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WO2017061403A1 - Matériau à dilatation thermique négative et matériau composite le comprenant - Google Patents

Matériau à dilatation thermique négative et matériau composite le comprenant Download PDF

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Publication number
WO2017061403A1
WO2017061403A1 PCT/JP2016/079397 JP2016079397W WO2017061403A1 WO 2017061403 A1 WO2017061403 A1 WO 2017061403A1 JP 2016079397 W JP2016079397 W JP 2016079397W WO 2017061403 A1 WO2017061403 A1 WO 2017061403A1
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Prior art keywords
thermal expansion
expansion material
negative thermal
zirconium
slurry
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PCT/JP2016/079397
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English (en)
Japanese (ja)
Inventor
純也 深沢
畠　透
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Nippon Chemical Industrial Co Ltd
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Nippon Chemical Industrial Co Ltd
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Priority claimed from JP2016192427A external-priority patent/JP6105140B1/ja
Application filed by Nippon Chemical Industrial Co Ltd filed Critical Nippon Chemical Industrial Co Ltd
Priority to KR1020187008487A priority Critical patent/KR102070738B1/ko
Priority to US15/759,333 priority patent/US10280086B2/en
Priority to CN201680055928.7A priority patent/CN108025915B/zh
Priority to EP16853557.3A priority patent/EP3360848B1/fr
Publication of WO2017061403A1 publication Critical patent/WO2017061403A1/fr
Anticipated expiration legal-status Critical
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Definitions

  • the present invention relates to a negative thermal expansion material that shrinks in response to a temperature rise and a composite material containing the same.
  • negative thermal expansion material a material exhibiting negative thermal expansion (hereinafter also referred to as “negative thermal expansion material”) whose volume becomes smaller when heated is known. It is known that a material exhibiting negative thermal expansion can be used together with other materials to suppress changes in the thermal expansion of the material due to temperature changes.
  • Examples of the material exhibiting negative thermal expansion include ⁇ -eucryptite, zirconium tungstate (ZrW 2 O 8 ), zirconium tungstate phosphate (Zr 2 WO 4 (PO 4 ) 2 ), Zn x Cd 1 ⁇ x (CN) 2 , manganese nitride, bismuth / nickel / iron oxide and the like are known.
  • the coefficient of linear expansion of zirconium tungstate phosphate is ⁇ 3.4 to ⁇ 3.0 ppm / ° C. in the temperature range of 0 to 400 ° C., which has a large negative thermal expansion property and exhibits positive thermal expansion (hereinafter “In combination with “positive thermal expansion material”), a low thermal expansion material can be produced.
  • Patent Document 1 As a method for producing zirconium tungstate phosphate, for example, in Patent Document 1 below, a reaction accelerator such as zirconium phosphate, tungsten oxide and MgO is mixed by a wet ball mill, and the resulting mixture is fired at 1200 ° C. Proposed.
  • Patent Document 2 proposes a method in which a phosphorus source such as ammonium phosphate, a tungsten source such as ammonium tungstate, and a zirconium source such as zirconium chloride are wet mixed and then calcined.
  • Non-Patent Document 1 below proposes a method of firing a mixture containing zirconium oxide, tungsten oxide and ammonium dihydrogen phosphate at 1200 ° C.
  • the particle shape of zirconium phosphate tungstate produced according to Patent Documents 1 and 2 and Non-Patent Document 1 is crushed, and as far as the present inventor is aware, no spherical particles have been reported.
  • Zirconium tungstate phosphate as a negative thermal expansion material is considered promising as a member for ultra-precision processing.
  • negative thermal expansion materials are used by being incorporated in positive thermal expansion materials such as metals, alloys, glass, ceramics, resins, rubbers, etc., but the dispersibility and filling characteristics in positive thermal expansion materials are even better. Development of negative thermal expansion material is desired. In particular, if a large amount of zirconium tungstate phosphate is added to the resin as a negative thermal expansion material, the viscosity tends to increase during the molding of the resin, so a sufficient amount of zirconium tungstate phosphate cannot be added to the resin. There is a problem that it is difficult to suppress the thermal expansion of the resin.
  • an object of the present invention is to provide a negative thermal expansion material having excellent dispersibility and filling characteristics with respect to a positive thermal expansion material, and a composite material including the same.
  • Step B in which the subsequent slurry is wet pulverized with a media mill
  • Step C in which the slurry after Step B is spray-dried to obtain a spherical reaction precursor, and then the spherical reaction precursor is calcined.
  • spherical zirconium tungstate phosphate By having the D step, spherical zirconium tungstate phosphate can be obtained, and the spherical zirconium tungstate phosphate has excellent negative thermal expansibility, and the spherical tungsten tungstate phosphate Among zirconium, those having a BET specific surface area within a specific range, even when blended in a resin, Has been found to be excellent in filling characteristics, such as being able to contain a sufficient amount of zirconium phosphate tungstate in the resin, and excellent in dispersibility, leading to the completion of the present invention. It was.
  • the first invention to be provided by the present invention is a negative thermal expansion material made of spherical zirconium tungstate phosphate having a BET specific surface area of 2 m 2 / g or less.
  • a second invention to be provided by the present invention is a composite material including the negative thermal expansion material and the positive thermal expansion material of the first invention.
  • FIG. 1 is an X-ray diffraction pattern of the reaction precursor obtained in Reference Example 1.
  • 2 (a) is an FT-IR spectrum chart of the reaction precursor obtained in Reference Example 1
  • FIG. 2 (b) is an FT-IR spectrum chart of zirconium hydroxide
  • FIG. 2 (c) is an FT-IR spectrum chart of phosphoric acid
  • FIG. 2D is an FT-IR spectrum chart of tungsten trioxide.
  • 3 is an X-ray diffraction pattern of the reaction precursor obtained in Example 1.
  • FIG. 4 is an FT-IR spectrum chart of the reaction precursor obtained in Example 1.
  • FIG. FIG. 5 is an X-ray diffraction diagram of the zirconium tungstate phosphate obtained in Example 1.
  • 6A is an SEM photograph (magnification 30000 times) of the zirconium tungstate phosphate obtained in Example 1
  • FIG. 6B is the same SEM photograph as FIG. 400 times).
