WO2013080455A1 - 不定形組成物 - Google Patents

不定形組成物 Download PDF

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Publication number
WO2013080455A1
WO2013080455A1 PCT/JP2012/007209 JP2012007209W WO2013080455A1 WO 2013080455 A1 WO2013080455 A1 WO 2013080455A1 JP 2012007209 W JP2012007209 W JP 2012007209W WO 2013080455 A1 WO2013080455 A1 WO 2013080455A1
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WIPO (PCT)
Prior art keywords
inorganic
weight
amorphous composition
composition according
inorganic powder
Prior art date
Application number
PCT/JP2012/007209
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English (en)
French (fr)
Inventor
賢 米内山
徹也 三原
智彦 岸木
鉄也 石原
Original Assignee
ニチアス株式会社
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Application filed by ニチアス株式会社 filed Critical ニチアス株式会社
Priority to CN201280059269.6A priority Critical patent/CN103958440B/zh
Priority to EP20120853336 priority patent/EP2786976A4/en
Priority to US14/361,863 priority patent/US20140378596A1/en
Publication of WO2013080455A1 publication Critical patent/WO2013080455A1/ja

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    • C04B2235/5445Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/608Green bodies or pre-forms with well-defined density
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607Thermal properties, e.g. thermal expansion coefficient
    • C04B2235/9615Linear firing shrinkage

