WO2022158457A1 - 積層部材およびガラス組成物 - Google Patents

積層部材およびガラス組成物 Download PDF

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Publication number
WO2022158457A1
WO2022158457A1 PCT/JP2022/001654 JP2022001654W WO2022158457A1 WO 2022158457 A1 WO2022158457 A1 WO 2022158457A1 JP 2022001654 W JP2022001654 W JP 2022001654W WO 2022158457 A1 WO2022158457 A1 WO 2022158457A1
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WIPO (PCT)
Prior art keywords
mol
glass
sic
laminated
linear expansion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/001654
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English (en)
French (fr)
Japanese (ja)
Inventor
優 塙
修平 小川
誠二 稲葉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to JP2022576695A priority Critical patent/JP7589757B2/ja
Priority to KR1020237024361A priority patent/KR20230135064A/ko
Priority to CN202280010574.XA priority patent/CN116745251A/zh
Publication of WO2022158457A1 publication Critical patent/WO2022158457A1/ja
Priority to US18/353,977 priority patent/US12410105B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
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    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6581—Total pressure below 1 atmosphere, e.g. vacuum
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
    • C04B2235/725—Metal content
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/36—Non-oxidic
    • C04B2237/365—Silicon carbide

Definitions

  • the present invention relates to a glass composition used for a laminated member and a glass member that constitutes the laminated member.
  • Worktop materials include stainless steel, artificial marble, and ceramics.
  • the heating cooker is built into the opening provided on the worktop.
  • a heating cooker includes a top plate on which an object to be heated (pot, etc.) is placed. Examples of materials for the top plate include crystallized glass (see Patent Document 1) and ceramics.
  • Patent Document 2 and Patent Document 3 disclose inspection apparatuses and test apparatuses for inspecting electrical characteristics of electronic devices.
  • the mounting table in the inspection apparatus of Patent Document 2 is made of ceramic, quartz, or glass. It has a structured stage lid and cooling unit.
  • the heating member used for the top plate has a structure capable of rapidly heating in order to control the temperature within a predetermined temperature range with respect to the set temperature, and cooling (heat absorption) for protecting the temperature sensor section including the electronic device. ) structure. Therefore, the heating member is required to have excellent temperature rise property and impact resistance.
  • the inventors of the present invention evaluated a laminated member having a glass member, a resin bonding layer, and a Si—SiC member as conventional heating members. It was found that there is room for improvement.
  • an object of the present invention is to provide a laminated member excellent in temperature rise property, impact resistance and thermal shock resistance, and a glass composition used for a glass member constituting the laminated member.
  • the present inventors have found a laminated member having a glass member with a predetermined in-line transmittance, a bonding layer containing a resin, and a Si—SiC member, wherein the composition of the glass member is is within a predetermined range, and the average linear expansion coefficient ⁇ of the Si—SiC member, the average linear expansion coefficient ⁇ of the glass member, and the absolute value of the difference between ⁇ and ⁇ (
  • the present inventors have found that, within the range, they are excellent in temperature rise property, impact resistance, and thermal shock resistance, and have completed the present invention.
  • the above glass member contains SiO 2 of 55.0 to 85.0 mol %, Al 2 O 3 of 1.5 to 22.0 mol %, and 2.0 to 14.0 mol % in terms of mol percentages based on oxides.
  • the total content of the SiO 2 , the Al 2 O 3 , the B 2 O 3 and the P 2 O 5 is 70.0 to 97.0% in terms of molar percentage based on oxides
  • the Si—SiC member has an average linear expansion coefficient ⁇ at 20 to 200° C.
  • the glass member has an average linear expansion coefficient ⁇ of 1.50 to 5.00 ppm/°C at 20 to 200°C,
  • of the value obtained by subtracting the average linear expansion coefficient ⁇ of the glass member at 20 to 200°C from the average linear expansion coefficient ⁇ of the Si—SiC member at 20 to 200°C is 2.00 ppm/°C or less.
  • a laminated member. [2] The glass member contains 60.0 to 78.0 mol % of SiO 2 , 8.0 to 18.0 mol % of Al 2 O 3 , and 2.0 mol % based on oxides.
  • the laminated member as described in . [3] The total content of RO and ZnO in the glass member is 2.0 to 25.0% in terms of molar percentage based on oxides; The laminated member according to [1] or [2], wherein the total content of R 2 O in the glass member is 0 to 15.0% in terms of molar percentage based on oxides. [4] The glass member has an average coefficient of linear expansion ⁇ of 2.00 to 3.50 ppm/° C., a Young's modulus of 40 to 120 GPa, and a melting temperature of 1000 to 2000° C.
  • Laminated member according to. [12] The laminated member according to any one of [1] to [11], wherein the Si—SiC member has a Young's modulus of 300 to 420 GPa. [13] The laminated member according to any one of [1] to [12], wherein the Si—SiC member has a metal Si content of 8 to 60% by mass. [14] The laminate member according to any one of [1] to [13], wherein the resin has a heat resistance temperature of 120 to 420°C.
  • a laminated member comprising a glass member, a bonding layer containing a resin on the glass member, and a Si—SiC member on the bonding layer, wherein the glass composition is used for the glass member,
  • the glass composition has a linear transmittance of 80% or more at a wavelength of 850 nm
  • the above glass composition contains 55.0 to 85.0 mol % SiO 2 , 1.5 to 22.0 mol % Al 2 O 3 , and 2.0 to 14 0 mol % B 2 O 3 and 0 to 5.0 mol % P 2 O 5 ,
  • the total content of SiO 2 , Al 2 O 3 , B 2 O 3 and P 2 O 5 is 70.0 to 97.0 in terms of molar percentage based on oxides.
  • the glass composition has an average linear expansion coefficient ⁇ of 1.50 to 5.00 ppm/°C at 20 to 200°C
  • the above glass composition is used for a laminated member having a Si—SiC member having an average linear expansion coefficient ⁇ of 2.85 to 4.00 ppm/° C. at 20 to 200° C.
  • of the value obtained by subtracting the average linear expansion coefficient ⁇ of the glass member at 20 to 200° C. from the average linear expansion coefficient ⁇ at 200° C. is used so that it is 2.00 ppm/° C. or less. glass composition.
  • the total content of the SiO 2 , the Al 2 O 3 , the B 2 O 3 and the P 2 O 5 is 70.0 to 97.0% in terms of molar percentage based on oxides
  • the average linear expansion coefficient ⁇ at 20 to 200 ° C. is 1.50 to 5.00 ppm / ° C.
  • the present invention it is possible to provide a laminated member excellent in temperature rise property, impact resistance, and thermal shock resistance, and a glass composition used for a glass member constituting the laminated member.
  • FIG. 1 is a cross-sectional view schematically showing a laminated member of one embodiment of the present invention.
  • a numerical range represented using “to” means a range including the numerical values described before and after “to” as lower and upper limits.
  • a laminated member of the present disclosure includes a glass member having a linear transmittance of 80% or more at a wavelength of 850 nm, a bonding layer containing a resin on the glass member, and a Si—SiC member on the bonding layer,
  • the above glass member contains SiO 2 of 55.0 to 85.0 mol %, Al 2 O 3 of 1.5 to 22.0 mol %, and 2.0 to 14.0 mol % in terms of mol percentages based on oxides.
  • the average linear expansion coefficient ⁇ of the Si—SiC member at 20 to 200 ° C. is 2.85 to 4.00 ppm/ ° C.
  • the average linear expansion coefficient ⁇ of the glass member at 20 to 200° C. is 1.50 to 5.00 ppm/° C.
  • the average linear expansion coefficient ⁇ of the Si—SiC member at 20 to 200° C. is 2.00 ppm/° C. or less.
  • the laminated member of the present disclosure is excellent in temperature rise, impact resistance, and thermal shock resistance. Although the details of this reason have not been clarified yet, it is presumed that the reason is generally as follows.