  • the negative thermal expansion material of the present invention is made of spherical zirconium tungstate phosphate having a BET specific surface area of 2 m 2 / g or less, and the negative thermal expansion material having such a configuration is compared to the positive thermal expansion material. It has excellent dispersibility and filling properties.
  • the zirconium phosphate tungstate having the above-described configuration is, for example, when the resin and the negative thermal expansion material are kneaded with the resin as compared with the conventional crushed zirconium phosphate tungstate. It has been found that the interaction is reduced and the viscosity at the time of molding the resin composition can be reduced.
  • conventional crushed zirconium tungstate phosphate has a portion where the particle strength is brittle due to the particle shape
  • a composite material of glass powder and zirconium phosphate tungstate is used as a sealing material.
  • the hard glass powder strongly collides with the zirconium tungstate phosphate particles, which causes the particles to break from the brittle portions of the zirconium tungstate phosphate particles.
  • the fine particles are easily generated, and the fine particles and the glass powder are easily dissolved in the heat treatment process, and the fluidity of the sealing material is lowered.
  • the spherical zirconium tungstate phosphate used as the negative thermal expansion material of the present invention is a spherical particle, it is possible to suppress generation of fine particles during mixing with a hard material. There is also.
  • the spherical zirconium tungstate phosphate means that when the zirconium tungstate phosphate is used as a negative thermal expansion material in the state of monodispersed primary particles, the zirconium tungstate phosphate particles of the primary particles are used. It is said that its own particle shape is spherical. In addition, when the zirconium tungstate phosphate is used as a negative thermal expansion material in the state of aggregated particles in which fine primary particles form aggregates to form secondary particles, the aggregated particles themselves have a spherical shape. Indicates that
  • the spherical zirconium tungstate phosphate does not necessarily have a true spherical shape.
  • Viewpoint of excellent dispersibility and filling properties for making a positive thermal expansion material when the sphericity of the spherical zirconium tungstate phosphate is preferably 0.90 or more and 1 or less, more preferably 0.93 or more and 1 or less. To preferred.
  • the sphericity is calculated from parameters obtained by performing image analysis processing on 50 particles arbitrarily extracted when the sample is observed with an electron microscope at a magnification of 400. That is, the sphericity is represented by an average value of 50 particles obtained by the following calculation formula (1).
  • Sphericality equivalent area circle equivalent diameter / circumscribed circle diameter (1)
  • Examples of the image analysis apparatus used for the image analysis processing include Luzex (manufactured by Nireco), PITA-04 (manufactured by Seishin Enterprise Co., Ltd.), and the like. The value of the sphericity becomes closer to a perfect sphere as it approaches 1.
  • the BET specific surface area is 2.0 m 2 / g or less.
  • the interaction between the resin and the negative thermal expansion material can be further reduced, and as a result, the resin has excellent dispersibility. become.
  • the BET specific surface area of the spherical zirconium tungstate phosphate is larger than 2.0 m 2 / g, for example, when kneading with the resin, the interaction with the resin increases, and the viscosity at the time of molding the resin is high.
  • BET specific surface area is preferably 0.01 m 2 / g or more 2.0 m 2 / g or less, more preferably 0.01 m 2 / G to 1.5 m 2 / g, more preferably 0.01 m 2 / g to 1.2 m 2 / g.
  • the firing temperature and firing time may be adjusted in a suitable method for producing zirconium tungstate phosphate described below.
  • the spherical zirconium tungstate phosphate used as the negative thermal expansion material in the present invention contains at least Mg and / or V as a subcomponent element in a solid solution (hereinafter, sometimes simply referred to as “subcomponent element”). ) Is preferable from the viewpoint of improving the dispersibility and filling characteristics of the resin.
  • “containing at least Mg and / or V as a sub-element component” essentially includes Mg and / or V as a sub-component element, and may also contain other sub-component elements. Means that.
  • sub-element components other than Mg and / or V include, for example, Zn, Cu, Fe, Cr, Mn, Ni, Li, Al, B, Na, K, F, Cl, Br, I, Ca, and Sr. Ba, Ti, Hf, Nb, Ta, Y, Yb, Si, S, Mo, Co, Bi, Te, Pb, Ag, Cd, In, Sn, Sb, Ga, Ge, La, Ce, Nd, Sm , Eu, Tb, Dy and Ho. 1 type, or 2 or more types may be sufficient as these components.
  • the subcomponent elements are only Mg and / or V.
  • the combined use of Mg and V is excellent in sphericity, and also improves the dispersibility and the filling characteristics for the positive thermal expansion material. To preferred.
  • the content of the subcomponent elements is preferably 0.1% by mass or more and 3% by mass or less, more preferably from the viewpoint of having excellent negative thermal expansibility and further excellent dispersibility and filling characteristics. Is 0.2 mass% or more and 2 mass% or less.
  • the molar ratio of V to Mg (V / Mg) is preferably 0.1 or more and 2.0 or less, more preferably from the viewpoint of increasing the synergistic effect of Mg and V. Is 0.2 or more and 1.5 or less.
  • the spherical zirconium tungstate phosphate used as the negative thermal expansion material of the present invention has an average particle diameter of preferably 1 ⁇ m or more and 50 ⁇ m or less, and more preferably 2 ⁇ m or more and 30 ⁇ m or less, from the viewpoint of filling properties with respect to the positive thermal expansion material.
  • the average particle diameter is an average value measured for 50 or more arbitrarily extracted particles by observation with a scanning electron microscope.
  • the average particle diameter of the spherical zirconium tungstate phosphate is the primary particle tungsten phosphate when the spherical zirconium tungstate phosphate is used as a negative thermal expansion material in the form of monodispersed primary particles. This is the average particle size of the zirconium oxide particles themselves.
  • the zirconium tungstate phosphate is used as a negative thermal expansion material in the form of aggregated particles in which fine primary particles form aggregates to form secondary particles, the average particle diameter of the aggregated particles themselves That is.
  • this definition is followed.
  • the spherical zirconium tungstate phosphate used as the negative thermal expansion material of the present invention has a tap density of preferably 1.3 ml / g or more, and more preferably 1.5 ml / g, from the viewpoint of filling properties with respect to the positive thermal expansion material. g to 2.5 ml / g.
