silicate Glass, and thermal diffusivity is low.
Therefore, as mentioned above, while forming the substrate of the thermal head shown in Fig. 1 with the low glass of thermal diffusivity, can power consumption be suppressed lowlyer, realize the raising of electrical efficiency.And thermal diffusivity is 0.31 (mm 2/ second) following phosphate-based glass can particularly preferably be used as the substrate of thermal head.In addition, phosphate-based glass of the present invention can form the glaze layer 12 shown in Fig. 2.Now, if use coefficient of thermal expansion coefficient (α) at the coefficient of thermal expansion coefficient 66～76 (* 10 of aluminum oxide -7/ ℃) scope in glass, be difficult for there is peeling off between substrate and glaze layer, therefore, can make the glaze layer of excellent in te pins of durability.
As shown in table 1, there is the phosphate-based glass of the moiety of embodiment 1～132, its second-order transition temperature (Tg) in the scope of 520～700 ℃, excellent heat resistance.In addition, coefficient of thermal expansion coefficient is 60～108 (* 10 -7/ ℃) scope in, the distortion being caused by heating is little, therefore, can be aptly as the substrate of thermal head.

Claims (6)

1. the phosphate-based glass of low thermal diffusivity, is characterized in that, it is with P 2o 5be the 1st principal constituent, with CeO 2be the 2nd main component, be calculated by mol%, contain 50～67% P 2o 5, contain 9～39% CeO 2, also contain 2～8% B 2o 3, and thermal diffusivity is 0.31mm 2below/second.
2. the phosphate-based glass of low thermal diffusivity according to claim 1, wherein, the Pr that contains 0.1～2 % by mole 6o 11.
3. the phosphate-based glass of low thermal diffusivity according to claim 1 and 2, wherein, the Cr that contains 0～10 % by mole 2o 3.
4. the phosphate-based glass of low thermal diffusivity, is characterized in that, it is with P 2o 5be the 1st principal constituent, with CeO 2be the 2nd main component, be calculated by mol%, contain 50～67% P 2o 5, contain 9～39% CeO 2, also contain 2～8% B 2o 3, thermal diffusivity is 0.27～0.39mm 2/ second.
5. a thermal head, it is formed with heating resistor layer and protective layer on substrate, it is characterized in that, utilizes the phosphate-based glass of low thermal diffusivity described in claim 1 to form described substrate.
6. thermal head according to claim 5 wherein, is formed with conductor layer on described heating resistor layer.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4742362A (en) * 1985-10-23 1988-05-03 Alps Electric Co., Ltd. Thermal head

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JP4597794B2 (en) * 2005-07-01 2010-12-15 アルプス電気株式会社 Phosphate glass, bonding material using phosphate glass, magnetic head using the bonding material, and plasma display panel
JP5080778B2 (en) * 2006-05-22 2012-11-21 アルプス電気株式会社 Phosphate glass and electronic components using phosphate glass
JP5140068B2 (en) * 2007-03-09 2013-02-06 アルプス電気株式会社 Phosphate glass and thermal head using phosphate glass

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4742362A (en) * 1985-10-23 1988-05-03 Alps Electric Co., Ltd. Thermal head

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* Cited by examiner, † Cited by third party
Title
JP特开2007-8777A 2007.01.18

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