  • the bonding layer functions as a cushioning material, improving impact resistance.
  • FIG. 1 is a cross-sectional view schematically showing a laminated member of one embodiment of the present invention.
  • the laminated member 100 has a glass member 101 , a bonding layer 103 arranged on the glass member 101 , and a Si—SiC member 105 arranged on the bonding layer 103 .
  • the laminated member 100 has a laminated structure in which a glass member 101, a bonding layer 103, and a Si—SiC member 105 are laminated in this order.
  • a Si—SiC member means a sintered member made of a composite material containing silicon carbide (SiC) and silicon (Si) (metallic Si).
  • the Si—SiC member 105 is preferably a ceramic containing 40 to 92% by mass of SiC and 8 to 60% by mass of Si with respect to the total mass of the Si—SiC member, and 50 to 87% by mass of Si. It is more preferably a ceramic containing SiC and 13 to 50% by mass of Si, more preferably a ceramic containing 55 to 82% by mass of SiC and 18 to 45% by mass of Si. Particularly preferred are ceramics containing 77% by weight SiC and 23-40% by weight Si, most preferably 65-72% by weight SiC and 28-35% by weight Si. preferable.
  • the Si--SiC member 105 has an excellent balance between thermal properties and mechanical properties.
  • the composition of the Si—SiC member 105 is not particularly limited as long as it contains SiC and Si.
  • sintering aids include, but are not limited to, BeO, B4C , BN, Al, and AlN.
  • the thickness of the Si--SiC member 105 is preferably 0.5-15 mm.
  • the thickness of the Si—SiC member 105 is more preferably 1.5 mm or more, more preferably 2.0 mm or more, and particularly preferably 2.5 mm or more.
  • the thickness of the Si—SiC member 105 is more preferably 10.0 mm or less, more preferably 7.5 mm or less, and particularly preferably 5.5 mm or less.
  • the Si--SiC member 105 can be made thinner by being supported by the glass member 101. Since the Si—SiC member 105 can be made thin, it is possible to raise and lower the temperature quickly.
  • the thickness of the Si--SiC member 105 can be measured, for example, with a vernier caliper or a digital measure.
  • the average linear expansion coefficient ⁇ of the Si—SiC member 105 at 20 to 200°C is 2.85 to 4.00 ppm/°C.
  • the average linear expansion coefficient ⁇ of the Si—SiC member 105 at 20 to 200° C. is also simply referred to as the average linear expansion coefficient ⁇ .
  • the average linear expansion coefficient ⁇ is preferably 2.90 ppm/°C or higher, more preferably 2.95 ppm/°C or higher, and particularly preferably 3.00 ppm/°C or higher.
  • the average coefficient of linear expansion ⁇ is preferably 3.40 ppm/°C or less, more preferably 3.20 ppm/°C or less, and particularly preferably 3.10 ppm/°C or less.
  • the average coefficient of linear expansion ⁇ of the Si—SiC member 105 is within the above range, the average coefficients of linear expansion of the Si—SiC member 105 and the glass member 101 can easily match or approach each other.
  • the thermal conductivity and strength of the Si—SiC member 105 can be increased, the impact resistance can be increased while increasing the rate of temperature rise.
  • the average linear expansion coefficient ⁇ can be measured with a thermal dilatometer (dilatometer) whose temperature range is 20°C to 200°C, or a thermomechanical analyzer (TMA).
  • dilatometer thermal dilatometer
  • TMA thermomechanical analyzer
  • a method for adjusting the average linear expansion coefficient ⁇ of the Si—SiC member 105 to the above range includes a method of adjusting the contents of SiC and Si within the above range.
  • the thermal conductivity of the Si—SiC member 105 at 20° C. is preferably 130 to 300 W/m ⁇ K.
  • the thermal conductivity of the Si—SiC member 105 at 20° C. is more preferably 190 W/m ⁇ K or more, more preferably 210 W/m ⁇ K or more, and particularly preferably 225 W/m ⁇ K or more.
  • the thermal conductivity of the Si—SiC member 105 at 20° C. is more preferably 270 W/m ⁇ K or less, even more preferably 260 W/m ⁇ K or less, and particularly preferably 250 W/m ⁇ K or less.
  • the thermal conductivity of the Si—SiC member 105 at 20° C. is within the above range, the uniformity of heat as a heating member is improved.
  • the thermal conductivity of the Si—SiC member 105 is within the above range, it is possible to prevent a decrease in yield due to variations in thermal conductivity when manufacturing the Si—SiC member 105, and the quality of the Si—SiC member 105 can be improved. easy to stabilize.
  • the thermal conductivity of the Si—SiC member 105 at 20° C. can be measured by, for example, a laser flash method.
  • the Young's modulus of the Si—SiC member 105 is preferably 300 to 420 GPa.
  • the Young's modulus of the Si—SiC member 105 is more preferably 320 GPa or higher, more preferably 350 GPa or higher, and particularly preferably 370 GPa or higher.
  • the Young's modulus of the Si—SiC member 105 is more preferably 410 GPa or less, more preferably 400 GPa or less, and particularly preferably 390 GPa or less.
  • the Si—SiC member 105 is preferable because the thermal shock resistance is improved when the Young's modulus satisfies the above range.
  • the Si—SiC member 105 has a lower Young's modulus than other silicon carbide ceramics, it has high thermal shock resistance, which is preferable.
  • the Young's modulus of the Si—SiC member 105 can be measured at 20° C. by the elastic modulus test method (ultrasonic pulse method: dynamic elastic modulus) described in Japanese Industrial Standards (JIS R1602:1995).
  • a method for adjusting the Young's modulus of the Si—SiC member 105 within the above range includes a method for adjusting the contents of SiC and Si within the above range.
  • the bending strength of the Si--SiC member 105 is preferably 130-300 MPa.
  • the bending strength of the Si—SiC member 105 is preferably 200 MPa or higher, more preferably 220 MPa or higher, and particularly preferably 230 MPa or higher.
  • the bending strength of the Si—SiC member 105 is more preferably 260 MPa or less, more preferably 250 MPa or less, and particularly preferably 240 MPa or less.
  • the bending strength of the Si-SiC member 105 can be measured at 20°C by the bending strength test method (4-point bending strength) described in Japanese Industrial Standards (JIS R1601:2008).
  • the Vickers hardness (Hv) of the Si--SiC member 105 is preferably 20-27 GPa.
  • the Vickers hardness is more preferably 21 GPa or higher, even more preferably 22 GPa or higher, and particularly preferably 23 GPa or higher.
  • the Vickers hardness is more preferably 26 GPa or less, more preferably 25 GPa or less, and particularly preferably 24 GPa or less.
  • the Vickers hardness of the Si-SiC member 105 can be measured at 20°C by a Vickers hardness meter system.
  • Glass member 101 examples include soda lime glass, borosilicate glass, aluminosilicate glass, and alkali-free glass.
  • the glass member 101 may be chemically strengthened glass (chemically strengthened glass), glass physically strengthened by air cooling or the like (physically strengthened glass), or glass subjected to crystallization treatment (crystallized glass). .
  • the glass composition of the glass member 101 will be described below.
  • the glass composition (the content of the target component of the glass member) in the present specification is expressed in terms of mol percentage (mol %) based on oxides.
  • the glass member 101 contains SiO2 .
  • SiO2 is the main component of glass.
  • the content of SiO2 is 55.0 mol% or more, preferably 57.0 mol% or more, more preferably 60.0 mol% or more, and 62.0 mol% or more, from the viewpoint of enhancing the weather resistance of the glass. is particularly preferred.
  • the content of SiO 2 is 85.0 mol % or less, preferably 83.0 mol % or less, more preferably 80.0 mol % or less, from the viewpoint of lowering the melting temperature of the glass and improving productivity, 78.0 mol % or less is particularly preferred.
  • Glass member 101 contains Al 2 O 3 .