  • the tap density indicates a filling characteristic in a state where the negative thermal expansion material is naturally mixed without being particularly pressurized, and a sample of about 50 g or more and 70 g or less is put in a measuring cylinder, Automatic graduated cylinder. It is set in the D measuring apparatus, and the tapping frequency is 500 times, the tapping height is 3.2 mm, and the tapping pace is 200 times / minute as measurement conditions (according to ASTM: B527-93, 85).
  • the spherical zirconium tungstate phosphate used as the negative thermal expansion material of the present invention has a bulk density of preferably 0.8 ml / g or more, and more preferably 1.0 ml, from the viewpoint of further improving the filling property to the positive thermal expansion material. ⁇ 1.6 ml / g.
  • the bulk density is a mass per unit volume when powder is filled into a fixed container by natural fall, and can be measured according to JIS K5101-12-1: 2004. Specifically, the bulk density can be measured using, for example, a bulk specific gravity measuring device (manufactured by Kuramochi Scientific Instruments).
  • the negative thermal expansion material of the present invention may be a mixture of spherical coarse particles of zirconium phosphate tungstate and fine particles smaller than the coarse particles in order to further improve the filling property.
  • the average particle diameter of the spherical particles of spherical zirconium tungstate phosphate is preferably 5 ⁇ m or more, more preferably 5 ⁇ m or more and 30 ⁇ m or less.
  • the average particle diameter of spherical zirconium tungstate phosphate fine particles is preferably less than 5 ⁇ m, more preferably 1 ⁇ m or more and 4 ⁇ m or less.
  • the average particle diameter is an average value measured for 50 or more arbitrarily extracted particles by scanning electron microscope observation.
  • the blending ratio of the spherical zirconium tungstate phosphate coarse particles and the spherical zirconium tungstate phosphate fine particles may be adjusted so that the tap density and bulk density are within the above ranges.
  • the negative thermal expansion material of the present invention has an angle of repose of preferably 50 ° or less, more preferably 30 ° or more and 50 ° or less, and particularly preferably 38 ° or more and 48 ° from the viewpoint of filling property and dispersibility with respect to the positive thermal expansion material. It is as follows.
  • the angle of repose is an angle formed by the slope of the mountain of the sediment and the horizontal plane that maintains stability without spontaneously collapsing when the powder is naturally dropped and deposited. Specifically, it can be measured using a measuring device such as a powder tester (PT-N type manufactured by Hosokawa Micron).
  • the spherical zirconium tungstate phosphate used as the negative thermal expansion material in the present invention is preferably an aggregated particle in which primary particles are aggregated to form secondary particles. Since the agglomerated particles have voids between the primary particles, the specific gravity of the particles themselves is smaller than when the spherical zirconium tungstate phosphate is used in the state of monodispersed primary particles. The specific gravity difference can be reduced. Due to this, the negative thermal expansion material can be prevented from settling in the resin.
  • the “primary particle” is an object that is recognized as a minimum unit as a particle as judged from an apparent geometric form.
  • the agglomerated particles used as the negative thermal expansion material are preferably 1.2 m 2 / g or less, more preferably 0.01 m 2 / g or more and 1.2 m 2 / g or less, particularly 0.01 m 2 / g or more.
  • the surface of the agglomerated particles can keep the voids between the primary particles low while the voids are present inside the agglomerated particles. The interaction with the thermal expansion material can be further reduced, and as a result, the dispersibility for the resin can be further improved.
  • the average particle diameter of the primary particles determined from observation with a scanning electron microscope is preferably 3 ⁇ m or less, more preferably 0.1 ⁇ m or more and 2 ⁇ m, from the viewpoint of keeping the particles spherical. It is as follows.
  • the average particle diameter of the primary particles is an average value measured for 50 or more arbitrarily extracted particles by observation with a scanning electron microscope.
  • the method for producing a negative thermal expansion material of the present invention preferably includes the following steps.
  • Step A A slurry containing a zirconium compound selected from zirconium hydroxide and zirconium carbonate, phosphoric acid, and a tungsten compound is heat-treated.
  • Step B The slurry after Step A is subjected to wet pulverization with a media mill.
  • Step C The slurry after Step B is spray-dried to obtain a spherical reaction precursor.
  • Step D Firing the spherical reaction precursor.
  • a compound containing at least a subcomponent element selected from a magnesium compound and / or a vanadium compound can be added before Step A to Step B.
  • each step will be described.
  • Step A In this step, a slurry containing a zirconium compound selected from zirconium hydroxide and zirconium carbonate, phosphoric acid, and a tungsten compound is heat-treated. As will be described later, the compound containing subcomponent elements is added before Step A to Step B.
  • a phosphoric acid and zirconium compound are added after preparing a slurry in which a tungsten compound is uniformly dispersed in advance, the viscosity of the slurry increases due to the tungsten compound, and it is difficult to uniformly mix the raw materials. There is.
  • the present inventor has found that a slurry containing a tungsten compound, phosphoric acid and a zirconium compound is heat-treated, thereby reducing the viscosity of the slurry and obtaining a slurry that can be wet pulverized by a media mill. It was.
  • the zirconium compound used in Step A is at least one of zirconium hydroxide and zirconium carbonate.
  • the zirconium compound can be used without particular limitation as long as it is industrially available.
  • the zirconium compound may be an anhydrous salt or a hydrated salt.
  • Zirconium carbonate used as the zirconium compound may be a basic salt or a double salt such as ammonia, sodium, or potassium.
  • the zirconium compound can be directly added to the slurry of Step A as a powder. Alternatively, the zirconium compound may be added as a suspension dispersed in an aqueous solvent or a solution dissolved in an aqueous solvent.
  • the tungsten compound used in Step A is preferably a compound that is insoluble or hardly soluble in water.
  • tungsten compounds include tungsten trioxide, ammonium tungstate and tungsten chloride. Of these, tungsten trioxide having a high purity is preferred from the viewpoint of being easily available industrially and easy to handle.
  • the type of phosphoric acid used in step A is not particularly limited as long as it is industrially available. Phosphoric acid can be used as an aqueous solution.
  • the amount of zirconium compound added to the slurry is such that the molar ratio (Zr / W) of the Zr element in the zirconium compound to the W element in the tungsten compound in the slurry is from the viewpoint of increasing the negative thermal expansion of the negative thermal expansion material.
  • the amount is preferably 1.7 to 2.3, and more preferably 1.9 to 2.1.
  • the amount of phosphoric acid added to the slurry is such that the molar ratio (P / W) of P element in phosphoric acid to W element in the tungsten compound in the slurry is increased from the viewpoint of increasing the negative thermal expansion of the negative thermal expansion material.
  • the amount is preferably 1.7 to 2.3, and more preferably 1.9 to 2.1.
  • the solvent for dispersing the tungsten compound, phosphoric acid and zirconium compound used in the step A is not limited to water but may be a mixed solvent of water and a hydrophilic solvent.
  • the concentration of the slurry containing these solvents is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 30% by mass or less, from the viewpoint of providing a slurry having a viscosity that is easy to handle and handle.
  • step A there is no particular limitation on the order of addition of the respective raw materials, and the order of addition can be determined as appropriate in consideration of the reactor and the like.
  • the order of addition can be determined as appropriate in consideration of the reactor and the like.
  • the slurry heat treatment temperature in the step A is preferably 40 ° C. or higher and 110 ° C. or lower, more preferably 60 ° C. or higher and 90 ° C. or lower, from the viewpoint of providing a slurry with viscosity that is easy to handle and easy to handle.
  • the heat treatment time in the step A is not critical in the present production method, and the reaction may be performed for a sufficient time until the slurry viscosity is appropriately lowered. In many cases, a satisfactory low-viscosity slurry can be produced by a heat treatment of preferably 0.5 hours or more, more preferably 1 hour or more and 4 hours or less.
  • a compound containing at least a subcomponent element selected from a magnesium compound and / or a vanadium compound (hereinafter sometimes simply referred to as “compound containing a subcomponent element”) is used before Step A to Step B. That is, it can be added to the slurry before completion of Step B. Specifically, at least of performing the A process, performing the A process, performing the A process, completing the A process, performing the B process, and performing the B process. In one scene, a compound containing subcomponent elements is added.
  • magnesium compound examples include magnesium oxide, hydroxide, carbonate, organic acid salt, nitrate, phosphate, sulfate, chloride, bromide, iodide and the like.
  • magnesium oxide and hydroxide is preferable from the viewpoint of easily controlling the purity of the obtained negative thermal expansion material and easily obtaining a high-purity product.
  • vanadium compound examples include vanadium oxide, hydroxide, carbonate, organic acid salt, ammonium salt, nitrate, phosphate, sulfate, chloride, bromide, iodide and the like.
  • oxides and hydroxides containing vanadium from the viewpoint of easily controlling the purity of the obtained negative thermal expansion material and easily obtaining a high-purity product.
  • a compound containing other subcomponent elements other than Mg and / or V can be used in combination.
  • the steps A to What is necessary is just to add to a slurry before B process, ie, before B process.
  • Examples of the compound containing subcomponent elements other than Mg and / or V include, for example, Zn, Cu, Fe, Cr, Mn, Ni, Li, Al, B, Na, K, F, Cl, Br, I, Ca, Sr, Ba, Ti, Hf, Nb, Ta, Y, Yb, Si, S, Mo, Co, Bi, Te, Pb, Ag, Cd, In, Sn, Sb, Te, Ga, Ge, La, Examples thereof include compounds containing at least one subcomponent element selected from Ce, Nd, Sm, Eu, Tb, Dy and Ho. These can be used individually by 1 type or in combination of 2 or more types.
  • Examples of the compound containing subcomponent elements other than Mg and / or V include oxides, hydroxides, carbonates, organic acid salts, ammonium salts, nitrates, phosphates, sulfates containing the subcomponent elements. , Chloride, bromide, iodide and the like. Among these, it is preferable to use oxides and hydroxides containing subcomponent elements from the viewpoint of easily controlling the purity of the obtained negative thermal expansion material and easily obtaining a high-purity product.
  • the pH of the slurry can be adjusted with an alkali or an acid as necessary for the purpose of dissolving or precipitating the compound containing the added subcomponent element in the slurry.
  • the amount of the magnesium compound and vanadium compound added to the slurry of the compound containing the auxiliary component element used as necessary is preferably 0.05% by mass or more and 5.0% as the auxiliary component element in the obtained spherical reaction precursor.
  • the amount is not more than mass%, more preferably not less than 0.1 mass% and not more than 3.0 mass%.
  • the zirconium compound, phosphoric acid, tungsten compound and the compound containing subcomponent elements used in this step are preferably high purity products in order to obtain high purity spherical zirconium tungstate phosphate.
  • Step B the slurry after step A is wet pulverized by a media mill to obtain a slurry in which each raw material is dispersed finely and uniformly.
  • a media mill a bead mill, a ball mill, a paint shaker, an attritor, a sand mill, or the like can be used. It is particularly preferable to use a bead mill. In that case, the operating conditions and the type and size of the beads may be appropriately selected according to the size of the apparatus and the processing amount.
  • a dispersant may be added to the slurry. What is necessary is just to select a suitable dispersing agent to use according to the kind of dispersion medium.
  • the dispersion medium is water, for example, various surfactants and polycarboxylic acid ammonium salts can be used as the dispersant.
  • the concentration of the dispersing agent in the slurry is 0.01% by mass or more and 10% by mass or less, particularly 0.1% by mass or more and 5% by mass or less, from the viewpoint of increasing the dispersion effect.
  • the wet pulverization treatment using a media mill preferably has an average particle diameter of a solid content determined by a laser diffraction / scattering method of 2 ⁇ m or less, from the viewpoint of obtaining a spherical reaction precursor with even better reactivity. Preferably it is carried out until it becomes 1 ⁇ m or less, particularly preferably 0.1 ⁇ m or more and 0.5 ⁇ m or less.
  • Step C The slurry after completion of Step B is subjected to the next Step C without solid-liquid separation, and the slurry is spray-dried in Step C to obtain a spherical reaction precursor.
  • the slurry is atomized by a predetermined means, and fine droplets generated thereby are dried to obtain a spherical reaction precursor.
  • the atomization of the slurry includes, for example, a method using a rotating disk and a method using a pressure nozzle. Any method can be used in this step.
  • the size of the atomized droplet is not particularly limited, but is preferably 1 ⁇ m or more and 40 ⁇ m or less, and particularly preferably 5 ⁇ m or more and 30 ⁇ m or less. It is desirable to determine the supply amount of the slurry to the spray dryer in consideration of this viewpoint.