  • Al 2 O 3 By containing Al 2 O 3 , the weather resistance of the glass can be enhanced and the coefficient of linear expansion can be lowered.
  • the content of Al 2 O 3 is 1.5 mol % or more, preferably 3.0 mol % or more, more preferably 5.0 mol % or more, more preferably 8.0 mol %, in order to increase the Young's modulus of the glass. mol % or more is particularly preferred.
  • the content of Al 2 O 3 is 22.0 mol % or less from the viewpoint of increasing the acid resistance of the glass.
  • the point of suppressing the devitrification of the glass the point of suppressing the generation of unmelted materials of the raw material, and the point of suppressing the increase in the melting temperature of the glass to improve the clarity
  • 18.0 mol % or less is preferable, 17.0 mol % or less is more preferable, and 16.0 mol % or less is particularly preferable.
  • Glass member 101 contains B 2 O 3 .
  • B 2 O 3 By containing B 2 O 3 , the coefficient of linear expansion of the glass can be adjusted.
  • the content of B 2 O 3 is 2.0 mol % or more, preferably 3.5 mol % or more, particularly preferably 5.0 mol % or more, from the viewpoint of suppressing the linear expansion coefficient of the glass.
  • the content of B 2 O 3 is 14.0 mol % or less from the viewpoint of improving the weather resistance of the glass. From the viewpoint of increasing the Young's modulus of the glass, it is preferably 11.0 mol% or less, more preferably 10.0 mol% or less, even more preferably 8.5 mol% or less, and particularly preferably 7.5 mol% or less. .
  • the glass member 101 may or may not contain RO.
  • RO means at least one of MgO, CaO, SrO and BaO.
  • the content of RO represents the total amount of MgO, CaO, SrO and BaO.
  • the total content of RO and ZnO is preferably 2.0 mol% or more, more preferably 3.0 mol% or more, from the viewpoint of lowering the melting temperature of the glass, improving the solubility, and controlling the coefficient of linear expansion. , more preferably 4.0 mol % or more, and particularly preferably 5.0 mol % or more.
  • the total content of RO and ZnO is preferably 25.0 mol% or less, more preferably 20.0 mol% or less, from the viewpoint of lowering the devitrification temperature of the glass, improving productivity, and controlling the coefficient of linear expansion. It is preferably 16.0 mol % or less, more preferably 15.0 mol % or less.
  • MgO may be contained in order to lower the melting temperature of the glass, improve the solubility, and control the coefficient of linear expansion.
  • the content of MgO is preferably 1.0 mol% or more, more preferably 2.0 mol% or more, still more preferably 2.5 mol% or more, and particularly preferably 3.0 mol% or more.
  • the content of MgO is preferably 15.0 mol % or less, more preferably 12.0 mol % or less, from the viewpoint of lowering the devitrification temperature of the glass to increase productivity and controlling the coefficient of linear expansion. 0 mol % or less is more preferable, and 9.0 mol % or less is particularly preferable.
  • CaO may be contained in order to lower the melting temperature of the glass, improve the solubility, and control the coefficient of linear expansion.
  • the content of CaO is preferably 0.5 mol% or more, more preferably 1.0 mol% or more.
  • the content of CaO is preferably 10.0 mol% or less, more preferably 8.0 mol% or less.
  • SrO may be contained in order to lower the melting temperature of the glass, improve the solubility, and control the coefficient of linear expansion.
  • the content of SrO is preferably 0 mol % or more, more preferably 0.01 mol % or more, and even more preferably 0.1 mol % or more.
  • the SrO content is preferably 5.0 mol% or less, more preferably 3.0 mol% or less, and even more preferably 2.0 mol% or less.
  • BaO may be contained in order to lower the melting temperature of glass, increase productivity, and control the coefficient of linear expansion.
  • the content of BaO is preferably 0 mol% or more, more preferably 0.01 mol% or more.
  • the content of BaO is preferably 3.0 mol% or less, more preferably 2.0 mol% or less.
  • BaO is not intentionally included, it may be mixed as an impurity derived from raw materials such as limestone, dolomite, strontium carbonate, etc. or from the manufacturing process.
  • the glass member 101 may or may not contain R 2 O.
  • R2O means at least one of Li2O, Na2O and K2O .
  • the content of R2O represents the total amount of Li2O, Na2O and K2O .
  • R 2 O is a useful component for promoting the melting of glass raw materials and adjusting the coefficient of linear expansion, melting temperature, and the like.
  • the content of R 2 O is preferably 0 mol % or more, more preferably 0.01 mol % or more, in order to satisfactorily exhibit the above effects.
  • the content of R 2 O is preferably 15.0 mol % or less, more preferably 10.0 mol % or less, from the viewpoint that the linear expansion coefficient of the glass can be reduced and the stress generated at the time of temperature change can be reduced. , is more preferably 6.0 mol % or less, and particularly preferably 5.0 mol % or less.
  • the total amount of R 2 O, that is, Na 2 O and K 2 O when Li 2 O is not contained is preferably 0 mol % or more, more preferably 0.01 mol % or more.
  • the total amount of R 2 O when Li 2 O is not contained, that is, Na 2 O and K 2 O, is preferably 13.0 mol% or less, and 10.0 mol% or less, from the viewpoint of reducing the coefficient of linear expansion. It is more preferably 5.0 mol % or less, and particularly preferably 3.0 mol % or less.
  • Li 2 O is a useful component for promoting the melting of glass raw materials and adjusting the linear expansion coefficient, melting temperature, and the like.
  • the content of Li 2 O is preferably 0 mol % or more, more preferably 0.01 mol % or more.
  • the content of Li 2 O is preferably 10.0 mol % or less, more preferably 7.0 mol % or less, from the viewpoint of reducing the linear expansion coefficient of the glass and reducing the stress generated at the time of temperature change. , is more preferably 5.0 mol % or less, and particularly preferably 4.0 mol % or less.
  • Na 2 O is a useful component for promoting the melting of glass raw materials and adjusting the coefficient of linear expansion, melting temperature, and the like.
  • the content of Na 2 O is preferably 0 to 13.0 mol %.
  • the content of Na 2 O is more preferably 0.01 mol % or more.
  • the Na 2 O content is more preferably 10.0 mol % or less, even more preferably 5.0 mol % or less, and particularly preferably 3.0 mol % or less. If the content of Na 2 O is 13.0 mol % or less, the coefficient of linear expansion of the glass can be reduced, and the stress generated when the temperature changes can be reduced.
  • K 2 O is a useful component for promoting the melting of glass raw materials and adjusting the linear expansion coefficient, melting temperature, and the like.
  • the content of K 2 O is preferably 0 mol % or more, more preferably 0.01 mol % or more.
  • the content of K 2 O is preferably 3.0 mol % or less, and preferably 1.0 mol % or less, in order to reduce the linear expansion coefficient of the glass and reduce the stress generated when exposed to high temperatures. More preferably, 0.1 mol % or less is even more preferable.
  • the glass member 101 may or may not contain ZrO 2 .
  • ZrO 2 When containing ZrO2, the chemical resistance of the glass can be improved.
  • the content of ZrO 2 is preferably 0 mol % or more, more preferably 0.01 mol % or more, and even more preferably 0.1 mol % or more, from the viewpoint that the above effects can be satisfactorily exhibited.
  • the content of ZrO2 is preferably 5.0 mol% or less, more preferably 3.0 mol% or less, and further preferably 2.0 mol% or less, from the viewpoint of lowering the devitrification temperature of the glass and improving productivity. preferable.
  • the glass member 101 may or may not contain TiO 2 .
  • TiO 2 When TiO 2 is contained, the chemical resistance of the glass can be improved.
  • the content of TiO 2 is preferably 0 mol % or more, more preferably 0.01 mol % or more, and even more preferably 0.1 mol % or more, from the viewpoint that the above effects can be satisfactorily exhibited.