  • the hot air temperature in the spray drying apparatus is preferably adjusted to 100 ° C. or higher and 270 ° C. or lower, and more preferably 150 ° C. or higher and 230 ° C. or lower, from the viewpoint of preventing moisture absorption of the powder and facilitating powder collection. preferable.
  • the spherical reaction precursor obtained by spray drying is a granulated particle containing the raw material components W, P and Zr for producing zirconium phosphate tungstate.
  • the spherical reaction precursor obtained by this step preferably has an infrared absorption peak at least from 950 cm ⁇ 1 to 1150 cm ⁇ 1 . Further, in this wave number range, the maximum value of the infrared absorption peak is preferably 1030 ( ⁇ 20) cm ⁇ 1 .
  • the reason for this is as follows. As shown in Reference Example 1 described later, when a reaction precursor containing no subcomponent element was obtained using phosphoric acid, tungsten trioxide and zirconium hydroxide, when the reaction precursor was subjected to X-ray diffraction analysis A diffraction peak of only tungsten trioxide was confirmed (see FIG. 1), and a diffraction peak of zirconium hydroxide was not observed.
  • the reaction precursor obtained in this step is considered to exhibit an infrared absorption peak pattern different from that of the raw material when the zirconium compound and phosphoric acid react in Step A.
  • the inventor presumes that the amorphous compound containing phosphorus and zirconium obtained by the reaction of phosphoric acid and zirconium hydroxide is amorphous zirconium phosphate.
  • step D the spherical reaction precursor obtained in step C is fired to obtain the target spherical zirconium tungstate phosphate.
  • the firing temperature for firing the spherical reaction precursor is preferably 900 ° C. or higher and 1300 ° C. or lower. The reason for this is that by setting the firing temperature to 900 ° C. or higher, unreacted oxides and the like are less likely to remain, and a single-phase zirconium tungstate phosphate tends to be easily obtained by X-ray diffraction, This is because, by setting the firing temperature to 1300 ° C. or less, it is difficult to form a lump in which particles are consolidated, and powder tends to be obtained.
  • the firing time is not critical in the present production method, and the reaction may be carried out for a sufficient time until single-phase zirconium tungstate phosphate is produced by X-ray diffraction.
  • zirconium phosphate tungstate having satisfactory physical properties can be produced by firing for preferably 1 hour or longer, more preferably 2 hours or longer and 20 hours or shorter.
  • the firing atmosphere is not particularly limited, and may be any of an inert gas atmosphere, a vacuum atmosphere, an oxidizing gas atmosphere, and air.
  • Calcination may be performed as many times as desired.
  • the fired material may be pulverized and then refired.
  • zirconium tungstate phosphate After firing, it is cooled as appropriate, and the target zirconium tungstate phosphate can be obtained by performing pulverization, crushing, classification, etc. as necessary.
  • This zirconium tungstate phosphate has a negative coefficient of thermal expansion, is single-phase in X-ray diffraction, and is spherical.
  • the negative thermal expansion material according to the present invention can be used as powder or paste. When used as a paste, it can be used in the state of a paste with a liquid resin having a low viscosity. Or you may use in the state of the paste containing a solvent and also a binder, a flux material, a dispersing agent, etc. if necessary.
  • the blending amount of the negative thermal expansion material in the paste is not particularly limited, but in many cases, it is preferably 5% by volume or more and 65% by volume or less.
  • the paste containing the negative thermal expansion material of the present invention and further containing a binder and a flux material can be suitably used as a sealing material, for example.
  • binder used in the paste those commonly used in the technical field are used.
  • nitrocellulose, ethyl cellulose, polyethylene carbonate, polypropylene carbonate, acrylic acid ester, methacrylic acid ester, polyethylene glycol derivative, polymethylstyrene and the like can be mentioned.
  • Examples of the flux material used in the paste include low-melting glass, and those common in the technical field are used.
  • PbO—B 2 O 3 system, PbO—SiO 2 —B 2 O 3 system, Bi 2 O 3 —B 2 O 3 system, Bi 2 O 3 —SiO 2 —B 2 O 3 system, SiO 2 —B 2 O 3 —Al 2 O 3 system, SiO 2 —B 2 O 3 —BaO system, SiO 2 —B 2 O 3 —CaO system, ZnO—B 2 O 3 —Al 2 O 3 system, ZnO—SiO 2 —B 2 O 3 system, P 2 O 5 system, SnO—P 2 O 5 system, V 2 O 5 —P 2 O 5 system, V 2 O 5 —Mo 2 O 3 system, and V 2 O 5 —P 2 O 5- TeO 2 etc. are listed.
  • the negative thermal expansion material of the present invention is contained in a positive thermal expansion material to form a composite material, and a material having negative thermal expansion, zero thermal expansion or low thermal expansion can be obtained depending on the blending ratio of the negative thermal expansion material.
  • the negative thermal expansion material of the present invention may be used in combination with other negative thermal expansion materials and fillers used for adjusting the thermal expansion coefficient as long as the effects of the present invention are not impaired.
  • Other negative thermal expansion materials and fillers used for adjusting the thermal expansion coefficient include, for example, zirconium tungstate (ZrW 2 O 8 ), Zn x Cd 1-x (CN) 2 , manganese nitride, bismuth / nickel / Iron oxide, zirconium phosphate, cordierite, zircon, zirconia, tin oxide, niobium oxide, quartz, ⁇ -quartz, ⁇ -spodumene, ⁇ -eucryptite, mullite, quartz glass, NbZr (PO 4 ) 3 , Although fused silica etc. are mentioned, it is not limited to these in particular.
  • Examples of the positive thermal expansion material containing the negative thermal expansion material of the present invention include various organic compounds or inorganic compounds.
  • the organic compound include rubber, polyolefin, polycycloolefin, polystyrene, ABS, polyacrylate, polyphenylene sulfide, phenol resin, polyamide resin, polyimide resin, epoxy resin, silicone resin, polycarbonate resin, polyethylene resin, and polypropylene resin.
  • PET resin polyethylene terephthalate resin
  • Examples of the inorganic compound include metals, alloys, silicon dioxide, graphite, sapphire, various glasses, concrete materials, and various ceramic materials.
  • the positive thermal expansion material is preferably at least one selected from metals, alloys, glass, ceramics, rubber and resin.
  • the addition amount of the negative thermal expansion material of the present invention may be a general addition amount in the technical field.
  • X-ray diffraction analysis Rigaku Ultima IV was used for X-ray diffraction analysis of zirconium phosphate tungstate and the reaction precursor. Cu-K ⁇ was used as the radiation source. The measurement conditions were a tube voltage of 40 kV, a tube current of 40 mA, and a scanning speed of 0.1 ° / sec. 2.
  • Infrared absorption spectrum (FT-IR) analysis Infrared absorption spectrum analysis of the reaction precursor was performed with a NICOLET6700 manufactured by Thermo Fisher Scientific, resolution: 4 cm ⁇ 1 , integration number: 256 times, measurement wave number region: 400 cm ⁇ Measurement was performed under conditions of 1 to 4000 cm ⁇ 1 .
  • Average particle diameter The average particle diameter of the solid content in each raw material and slurry was measured by a laser diffraction / scattering method using a Microtrac MT3300EXII particle size analyzer (manufactured by Microtrac Bell).
  • the obtained reaction precursor was subjected to a calcination reaction in the air at 1050 ° C. for 2 hours to obtain a white baked product.
  • the baked product was single-phase Zr 2 (WO 4 ) (PO 4 ) 2 . This was pulverized by an airflow pulverizer to obtain a negative thermal expansion material sample.
  • Example 1 15 parts by mass of commercially available tungsten trioxide (WO 3 ; average particle size 1.2 ⁇ m) was placed in a beaker, and 84 parts by mass of pure water was further added. The mixture was stirred at room temperature (25 ° C.) for 120 minutes to prepare a 15% by mass slurry containing tungsten trioxide. The average particle size of the solid content in the slurry was 1.2 ⁇ m. Next, zirconium hydroxide, 85 mass% phosphoric acid aqueous solution and magnesium hydroxide are added to this slurry, and the molar ratio of Zr: W: P: Mg in the slurry is 2.00: 1.00: 2.00: 0.
  • the obtained reaction precursor was subjected to a calcination reaction in the air at 1050 ° C. for 2 hours to obtain a white baked product.
  • the baked product was single-phase Zr 2 (WO 4 ) (PO 4 ) 2 . This was used as a negative thermal expansion material sample.
  • Example 2 15 parts by mass of commercially available tungsten trioxide (WO 3 ; average particle size 1.2 ⁇ m) was placed in a beaker, 84 parts by mass of pure water was further added, and 1 part by mass of polycarboxylic acid ammonium salt was charged as a dispersant. The mixture was stirred at room temperature (25 ° C.) for 120 minutes to prepare a 15% by mass slurry containing tungsten trioxide. The average particle size of the solid content in the slurry was 1.2 ⁇ m.
  • tungsten trioxide WO 3 ; average particle size 1.2 ⁇ m
  • zirconium hydroxide, 85 mass% phosphoric acid aqueous solution, magnesium hydroxide, and divanadium pentoxide were added to this slurry, and the molar ratio of Zr: W: P: Mg: V in the slurry was 2.00: 1.
  • the temperature was raised to 80 ° C. and the reaction was carried out with stirring for 4 hours.
  • the slurry was supplied to a media stirring type bead mill charged with zirconia beads having a diameter of 0.5 mm, mixed for 15 minutes, and wet pulverized.
  • the average particle size of the solid content in the slurry after the wet pulverization was 0.3 ⁇ m.
  • the slurry was supplied to a spray dryer set at 220 ° C. at a supply rate of 2.4 L / h to obtain a reaction precursor.
  • a spray dryer set at 220 ° C. at a supply rate of 2.4 L / h to obtain a reaction precursor.
  • a diffraction peak of tungsten trioxide was observed.
  • analysis by FT-IR showed an infrared absorption peak at 950 to 1150 cm ⁇ 1, and the maximum value of the infrared absorption peak during this period appeared at 1030 cm ⁇ 1 .
  • the obtained reaction precursor was subjected to a calcination reaction in the air at 1050 ° C.
  • the baked product was single-phase Zr 2 (WO 4 ) (PO 4 ) 2 . This was used as a negative thermal expansion material sample.
  • Example 3 15 parts by mass of commercially available tungsten trioxide (WO 3 ; average particle size 1.2 ⁇ m) was placed in a beaker, and 84 parts by mass of pure water was further added. The mixture was stirred at room temperature (25 ° C.) for 120 minutes to prepare a 15% by mass slurry containing tungsten trioxide. The average particle size of the solid content in the slurry was 1.2 ⁇ m. Subsequently, zirconium hydroxide and 85 mass% phosphoric acid aqueous solution were added to this slurry at room temperature (25 ° C. so that the molar ratio of Zr: W: P in the slurry was 2.00: 1.00: 2.00.
  • WO 3 tungsten trioxide
  • the temperature was raised to 80 ° C. and the reaction was carried out with stirring for 4 hours.
  • 1 part by weight of polycarboxylic acid ammonium salt as a dispersing agent is charged, and while stirring the slurry, it is supplied to a media stirring type bead mill charged with 0.5 mm diameter zirconia beads, mixed for 15 minutes and wet pulverized Went.
  • the average particle size of the solid content in the slurry after the wet pulverization was 0.3 ⁇ m.
  • the slurry was supplied to a spray dryer set at 220 ° C. at a supply rate of 2.4 L / h to obtain a reaction precursor.
  • the obtained reaction precursor was subjected to a calcination reaction in the air at 1220 ° C. for 8 hours to obtain a white baked product.
  • the baked product was single-phase Zr 2 (WO 4 ) (PO 4 ) 2 . This was used as a negative thermal expansion material sample.
  • the obtained reaction precursor was subjected to a calcination reaction at 1050 ° C. for 2 hours in the air to obtain a white baked product.
  • the baked product was single-phase Zr 2 (WO 4 ) (PO 4 ) 2 . This was used as a negative thermal expansion material sample.
  • the average primary particle diameter of zirconium phosphate tungstate was determined by the average value of 50 or more particles arbitrarily extracted at a magnification of 5,000 in a scanning electron microscope. The particle diameter was the maximum transverse length of each particle.