  • the content of TiO 2 is preferably 5.0 mol % or less, more preferably 3.0 mol % or less, from the viewpoints of lowering the devitrification temperature of the glass to increase productivity and suppressing unnecessary coloring. 2.0 mol % or less is more preferable.
  • the glass member 101 may or may not contain P 2 O 5 .
  • P 2 O 5 When P 2 O 5 is contained, crystallization of the glass can be suppressed and the glass can be stabilized.
  • the content of P 2 O 5 is 0 mol % or more. Moreover, from the point that the said effect can be exhibited satisfactorily, 0.05 mol% or more is preferable and 0.1 mol% or more is more preferable.
  • the content of P 2 O 5 is 5.0 mol % because the glass can be stabilized without increasing the melting temperature of the glass too much and the phase separation of the glass can be suppressed to improve the transparency.
  • 4.0 mol % or less is preferable, 3.5 mol % or less is more preferable, and 3.0 mol % or less is particularly preferable.
  • the glass member 101 may or may not contain Fe 2 O 3 .
  • Fe 2 O 3 When Fe 2 O 3 is contained, the clarity of the glass can be improved without impairing the color of the glass, and the temperature of the bottom base of the melting furnace can be controlled. In addition, it becomes easy to adjust the in-line transmittance of the glass member 101 at a wavelength of 850 nm within the range described later, and a stable product can be obtained.
  • the content of Fe 2 O 3 is preferably 0.0001 mol % or more, more preferably 0.0005 mol % or more, and even more preferably 0.0010 mol % or more, from the viewpoint that the above effects can be satisfactorily exhibited.
  • the content of Fe 2 O 3 is preferably 0.0115 mol % or less, more preferably 0.0100 mol % or less, still more preferably 0.0080 mol % or less, and 0.0115 mol % or less, more preferably 0.0080 mol % or less, from the viewpoint of maintaining the color of the glass. 0050 mol % or less is particularly preferred.
  • the glass member 101 may or may not contain ZnO.
  • the ZnO content is preferably 0 mol % or more, more preferably 0.01 mol % or more, still more preferably 0.1 mol % or more, and particularly preferably 0.5 mol % or more.
  • the content of ZnO is preferably 15.0 mol% or less, more preferably 12.0 mol% or less, and even more preferably 10.0 mol% or less from the viewpoint of lowering the devitrification temperature of the glass and improving productivity. , 8.0 mol % or less is particularly preferred.
  • the glass member 101 may contain other components (for example, TiO 2 , Y 2 O 3 , Gd 2 O 3 etc.) other than the above, as long as the effects of the present invention are not impaired.
  • the total content of other components is preferably 10.0 mol % or less.
  • the glass member 101 may appropriately contain sulfates, chlorides, fluorides, halides, hydroxides, SnO 2 , Sb 2 O 3 , As 2 O 3 and the like as fining agents when melting the glass. good.
  • coloring components such as Ni, Co, Cr, Mn, V, Se, Au, Ag, and Cd may be contained for color adjustment.
  • it may contain a coloring component such as Fe, Ni, Co, Cr, Mn, V, Se, Au, Ag, Cd in the range of 0.0001 mol% or more. .
  • At least one selected from the group consisting of sulfates, chlorides, fluorides, halides, hydroxides, SnO 2 , Sb 2 O 3 and As 2 O 3 is contained.
  • the total content of these groups is preferably 0.01 mol % or more, more preferably 0.02 mol % or more, and even more preferably 0.05 mol % or more, from the viewpoint of clarity.
  • the total content of these groups is preferably 5.0 mol% or less, more preferably 2.0 mol% or less, and even more preferably 1.0 mol% or less, from the viewpoint of not affecting the glass properties.
  • SiO 2 , Al 2 O 3 , B 2 O 3 and P 2 O 5 are glass network formers.
  • the total content of SiO 2 , Al 2 O 3 , B 2 O 3 and P 2 O 5 in the glass member 101 is 70.0 mol % or more from the viewpoint of enhancing the stability of the glass structure and chemical durability. and is preferably 75.0 mol % or more, more preferably 78.0 mol % or more, and particularly preferably 80.0 mol % or more.
  • the total content of SiO 2 , Al 2 O 3 , B 2 O 3 and P 2 O 5 is 97.0 mol % or less from the viewpoint of suppressing an increase in the melting temperature of the glass and improving the clarity. , is preferably 95.0 mol % or less, more preferably 93.0 mol % or less, and particularly preferably 90.0 mol % or less.
  • a preferable aspect of the glass composition of the glass member 101 is 55.0 to 85.0 mol % of SiO 2 , 1.5 to 14.5 mol % of Al 2 O 3 , and 3.0 to 14.0 mol. % B 2 O 3 and 0 to 3.5 mol % P 2 O 5 , and the content of SiO 2 , Al 2 O 3 , B 2 O 3 and P 2 O 5 in the glass member 101 is 70.0 to 97.0% in terms of molar percentage based on the oxide. Thereby, the glass properties are more excellent.
  • the thickness of the glass member 101 is not particularly limited as long as it can support the Si—SiC member 105 . Specifically, the thickness of the glass member 101 is preferably 2 to 40 mm.
  • the thickness of the glass member 101 is more preferably 3 mm or more, more preferably 5 mm or more, particularly preferably 10 mm or more, and most preferably 15 mm or more.
  • the thickness of the glass member 101 is more preferably 35 mm or less, more preferably 30 mm or less, and particularly preferably 25 mm or less.
  • the thickness of the glass member 101 is within the above range, it can maintain sufficient strength as a supporting member.
  • the thickness of the glass member 101 can be measured, for example, with a vernier caliper, a digital measure, or the like.
  • the average linear expansion coefficient ⁇ of the glass member 101 at 20 to 200°C is 1.50 to 5.00 ppm/°C.
  • the average linear expansion coefficient ⁇ of the glass member 101 at 20 to 200° C. is also simply referred to as the average linear expansion coefficient ⁇ .
  • the average linear expansion coefficient ⁇ is preferably 2.00 ppm/°C or higher, more preferably 2.50 ppm/°C or higher, and particularly preferably 2.60 ppm/°C or higher.
  • the average linear expansion coefficient ⁇ is preferably 3.50 ppm/°C or less, more preferably 3.25 ppm/°C or less, even more preferably 3.10 ppm/°C or less, and particularly preferably 3.00 ppm/°C or less.
  • the average linear expansion coefficient ⁇ of the glass member 101 is within the above range, the average linear expansion coefficients of the glass member 101 and the Si—SiC member 105 can be easily matched, and the smaller the ⁇ , the greater the temperature difference inside the glass member. It is possible to reduce the distortion generated inside the glass at the time of bending.
  • the average coefficient of linear expansion ⁇ can be measured with a thermal dilatometer (dilatometer) whose temperature range is 20°C to 200°C, or a thermomechanical analyzer (TMA).
  • dilatometer thermal dilatometer
  • TMA thermomechanical analyzer
  • of the value obtained by subtracting the average linear expansion coefficient ⁇ of the glass member 101 from the average linear expansion coefficient ⁇ of the Si—SiC member 105 is 2.00 ppm/°C or less.
  • is preferably 1.00 ppm/°C or less, more preferably 0.50 ppm/°C or less, and particularly preferably 0.30 ppm/°C or less.
  • Si--SiC member 105 and the glass member 101, since Si--SiC has a higher thermal conductivity than glass, a temperature difference may occur during use. In particular, during cooling, a tensile stress is applied to the surface of the glass opposite to the bonding layer, so that the glass tends to break. Small is preferred.
  • the linear transmittance of the glass member 101 at a wavelength of 850 nm is 80% or higher, preferably 85% or higher, more preferably 88% or higher, and even more preferably 90% or higher. If the in-line transmittance of the glass member 101 at a wavelength of 850 nm is 80% or more, a sufficient amount of infrared rays can be transmitted for use in heating. The upper limit of the in-line transmittance of the glass member 101 is 100%.
  • the linear transmittance is the transmittance of light that is linearly transmitted through the glass member 101 in its thickness direction when the incident angle of incident light is 0°, and can be measured at 20°C with a spectrophotometer.
  • Methods for adjusting the in-line transmittance of the glass member 101 within the above range include a method for adjusting the content of Fe 2 O 3 in the glass member 101 within the above range, and a method for suppressing surface reflection of the glass member 101 .
  • a method of forming a protective film is mentioned.
  • As a method for forming the antireflection film generally known methods such as wet coating such as spray coating, spin coating and flow coating, and dry coating such as sputtering and vapor deposition can be used.
  • the Young's modulus of the glass member 101 is preferably 40 to 120 GPa.
  • the Young's modulus of the glass member 101 is more preferably 60 GPa or higher, more preferably 65 GPa or higher, and particularly preferably 70 GPa or higher.
  • the Young's modulus of the glass member 101 is more preferably 100 GPa or less, more preferably 95 GPa or less, and particularly preferably 90 GPa or less.
  • the Young's modulus of the glass member 101 is within the above range, it is possible to maintain sufficient strength as a supporting member and reduce the amount of warpage.
  • the Young's modulus of the glass member 101 can be measured at 20°C by the ultrasonic pulse method described in Japanese Industrial Standards (JIS R1602:1995).
  • the melting temperature of the glass member 101 is preferably 1000-2000°C.
  • the melting temperature of the glass member 101 is more preferably 1300°C or higher, more preferably 1400°C or higher, and particularly preferably 1500°C or higher.
  • the melting temperature of the glass member 101 is more preferably 1900°C or lower, more preferably 1800°C or lower, and particularly preferably 1700°C or lower.
  • the melting temperature of the glass member 101 is within the above range, the clarity of the glass and the meltability of the raw material are excellent, and defects in the glass can be suppressed.
  • the melting temperature of the glass member 101 indicates the temperature T2 (° C.) at which the viscosity is 10 2 dPa ⁇ s when the viscosity is measured using a rotational viscometer.
  • the devitrification temperature of the glass member 101 is preferably 800 to 1600°C.
  • the devitrification temperature of the glass member 101 is more preferably 900°C or higher, more preferably 1000°C or higher, and particularly preferably 1100°C or higher.
  • the devitrification temperature of the glass member 101 is more preferably 1500°C or lower, more preferably 1450°C or lower, and particularly preferably 1400°C or lower.
  • the devitrification temperature of the glass member 101 is within the above range, defects that occur during glass production are reduced.
  • the devitrification temperature of the glass member 101 was determined by placing crushed glass particles in a platinum dish and heat-treating them in an electric furnace controlled at a constant temperature for 17 hours. It is the maximum temperature at which crystals do not precipitate.
  • the bonding layer 103 is a member that bonds the glass member 101 and the Si—SiC member 105 together.
  • Examples of the resin contained in the bonding layer 103 include epoxy resin, silicone resin, fluororesin, polyimide resin, and the like. Epoxy resins, silicone resins, and fluororesins are preferred because of their superior heat resistance. The resin may be used singly or in combination of two or more.
  • the resin content is preferably 40 to 100% by mass, more preferably 50 to 90% by mass, and even more preferably 60 to 80% by mass with respect to the total mass of the bonding layer 103.
  • the adhesion between the glass member 101 and the Si--SiC member 105 via the bonding layer 103 is superior, and the difference in expansion coefficient from the Si--SiC member can be reduced.
  • the bonding layer 103 may or may not contain components other than resin (hereinafter also referred to as "other components"). Specific examples of other components include plasticizers and fillers.
  • the content of the other components is preferably 10 to 50% by mass, more preferably 20 to 40% by mass, and more preferably 25 to 35% by mass with respect to the total mass of the bonding layer 103. % is more preferred. If the content of other components is 50% by mass or less, the adhesion between the glass member 101 and the Si—SiC member 105 via the bonding layer 103 is more excellent.
  • the bonding layer 103 may be composed of a resin film, a coating type adhesive, or the like.
  • the bonding layer 103 When the bonding layer 103 is composed of a resin film, it can be produced using, for example, a hot press device. A resin film forming the bonding layer 103 is sandwiched between the glass member 101 and the Si—SiC member 105 (this structure is referred to as a temporary laminate). The temporary laminate is heated to a temperature higher than the softening point of the resin film, pressure is applied to the temporary laminate, and the glass member 101 and the Si—SiC member 105 are joined. In order to prevent inclusion of bubbles during bonding, it is preferable to press the temporary laminate in a vacuum atmosphere.
  • the bonding layer 103 is composed of a coating type adhesive, it is coated on the glass member 101 by any conventionally known method, and the Si--SiC member 105 is laminated thereon.
  • the contact surface of the glass member 101 with the bonding layer 103 and the contact surface of the Si--SiC member 105 with the bonding layer 103 may be roughened by blasting or the like.
  • the thickness of the bonding layer 103 is preferably 0.001 to 0.300 mm.
  • the thickness of the bonding layer 103 may be 0.005 mm or more, 0.008 mm or more, or 0.010 mm or more.
  • the thickness of the bonding layer 103 may be 0.150 mm or less, 0.050 mm or less, or 0.030 mm or less.
  • the thickness of the bonding layer 103 can be calculated using digital data captured by SEM cross-sectional observation and image processing software.
  • the linear transmittance of the bonding layer 103 at a wavelength of 850 nm is preferably 88% or higher, more preferably 91% or higher, still more preferably 93% or higher, and particularly preferably 95% or higher. If the bonding layer 103 has a linear transmittance of 88% or more, it is possible to achieve a sufficient amount of infrared rays to be transmitted for use in heating. The upper limit of the in-line transmittance of the bonding layer 103 is 100%.
  • the linear transmittance is the transmittance of light linearly transmitted through the bonding layer 103 in the thickness direction when the incident angle of incident light is 0°, and can be measured at 20°C with a spectrophotometer.
  • the heat resistance temperature of the resin contained in the bonding layer 103 is preferably 120 to 420°C. Further, from the viewpoint of stress relaxation during use at high temperatures, a temperature of 120 to 300° C. is more preferable.
  • the heat resistance temperature of the resin contained in the bonding layer 103 is more preferably 140°C or higher, particularly preferably 160°C or higher, and most preferably 180°C or higher.
  • the heat resistance temperature of the resin contained in the bonding layer 103 may be 280°C or lower, 260°C or lower, or 240°C or lower.
  • the heat resistance temperature of the resin contained in the bonding layer 103 is the temperature at which the mass of the object to be measured decreases by 1% by mass when thermogravimetric measurement (TGA) is performed in an air atmosphere.
  • the average linear expansion coefficient ⁇ of the bonding layer 103 at 20-200°C is preferably 2-200 ppm/°C.
  • the average linear expansion coefficient ⁇ of the bonding layer 103 at 20 to 200° C. is also simply referred to as the average linear expansion coefficient ⁇ .
  • the average linear expansion coefficient ⁇ is more preferably 4 ppm/°C or higher, more preferably 7 ppm/°C or higher, and particularly preferably 10 ppm/°C or higher.
  • the average linear expansion coefficient ⁇ is more preferably 100 ppm/°C or less, more preferably 50 ppm/°C or less, particularly preferably 30 ppm/°C or less, and most preferably 20 ppm/°C or less.
  • the average coefficient of linear expansion ⁇ of the bonding layer 103 is within the above range, the adhesion is excellent and the difference in expansion coefficient from the Si—SiC member can be reduced, so the laminated member 100 has excellent thermal shock resistance.
  • the average coefficient of linear expansion ⁇ can be measured with a thermal dilatometer (dilatometer) whose temperature range is 20°C to 200°C, or a thermomechanical analyzer (TMA).