  • the average secondary particle diameter of zirconium phosphate tungstate was determined by an average value of 50 or more particles arbitrarily extracted at a magnification of 400 times in a scanning electron microscope observation.
  • the particle diameter was the maximum transverse length of each particle.
  • the sphericity was determined by the following calculation formula for 50 particles arbitrarily extracted at a magnification of 400 using an image analyzer Luzex (manufactured by Nireco).
  • Sphericality Equivalent circle equivalent diameter / circumscribed circle diameter
  • Equivalent circle equivalent diameter diameter of the circle whose circumference corresponds to the circumference of the particle circumscribed circle diameter: longest diameter of the particle
  • the sample is received in the bulk density measuring device (capacity 30 mL) of the bulk specific gravity measuring device (capacity of 30 ml) through the sieve until it overflows from the receiver.
  • the bulk density (g / mL) was calculated by measuring the mass of the sample accumulated in the receptor.
  • Example 4 Example 1 5.8 g of the obtained negative thermal expansion material sample and 4.2 g of liquid epoxy resin (Mitsubishi Chemical jER807, epoxy equivalents 160 to 175) were weighed and measured with a vacuum mixer (Shinky Awatori Kentaro ARV-310). 30 vol% paste was prepared by mixing at a rotational speed of 2000 rpm. The viscosity of this paste was measured with a rheometer (HAAKE MARSII manufactured by Thermo Fisher Scientific) at a shear rate of 1 [1 / s] and a shear rate of 10 [1 / s] at 25 ° C.
  • HAAKE MARSII manufactured by Thermo Fisher Scientific
  • a curing agent (Curesol manufactured by Shikoku Kasei) is added to the paste, and mixed at a rotational speed of 1500 rpm with a vacuum mixer (Shinky Awatori Nertaro ARV-310) and cured at 150 ° C. for 1 hour to obtain a resin composite.
  • This resin composite was cut into 5 mm square ⁇ 10 mm, and a linear expansion coefficient of 30 to 120 ° C. was measured at a temperature rising rate of 1 ° C./min using a thermomechanical analyzer (TMA).
  • Example 5 Example 2 5.8 g of the obtained negative thermal expansion material sample and 4.2 g of an epoxy resin (Mitsubishi Chemical jER807, epoxy equivalent 160 to 175) were weighed and rotated with a vacuum mixer (Shinky Awatori Netaro ARV-310). A paste of 30 vol% was prepared by mixing at a speed of 2000 rpm. The viscosity of this paste was measured with a rheometer (HAAKE MARSII manufactured by Thermo Fisher Scientific) at a shear rate of 1 [1 / s] and a shear rate of 10 [1 / s] at 25 ° C.
  • HAAKE MARSII manufactured by Thermo Fisher Scientific
  • a curing agent (Curesol manufactured by Shikoku Kasei) is added to the paste, and mixed at a rotational speed of 1500 rpm with a vacuum mixer (Shinky Awatori Nertaro ARV-310) and cured at 150 ° C. for 1 hour to obtain a resin composite.
  • This resin composite was cut into 5 mm square ⁇ 10 mm, and a linear expansion coefficient of 30 to 120 ° C. was measured at a temperature rising rate of 1 ° C./min using a thermomechanical analyzer (TMA).
  • Example 6 5.8 g of the negative thermal expansion material sample obtained in Example 3 and 4.2 g of liquid epoxy resin (Mitsubishi Chemical jER807, epoxy equivalents 160 to 175) were weighed and placed in a vacuum mixer (Shinky Awatori Nerita ARV-310). And 30 vol% paste was prepared by mixing at a rotational speed of 2000 rpm. The viscosity of this paste was measured with a rheometer (HAAKE MARSII manufactured by Thermo Fisher Scientific) at a shear rate of 1 [1 / s] and a shear rate of 10 [1 / s] at 25 ° C.
  • HAAKE MARSII manufactured by Thermo Fisher Scientific
  • a curing agent (Curesol manufactured by Shikoku Kasei) is added to the paste, and mixed at a rotational speed of 1500 rpm with a vacuum mixer (Shinky Awatori Nertaro ARV-310) and cured at 150 ° C. for 1 hour to obtain a resin composite.
  • This resin composite was cut into 5 mm square ⁇ 10 mm, and a linear expansion coefficient of 30 to 120 ° C. was measured at a temperature rising rate of 1 ° C./min using a thermomechanical analyzer (TMA).
  • Reference Example 3 Reference Example 1 5.8 g of the obtained negative thermal expansion material and 4.2 g of an epoxy resin (Mitsubishi Chemical jER807, epoxy equivalent 160 to 175) were weighed and rotated at a rotational speed with a vacuum mixer (Shinky Awatori Nertaro ARV-310). 30 vol% paste was prepared by mixing at 2000 rpm. The viscosity of this paste was measured with a rheometer (HAAKE MARSII manufactured by Thermo Fisher Scientific) at a shear rate of 1 [1 / s] and a shear rate of 10 [1 / s] at 25 ° C.
  • HAAKE MARSII manufactured by Thermo Fisher Scientific
  • a curing agent (Curesol manufactured by Shikoku Kasei) is added to the paste, and mixed at a rotational speed of 1500 rpm with a vacuum mixer (Shinky Awatori Nertaro ARV-310) and cured at 150 ° C. for 1 hour to obtain a resin composite.
  • This resin composite was cut into 5 mm square ⁇ 10 mm, and a linear expansion coefficient of 30 to 120 ° C. was measured at a temperature rising rate of 1 ° C./min using a thermomechanical analyzer (TMA).
  • Reference Example 2 5.8 g of the obtained negative thermal expansion material and 4.2 g of an epoxy resin (Mitsubishi Chemical jER807, epoxy equivalent 160 to 175) were weighed and rotated with a vacuum mixer (Shinky Awatori Nertaro ARV-310). 30 vol% paste was prepared by mixing at 2000 rpm. The viscosity of this paste was measured with a rheometer (HAAKE MARSII manufactured by Thermo Fisher Scientific) at a shear rate of 1 [1 / s] and a shear rate of 10 [1 / s] at 25 ° C.
  • HAAKE MARSII manufactured by Thermo Fisher Scientific
  • a curing agent (Curesol manufactured by Shikoku Kasei) is added to the paste, and mixed at a rotational speed of 1500 rpm with a vacuum mixer (Shinky Awatori Nertaro ARV-310) and cured at 150 ° C. for 1 hour to obtain a resin composite.