  • dilatometer thermal dilatometer
  • TMA thermomechanical analyzer
  • the Young's modulus of the resin film is preferably 0.05 GPa or more in terms of increasing the adhesion between the Si—SiC member 105 and the glass member 101 and maintaining the shape of the entire member. , more preferably 0.10 GPa or more, and more preferably 0.15 GPa or more.
  • the Young's modulus of the resin film is preferably 3.5 GPa or less, more preferably 3.0 GPa or less, in order to reduce the stress generated by the difference in expansion coefficient from that of the Si—SiC member. It is more preferably 2.0 GPa or less, particularly preferably 1.0 GPa or less, and most preferably 0.5 GPa or less.
  • the stress generated from the difference in expansion coefficient from the Si-SiC member increases as the Young's modulus of the resin layer increases, and decreases as the Young's modulus decreases.
  • the Young's modulus of the resin layer can be measured at 25°C by the elastic modulus test method described in Japanese Industrial Standards (JIS K7171).
  • the warp amount of the laminated member 100 is preferably 0.25 mm or less, more preferably 0.20 mm or less, still more preferably 0.10 mm or less, and particularly preferably 0.05 mm or less.
  • the amount of warpage of the laminated member 100 is equal to or less than the above value, it is possible to prevent stress from concentrating on a specific portion when stress occurs, so that impact resistance can be further improved.
  • the laminated member 100 is used for a kitchen or the like, it is possible to prevent the surroundings from being distorted due to warping of the laminated member 100 and being reflected in the laminated member 100, thereby reducing the design.
  • the object to be heated when the object to be heated is placed on the laminated member 100, the object to be heated can be prevented from wobbling.
  • the lower limit of the warp amount of the laminated member 100 is 0 mm.
  • the warp amount of the laminated member 100 can be measured by a non-contact three-dimensional shape measuring device.
  • the thicknesses of the glass member 101, the bonding layer 103 and the Si—SiC member 105, the types and contents of the components constituting each member (layer), and the like are adjusted as described above. There is a method of doing as follows.
  • the density of the laminated member 100 is preferably 2.40-2.85 g/cm 3 .
  • the density of the laminated member 100 is more preferably 2.45 g/cm 3 or higher, still more preferably 2.50 g/cm 3 or higher, and particularly preferably 2.55 g/cm 3 or higher.
  • the density of the laminated member 100 is more preferably 2.80 g/cm 3 or less, even more preferably 2.75 g/cm 3 or less, and particularly preferably 2.70 g/cm 3 or less.
  • the density is a value obtained by dividing the total mass of the lamination member 100 by the total volume of the lamination member 100 .
  • the total mass of the laminated member 100 can be measured with a mass measuring instrument.
  • the total volume of the laminated member 100 can be measured with a digital measure.
  • the thicknesses of the glass member 101, the bonding layer 103 and the Si—SiC member 105, the types and contents of the components constituting each member (layer), etc. There is a way to do it.
  • the area of the uppermost surface of the laminated member 100 on the Si—SiC member 105 side (main surface of the laminated member 100 on the Si—SiC member 105 side) is preferably 0.01 to 10 m 2 .
  • the area of the uppermost surface of the laminated member 100 is more preferably 0.07 m 2 or more, still more preferably 0.15 m 2 or more, particularly preferably 0.30 m 2 or more, and most preferably 0.60 m 2 or more.
  • the area of the uppermost surface of the laminated member 100 is more preferably 8 m 2 or less, even more preferably 4 m 2 or less, particularly preferably 2 m 2 or less, and most preferably 1 m 2 or less.
  • the area of the uppermost surface of the laminated member 100 is within the above range, workability is improved when incorporating it into the housing as a heating member.
  • the area of the top surface is calculated by measuring the dimensions of the laminated member 100 with a digital measure.
  • the bonding layer 103 is arranged between the glass member 101 and the Si—SiC member 105, and the glass member 101 and the Si—SiC member 105 are attached via the bonding layer 103. There is a method of matching.
  • the laminated member 100 As an example of a more detailed manufacturing method of the laminated member 100, after laminating the glass member 101, the bonding layer 103, and the Si—SiC member 105 in this order, they are bonded together at a temperature of 150 to 380°C. are mentioned.
  • a laminated member of another aspect includes a second bonding layer provided on the Si—SiC member 105, and a second Si—SiC member bonded to the Si—SiC member 105 via the second bonding layer. and a member. Since the second Si--SiC member is configured in the same manner as the Si--SiC member 105, the description thereof is omitted.
  • the Si--SiC member 105 and the second Si--SiC member are laminated, it becomes easier to manufacture a laminated member having a complicated shape. For example, when providing a space for inserting a sensor for temperature measurement in the laminated member, one of the Si—SiC member 105 and the second Si—SiC member is grooved in advance, and the other is bonded together. This makes it easy to provide a space in the laminated member.
  • the method of bonding the Si—SiC member 105 and the second Si—SiC member by the second bonding layer is not particularly limited, but for example, bonding using a resin such as epoxy resin or fluororesin, tin or indium, etc. bonding using molten metal and bonding using glass frit. Assuming that the laminated member is used as a heating member, joining using metal is preferable from the viewpoint of heat resistance and thermal conductivity.
  • glass frit has high heat resistance but low thermal conductivity, and resin has low heat resistance and thermal conductivity, so it is preferable to use metal for joining.
  • metals include indium, tin, tin-based alloys, and lead-based alloys. Among them, tin metals and tin alloys are preferable from the viewpoint of thermal conductivity, heat resistance and environmental load.
  • the Si--SiC member 105 and the second Si--SiC member are heated to a desired temperature, eg, 250.degree. C. to 270.degree.
  • a desired temperature eg, 250.degree. C. to 270.degree.
  • ultrasonic waves to the joint surface of the heated Si--SiC member and the second Si--SiC member, after applying a metal melted at a temperature near a desired temperature (for example, 250° C. to 270° C.) , the joint surfaces may be superimposed on each other.
  • a laminated member according to another aspect includes a third bonding layer provided on the second Si—SiC member, and a third Si—SiC member bonded to the second Si—SiC member via the third bonding layer. - a SiC member;
  • the third bonding layer is configured similarly to the second bonding layer.
  • the third Si--SiC member is configured in the same manner as the Si--SiC member 105 .
  • the laminated member of another aspect does not have the third bonding layer and the third ceramic member.
  • the laminated member of the present invention may have a configuration that allows rapid cooling of the laminated member.
  • the lamination member 100 may have flow paths between the glass member 101 and the bonding layer 103 and between the Si—SiC member 105 and the bonding layer 103 .
  • the laminated member 100 may be processed so that at least one of the glass member 101 and the Si—SiC member 105 serves as a flow channel.
  • the lamination member of another embodiment is between the glass member 101 and the bonding layer 103, between the Si—SiC member 105 and the bonding layer 103, between the Si—SiC member 105 and the second bonding layer, and , between the second Si—SiC member and the second bonding layer.
  • at least one of the glass member 101, the Si--SiC member 105, and the second Si--SiC member may be processed to form the flow path.
  • the laminated member can be cooled by running water through the channels.
  • the laminated member of the present invention may be provided with an antireflection film that enhances transmittance and irradiation efficiency.
  • the laminated member 100 may have an antireflection film on the main surface of the glass member 101 opposite to the bonding layer 103 side and/or the main surface of the glass member 101 on the bonding layer 103 side.
  • the laminated member of another embodiment may have an antireflection film on the main surface of the Si—SiC member 105 on the bonding layer 103 side or on the main surface of the second Si—SiC member on the second bonding layer side. .
  • the irradiation efficiency (heating efficiency) can be increased.
  • the laminated member of the present invention may be equipped with a temperature sensor.
  • the lamination member 100 may have a temperature sensor inside the Si—SiC member 105 .
  • another aspect of the laminated member may include a temperature sensor inside the Si—SiC member 105 or inside the second Si—SiC member.
  • a specific example of a configuration having a temperature sensor is a configuration in which a temperature sensor is inserted into a hole opened in the side surface of the Si--SiC member 105 or the second Si--SiC member.
  • the temperature sensor is directly below the main surface of the Si—SiC member 105 opposite to the bonding layer 103 side, or on the main surface of the second Si—SiC member opposite to the second bonding layer. Place directly below.
  • the temperature sensor is arranged so as not to be in contact with the bonding layer 103 or the second bonding layer and not to be exposed.
  • the temperature sensor can measure the main surface temperature of the Si—SiC member 105 opposite to the bonding layer 103 side or the main surface temperature of the second Si—SiC member opposite to the second bonding layer.
  • the laminated member of the present invention can be suitably used as a heating member.
  • the laminated member of the present invention can be suitably used, for example, as a heating member of a heating cooker.
  • the laminated member of the present invention may be used as a kitchen worktop (top plate).
  • the laminated member of the present invention may be used as a material for a mounting table on which an electronic device is placed in an inspection apparatus or test apparatus for conducting electrical tests on electronic devices.
  • the laminated member of the present invention may also function as a top plate of an inspection apparatus or a test apparatus for conducting electrical tests of a heating cooker or an electronic device, and as a kitchen worktop.
  • Glass composition One aspect of the glass composition of the present disclosure is a laminated member comprising a glass member, a bonding layer containing a resin on the glass member, and a Si—SiC member on the bonding layer, wherein the glass used for the glass member
  • the composition the glass composition has a linear transmittance of 80% or more at a wavelength of 850 nm, and the glass composition has a 55.0 to 85.0 mol% SiO 2 , 1.5-22.0 mol % Al 2 O 3 , 2.0-14.0 mol % B 2 O 3 , 0-5.0 mol % P 2 O 5
  • the total content of the SiO 2 , the Al 2 O 3 , the B 2 O 3 and the P 2 O 5 is from 70.0 to 97.0%
  • the glass composition has an average linear expansion coefficient ⁇ at 20 to 200° C.
  • the glass composition has an average linear expansion coefficient ⁇ at 20 to 200° C. It is used for a laminated member having a Si—SiC member having an expansion coefficient ⁇ of 2.85 to 4.00 ppm/° C., and the glass member is obtained from the average linear expansion coefficient ⁇ of the Si—SiC member at 20 to 200° C. obtained by subtracting the average coefficient of linear expansion ⁇ at 20 to 200°C of the absolute value
  • Another aspect of the glass composition of the present disclosure is 55.0 to 85.0 mol % SiO 2 and 1.5 to 22.0 mol % Al 2 O 3 , expressed as mole percentages on an oxide basis. , 2.0 to 14.0 mol % of B 2 O 3 and 0 to 5.0 mol % of P 2 O 5 , wherein the SiO 2 , the Al 2 O 3 , the B 2 O 3 and The total content of P 2 O 5 is 70.0 to 97.0% in terms of molar percentage based on the oxide, and the average coefficient of linear expansion ⁇ at 20 to 200° C. is 1.50 to 5.0%. 00 ppm/° C. and a linear transmittance of 80% or more at a wavelength of 850 nm.
  • the above glass composition is suitably used as a glass member that constitutes the laminated member described above.
  • the laminated member has excellent temperature rise property, impact resistance, and thermal shock resistance.
  • each physical property value, and the like in the above glass composition are the same as those described above with respect to the glass member of the laminated member of the present disclosure.
  • the linear transmittance at a wavelength of 850 nm in the above glass composition means a value when the glass composition is measured as a glass member.
  • the above explanation regarding the glass member of the laminated member also applies to the bonding layer and the Si—SiC member constituting the laminated member.
  • the glasses (iA) to (v) and (vii) to (xxix) in Tables 1 and 2 are each glass composition expressed in mole percentage based on oxides shown in Tables 1 and 2. , was prepared as follows. A blank in Tables 1 and 2 means that the corresponding component is not contained. First, commonly used glass raw materials such as oxides, hydroxides, carbonates, sulfates, halides and nitrates were appropriately selected and weighed to 10000 g as glass. Next, the mixed raw material was placed in a platinum crucible, placed in a resistance heating electric furnace at 1500 to 1700° C., melted for about 12 hours, degassed and homogenized. The obtained molten glass was poured into a mold material, held at a temperature of +50°C of the glass transition point for 1 hour, and then cooled to room temperature at a rate of 0.5°C/min to obtain a glass block.
  • commonly used glass raw materials such as oxides, hydroxides, carbonates, sulfates, halides
  • Each obtained glass block was cut, ground, and polished to obtain a glass member (300 mm long and 300 mm wide).
  • the thickness was measured at 20°C using a digital measure.
  • the average coefficient of linear expansion ⁇ was measured in a temperature range of 20°C to 200°C using a high-precision thermal expansion meter "DIL402 Expedis” manufactured by Netsch.
  • the average coefficient of linear expansion ⁇ of the glass (xi) in Table 1 was not measured because it was cloudy due to phase separation and clearly could not be used as a glass member.
  • the linear transmittance was measured with a spectrophotometer at 20° C. and a wavelength of 850 nm.
  • the glass of (xi) in Table 1 was cloudy due to phase separation, and the in-line transmittance was clearly less than 80%, so the in-line transmittance was not measured.
  • the Young's modulus was measured at 20°C by the ultrasonic pulse method described in Japanese Industrial Standards (JIS R1602:1995).
  • the Young's modulus was not measured for the glass of (xi) in Table 1, because it was cloudy due to phase separation and clearly could not be used as a glass member.
  • the dissolution temperature (T2) is the temperature T2 (°C) at which the viscosity is 10 2 dPa ⁇ s when measured using a rotational viscometer.
  • the melting temperatures (T2) of the glass (iv) and the glass (v) in Table 1 could not be measured, so they were calculated by extrapolation.
  • the glass of (vi) could not be measured with a rotational viscometer because its viscosity was too high.
  • the devitrification temperature was determined by placing crushed glass particles in a platinum dish and heat-treating them in an electric furnace controlled at a constant temperature for 17 hours. Maximum temperature (°C). The devitrification temperature was not measured for the glass of (xi) in Table 1, because it was cloudy due to phase separation and could not be used as a glass member.
  • the density was measured by the Archimedes method.
  • phase separation was evaluated by observing the glass member with a SEM (scanning electron microscope), and "O” was given when phase separation was not confirmed, and "X” was given when phase separation was confirmed.
  • Si—SiC members (a-1) to (a-3) were produced as follows.
  • the ⁇ -SiC powder A1 was classified with a 325-mesh sieve to obtain an ⁇ -SiC powder A2 (maximum particle size: 44 ⁇ m, average particle size: 8 ⁇ m).
  • ⁇ -SiC powder A3, pure water, and acrylic resin emulsion (binder) were mixed to obtain slurry (solid content concentration: about 75% by mass).
  • the slurry was poured into a gypsum mold to obtain a compact (size: 320 mm ⁇ 320 mm ⁇ 16 mm). After drying the obtained molded body at 50° C. for 14 days, it was fired at 1900° C. in an electric furnace in an inert atmosphere of argon to obtain a sintered body. The porosity of the sintered body was 18.2%.
  • the sintered body A1 is transferred to another electric furnace, and the sintered body A1 is melted and impregnated with high-purity silicon under the condition of 1500 ° C. in a vacuum, so that all the pores are filled with high-purity silicon.
  • - A SiC member was obtained. The content of iron contained in the Si—SiC member was 2.2 ppm.
  • the Si--SiC member was processed to have a length of 30 cm, a width of 30 cm, and a thickness shown in Table 3 to obtain Si--SiC members (a-1) to (a-3).
  • the Si--SiC member (b) was produced in the same manner as the Si--SiC member (a-1) except that the solid content concentration of the slurry was changed to about 79% by mass.