  • This resin composite was cut into 5 mm square ⁇ 10 mm, and a linear expansion coefficient of 30 to 120 ° C. was measured at a temperature rising rate of 1 ° C./min using a thermomechanical analyzer (TMA).
  • a curing agent (Curesol manufactured by Shikoku Kasei) is added to the paste, and mixed at a rotational speed of 1500 rpm with a vacuum mixer (Shinky Awatori Nertaro ARV-310) and cured at 150 ° C. for 1 hour to obtain a resin composite.
  • This resin composite was cut into 5 mm square ⁇ 10 mm, and a linear expansion coefficient of 30 to 120 ° C. was measured at a temperature rising rate of 1 ° C./min using a thermomechanical analyzer (TMA).
  • Example 1 From the results in Table 2, the negative thermal expansion materials of Example 1, Example 2 and Example 3 have a lower viscosity at the time of molding the resin even when blended with the resin than in Reference Examples 1 and 2. Moreover, it turns out that it can shape

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Abstract

Le problème décrit par la présente invention est de fournir un matériau à dilatation thermique négative présentant une excellente dispersibilité et d'excellentes caractéristiques de remplissage par rapport à un matériau à dilatation thermique positive. La solution de la présente invention porte sur le matériau à dilatation thermique négative comprenant du phosphate de tungstène et de zirconium sphérique doté d'une surface spécifique BET égale ou inférieure à 2 m2/g. La sphéricité du matériau à dilatation thermique négative est idéalement de 0,90 à 1. Le matériau à dilatation thermique négative contient idéalement au moins du Mg et/ou du V en tant qu'éléments sous-constituants. La teneur en éléments sous-constituants du matériau à dilatation thermique négative est idéalement de 0,1 à 3 % en poids. La taille moyenne de particules du matériau à dilatation thermique négative est idéalement de 1 à 50 µm.
PCT/JP2016/079397 2015-10-07 2016-10-04 Matériau à dilatation thermique négative et matériau composite le comprenant Ceased WO2017061403A1 (fr)

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KR1020187008487A KR102070738B1 (ko) 2015-10-07 2016-10-04 부열팽창재 및 그것을 포함하는 복합재료
US15/759,333 US10280086B2 (en) 2015-10-07 2016-10-04 Negative thermal expansion material and composite material comprising same
CN201680055928.7A CN108025915B (zh) 2015-10-07 2016-10-04 负热膨胀材料和含有该负热膨胀材料的复合材料
EP16853557.3A EP3360848B1 (fr) 2015-10-07 2016-10-04 Matériau à dilatation thermique négative et matériau composite le comprenant

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JP2019112614A (ja) * 2017-12-04 2019-07-11 ショット アクチエンゲゼルシャフトＳｃｈｏｔｔ ＡＧ 少なくとも１つの第１の材料と粒子とを含み、前記粒子が負の熱膨張係数αを有する複合材料、および前記複合材料を含む接着材料
WO2020179703A1 (fr) * 2019-03-07 2020-09-10 日本化学工業株式会社 Tungstate de phosphate de zirconium modifié, charge de dilatation thermique négative et composition polymère
JP2020147486A (ja) * 2019-03-07 2020-09-17 日本化学工業株式会社 改質リン酸タングステン酸ジルコニウム、負熱膨張フィラー及び高分子組成物
CN112384471A (zh) * 2018-06-26 2021-02-19 日本化学工业株式会社 负热膨胀材料、其制造方法和复合材料
CN115637089A (zh) * 2021-07-18 2023-01-24 云南光电辅料有限公司 一种红外杂散辐射消光材料及其制备方法
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WO2019087722A1 (fr) * 2017-10-31 2019-05-09 日本化学工業株式会社 Tungstate de phosphate de zirconium modifié, charge à expansion thermique négative et composition polymère
JP6553831B1 (ja) * 2017-10-31 2019-07-31 日本化学工業株式会社 改質リン酸タングステン酸ジルコニウム、負熱膨張フィラー及び高分子組成物
TWI846677B (zh) * 2017-10-31 2024-07-01 日商日本化學工業股份有限公司 改質磷酸鎢酸鋯、負熱膨脹填料和高分子組成物
JP2019102782A (ja) * 2017-11-28 2019-06-24 住友ベークライト株式会社 熱硬化性樹脂組成物、磁性コアおよび／または外装部材を備えるコイルおよび成形品の製造方法
JP2019112614A (ja) * 2017-12-04 2019-07-11 ショット アクチエンゲゼルシャフトＳｃｈｏｔｔ ＡＧ 少なくとも１つの第１の材料と粒子とを含み、前記粒子が負の熱膨張係数αを有する複合材料、および前記複合材料を含む接着材料
JP7254493B2 (ja) 2017-12-04 2023-04-10 ショット アクチエンゲゼルシャフト 少なくとも１つの第１の材料と粒子とを含み、前記粒子が負の熱膨張係数αを有する複合材料、および前記複合材料を含む接着材料
CN112384471A (zh) * 2018-06-26 2021-02-19 日本化学工业株式会社 负热膨胀材料、其制造方法和复合材料
CN112384471B (zh) * 2018-06-26 2023-08-04 日本化学工业株式会社 负热膨胀材料、其制造方法和复合材料
US11332599B2 (en) 2019-03-07 2022-05-17 Nippon Chemical Industrial Co., Ltd. Modified zirconium phosphate tungstate, negative thermal expansion filler and polymer composition
JP2020147486A (ja) * 2019-03-07 2020-09-17 日本化学工業株式会社 改質リン酸タングステン酸ジルコニウム、負熱膨張フィラー及び高分子組成物
WO2020179703A1 (fr) * 2019-03-07 2020-09-10 日本化学工業株式会社 Tungstate de phosphate de zirconium modifié, charge de dilatation thermique négative et composition polymère
CN115637089A (zh) * 2021-07-18 2023-01-24 云南光电辅料有限公司 一种红外杂散辐射消光材料及其制备方法
WO2023037930A1 (fr) * 2021-09-07 2023-03-16 日本化学工業株式会社 Matériau à dilatation thermique négative, son procédé de production et pâte

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