  • the Si--SiC member (c) was produced in the same manner as the Si--SiC member (a-1) except that the solid content concentration of the slurry was changed to about 61% by mass.
  • the Si—SiC member (d) was produced as follows. SiC powder (manufactured by Taiheiyo Rundum Co., Ltd., model number: GMF-12S (average particle size 0.7 ⁇ m)) 48.2% by mass and silicon powder (mountain stone Metal Co., Ltd., model number: No. 700 (average particle size 2.5 ⁇ m)) 25.0% by mass, Metolose (manufactured by Shin-Etsu Chemical Co., Ltd., model number SM8000) as a binder 5.5% by mass, and pure water 21. 5% by mass were added and kneaded for 6 hours to obtain a clay.
  • the clay thus obtained was put into an extruder (manufactured by Miyazaki Tekko Co., Ltd., model number: FM100) and extruded under the conditions of a head pressure of 1.0 MPa and a discharge rate of 1200 g/min to obtain a compact.
  • the molded body obtained was dried at 50° C. for 14 days, and then heated at 450° C. in an air atmosphere for 3 hours for degreasing to obtain a degreased body.
  • the resulting degreased body was fired in a carbon firing furnace under a vacuum atmosphere of 10 ⁇ 3 Pa at 1700° C. for 2 hours to obtain a sintered body.
  • the obtained sintered body was impregnated with Si at 1500° C.
  • Si—SiC member in an argon atmosphere to obtain a Si—SiC member.
  • the obtained Si—SiC member was processed to have a length of 30 cm, a width of 30 cm, and a thickness shown in Table 3 to obtain a Si—SiC member (d).
  • the Si--SiC member (e) was produced in the same manner as the Si--SiC member (a-1) except that the solid content concentration of the slurry was changed to about 77% by mass.
  • the Si--SiC member (f) was produced in the same manner as the Si--SiC member (a-1) except that the solid content concentration of the slurry was changed to about 58% by mass.
  • Si—SiC member [Physical properties of Si—SiC member]
  • the Si—SiC members (a-1) to (f) thus obtained were subjected to the following measurements. Table 3 shows the measurement results.
  • the amount (composition) of each component of the Si--SiC member was measured by an inductively coupled plasma mass spectrometer ICP-MS (manufactured by Shimadzu Corporation).
  • the thickness was measured at 20°C using a vernier caliper (AD-5764A) manufactured by A&D Co., Ltd.
  • the average coefficient of linear expansion ⁇ was measured in a temperature range of 20°C to 200°C using a differential thermal expansion meter (TMA) "TMA4000SA” manufactured by Bruker AXS.
  • TMA differential thermal expansion meter
  • the thermal conductivity was measured at a temperature of 20°C using a laser flash thermophysical property measuring device "MODEL LFA-502" manufactured by Kyoto Electronics Industry Co., Ltd.
  • the Young's modulus is determined by the elastic modulus test method (dynamic elastic modulus method) at 20°C.
  • Bending strength is measured using an Autocom universal testing machine "AC-300KN” manufactured by TSE Co., Ltd., using a bending strength test method (4-point bending strength) at 20°C.
  • the Vickers hardness was measured at 20°C by using a Vickers hardness tester system (manufactured by Nippon Steel & Sumikin Technology Co., Ltd.) by pressing for 15 seconds with a pressing load of 10 kgf.
  • the thickness was measured with a digital measure.
  • the linear transmittance was measured with a spectrophotometer at 20°C and a wavelength of 850 nm.
  • the heat resistance temperature is the temperature at which the mass of the resin film or coating type adhesive decreases by 1% by mass by performing thermogravimetric measurement (TGA) in an air atmosphere.
  • the average coefficient of linear expansion ⁇ was measured in a temperature range of 20° C. to 200° C. using a differential thermal expansion meter (TMA4000SA) manufactured by Bruker AXS. Note that the average linear expansion coefficient ⁇ of the resin film or coating type adhesive and the average linear expansion coefficient ⁇ of the bonding layer obtained using the resin film or coating type adhesive, which will be described later, were the same value. .
  • the Young's modulus was measured at 25°C using an Instron universal testing machine (model 5966) according to the elastic modulus test method described in Japanese Industrial Standards (JIS K7171).
  • the resin film shown in Table 4 was sandwiched between the glass member and the Si—SiC member, heated to a temperature of the softening point of the resin film +20 degrees, and pressed for 5 minutes under a pressure of 2 MPa. The glass member and the Si—SiC member were bonded via the bonding layer.
  • the coating type adhesive shown in Table 4 is applied to the glass member with a thickness of 0.080 mm using a dispenser ND type manufactured by Hyojin Shrine, and a Si—SiC member is laminated thereon, and a pressure of 1.0 MPa is applied.
  • the glass member and the Si—SiC member were bonded via the bonding layer by pressing the glass member and heating at 120° C. for 4 hours for curing.
  • samples (laminated members) of Examples 1 to 14 and 18 to 43 were obtained.
  • Heat resistance evaluation A sample of each example was heated at a temperature of 230° C. for 24 hours and visually evaluated for changes in appearance.
  • the evaluation criteria were as follows: ⁇ when there was no change in appearance (discoloration, bubbles, generation of foreign matter, exudation of the bonding layer, etc.), and x when there was a change in appearance.
  • the sample of Example 25 was not evaluated for heat resistance.
  • the amount of warp of the sample in each example is measured by measuring the three-dimensional properties of the sample surface in accordance with ISO25178-605 using a non-contact three-dimensional shape measuring device "NH-5Ns" manufactured by Mitaka Koki Co., Ltd. It was measured by determining the maximum slanted flatness of the surface. Specifically, the sample is placed on a precision surface plate, and the height of each point on the top surface of the sample is measured using a laser autofocus microscope. A value, that is, the maximum inclined flatness was obtained as the amount of warpage.
  • the thickness of the bonding layer (resin) of the samples of Examples 1 to 14 and 18 to 43 was calculated by SEM cross-sectional observation.
  • thermo shock resistance evaluation A laminated member with a width of 15 mm and a length of 100 mm was produced in the same combination as the samples of Examples 1 to 14 and 18 to 43, and the Si—SiC member side was heated using a hot plate to increase the temperature between it and the glass. A difference was given to evaluate thermal shock resistance. Specifically, the surface of the Si—SiC member was heated using a hot plate set at 220° C., and the glass member side was cooled using a cooling plate cooled to 10° C. by flowing cooling water to give a temperature difference. This state was held for 1 hour. The evaluation criteria were as follows: x when cracks or cloudiness was observed in the adhesive layer by visual observation, and ⁇ when no change was observed. The samples of Examples 15-17 and 25 were not evaluated for thermal shock resistance.
  • the laminated member of the present invention has a high temperature rise rate, high impact resistance and thermal shock resistance, and is suitable as a heating member (Examples 1 to 5, 7, 9-13, 20-24, 26-43).
  • the laminated member of Example 6 had a low average linear expansion coefficient ⁇ of less than 2.85 ppm/°C at 20 to 200°C of the Si—SiC member, and had low thermal shock resistance.
  • the average linear expansion coefficient ⁇ of the Si—SiC member at 20 to 200° C. was as low as less than 2.85 ppm/° C., and the impact resistance and thermal shock resistance were low.
  • the laminated member of Example 14 had a high rate of temperature rise, high impact resistance and high thermal shock resistance, but had a large amount of warpage.
  • the samples of Examples 15-17 had poor temperature rise rates or impact resistance.
  • the average linear expansion coefficient ⁇ of the Si—SiC member at 20 to 200°C was as low as less than 2.85 ppm/°C, and the thermal shock resistance was low.
  • the laminated member of Example 23 had low impact resistance and a large amount of warpage.
  • the laminated member of Example 25 had a low rate of temperature rise.

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  • Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
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  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Glass Compositions (AREA)
  • Laminated Bodies (AREA)
  • Joining Of Glass To Other Materials (AREA)
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