Definitions

  • the present invention is, for example, an amorphous composition used as a joint material for filling a gap in a heat treatment apparatus, an industrial furnace or an incinerator, particularly a fireproof tile, a heat insulating brick, an iron skin, a mortar refractory, More specifically, the present invention relates to an amorphous composition containing specific biosoluble inorganic fibers.
  • amorphous compositions have contained inorganic fibers such as glass fibers, glass wool, ceramic wool, rock wool, alumina fibers, zirconia fibers, silica / alumina fibers as reinforcing fibers.
  • the amorphous composition is inserted into a gap such as a tile by, for example, glazing, spraying, or pouring to form a joint.
  • the inorganic fibers contained in the amorphous composition become dust and are scattered in the air, and the operator inhales the dust. Since inorganic fibers are in danger of health damage if they are inhaled by humans and enter the lungs, at present, amorphous compositions using biosoluble fibers as inorganic fibers have been developed (for example, Patent Documents 1 to 5). .
  • the amorphous composition is usually stored after production. As described above, it is dried after being applied or embedded in the repair of the furnace or the formation of joints. It is then exposed to high temperatures in a furnace. Therefore, the following practical characteristics are required when the equipment is dried after being applied and dried after the paste is in storage and use. When pasting, the consistency (viscosity) is appropriate, the workability is excellent, and the long-term stability is excellent (the storage property is excellent). After drying, there is little drying shrinkage, little change in shape, and high drying strength. At the time of heating, the heat shrinkage rate is small and heat resistance and thermal conductivity are excellent. For example, it is practically preferable that the heat shrinkage ratio after heating at 1100 ° C. is less than 50%, or that there is no obvious vitrification or deformation in appearance.
  • the present inventors have developed a novel biosoluble fiber excellent in fire resistance and biosolubility (Japanese Patent Application No. 2011-59354).
  • One object of the present invention is to provide an amorphous composition having practical properties, including such biosoluble fibers having excellent fire resistance and biosolubility.
  • the following amorphous composition is provided.
  • composition of inorganic fiber SiO 2 66-82% by weight CaO 10-34% by weight MgO 3 wt% or less Al 2 O 3 5 wt% or less The total of SiO 2 , CaO, MgO and Al 2 O 3 is 98 wt% or more.
  • the amorphous composition according to 1 comprising the inorganic powder.
  • the amorphous composition according to 2 wherein the inorganic powder is composed of one or more selected from silica, alumina, mullite, zircon, zirconia, titania, clay mineral, calcia and magnesia. 5.
  • the inorganic binder comprises one or more selected from colloidal silica, alumina sol, zirconia sol, titania sol, and an aluminum phosphate aqueous solution.
  • the inorganic binder is contained in an amount of 1 to 30 parts by weight as a solid content when the total of the inorganic fibers and the inorganic powder is 100 parts by weight.
  • the organic binder comprises one or more selected from acrylic emulsion, starch, and thickener.
  • 14. A molded product obtained by drying the amorphous composition according to any one of 1 to 13.
  • an amorphous composition having practical properties, including biosoluble fibers excellent in fire resistance and biosolubility.
  • the amorphous composition of the present invention contains a specific biosoluble fiber excellent in fire resistance and biosolubility as a reinforcing fiber.
  • Biosoluble fibers can be broadly classified into Mg silicate fibers containing a lot of MgO and Ca silicate fibers containing a lot of CaO.
  • Ca silicate fibers are used. Since the biosoluble fiber is easily soluble in water, it is usually dissolved in water contained in the composition and the contained components are eluted. It may react with other components in the composition, the object to be applied, and the like, causing inconvenience. Accordingly, a composition containing ceramic fibers that are hardly soluble in water may behave differently from a composition containing biosoluble fibers, and among biosoluble fibers, a composition containing Mg silicate fibers and Ca silicate fibers. Since the composition and the amount of the eluted component are different, the composition containing may sometimes show different behavior.
  • Mg silicate fiber When using Mg silicate fiber for the amorphous composition, organic fiber is added as a binder in order to ensure necessary strength, but addition of organic fiber is not necessary for Ca silicate fiber. Further, when using Mg silicate fiber, it is necessary to add a pH adjusting agent (buffer solution such as phosphate buffer and borate buffer, and acid such as acetic acid). If a pH adjuster is not added, there is a risk of solidifying during storage, resulting in increased drying shrinkage. However, the addition of a pH adjusting agent is not necessary for Ca silicate fibers. Furthermore, when Mg silicate fiber is used, it is dissolved during storage unless the fiber surface is coated with phosphate or the like, but Ca silicate fiber does not require coating.
  • a pH adjusting agent buffer solution such as phosphate buffer and borate buffer, and acid such as acetic acid
  • the Ca silicate fiber used in the present invention has the following composition. SiO 2 66-82% by weight (for example, 66-75% by weight, 68-80% by weight, 70-80% by weight, 71-75% by weight, 71-80% by weight or 71-76% by weight) ) CaO 10-34% by weight (for example, it can be 20-30% by weight or 21-26% by weight) MgO 3 wt% or less (eg, 1 wt% or less) Al 2 O 3 5% by weight or less (eg, 3.5% by weight or less or 3% by weight or less. Also, 1% by weight or more or 2% by weight or more) Other oxides ⁇ 2% by weight
  • the Al 2 O 3 content can be, for example, 3.4% by weight or less or 3.0% by weight or less. Moreover, it can be 1.1 weight% or more or 2.0 weight% or more. The content is preferably 0 to 3% by weight, more preferably 1 to 3% by weight. If Al 2 O 3 is contained within this range, the strength becomes high.
  • the above inorganic fibers include other oxides such as alkali metal oxides (K 2 O, Na 2 O, etc.), Fe 2 O 3 , ZrO 2 , P 2 O 5 , B 2 O 3 , TiO 2 , MnO, R 2 O 3 (R is selected from Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, or a mixture thereof) The above may or may not be included. Other oxides may be 0.2 wt% or less or 0.1 wt% or less, respectively.
  • the alkali metal oxide may contain 0.2% by weight or less of each oxide, and the total of the alkali metal oxides may be 0.2% by weight or less.
  • the biosoluble fiber may have a total of SiO 2 , CaO, MgO, Al 2 O 3 of more than 98% by weight or more than 99% by weight.
  • the biologically soluble inorganic fiber is, for example, an inorganic fiber having a physiological saline dissolution rate at 40 ° C. of 1% or more.
  • the physiological saline dissolution rate is measured, for example, as follows. That is, first, 1 g of a sample prepared by pulverizing inorganic fibers to 200 mesh or less and 150 mL of physiological saline are placed in an Erlenmeyer flask (volume: 300 mL) and placed in an incubator at 40 ° C. Next, a horizontal vibration of 120 revolutions per minute is continuously applied to the Erlenmeyer flask for 50 hours.
  • the concentration (mg / L) of each element contained in the filtrate obtained by filtration is measured with an ICP emission analyzer. Then, based on the measured concentration of each element and the content (% by weight) of each element in the inorganic fiber before dissolution, the physiological saline dissolution rate (%) is calculated. That is, for example, when the measurement element is silicon (Si), magnesium (Mg), calcium (Ca), and aluminum (Al), the physiological saline dissolution rate C (%) is calculated by the following equation.
  • C (%) [filtrate amount (L) ⁇ (a1 + a2 + a3 + a4) ⁇ 100] / [weight of inorganic fiber before dissolution (mg) ⁇ (b1 + b2 + b3 + b4) / 100].
  • a1, a2, a3 and a4 are the measured concentrations of silicon, magnesium, calcium and aluminum (mg / L), respectively, and b1, b2, b3 and b4 are respectively in the inorganic fibers before dissolution. It is content (weight%) of silicon, magnesium, calcium, and aluminum.
  • the fiber used in the present invention may be pretreated with a surfactant or a dispersant.
  • a surfactant or a dispersant When pre-treated, the surface becomes smooth, and when mixed with other ingredients to produce a composition, it is difficult to break and is included in the composition in a long state. As a result, workability is improved and strength is increased, and shrinkage is reduced. Furthermore, moisture resistance is improved and storage stability is improved.
  • the inorganic fiber has an average fiber diameter of usually 1 to 50 ⁇ m, preferably 2 to 10 ⁇ m, particularly preferably 2 to 5 ⁇ m, and an average fiber length of usually 1 to 200 mm, preferably 2 to 50 mm.
  • the amount of shots having a particle diameter of 45 ⁇ m or more contained in the inorganic fibers may be over 10% by weight. This is because in the process of reducing the amount of shots, the fiber length becomes too short, which may affect the heat shrinkage, strength, and the like.
  • the surface of the inorganic fiber contained in the amorphous composition of the present invention does not need to be coated with a coating layer.
  • substances that form a coating layer on the surface of inorganic fibers include phosphates, molybdenum compounds, polyamidine compounds, and ethyleneimine compounds.
  • the phosphate include aluminum tripolyphosphate, aluminum dihydrogen tripolyphosphate, aluminum metaphosphate, zinc phosphate, and calcium phosphate.
  • the molybdenum compound include zinc molybdate, aluminum molybdate, calcium molybdate, calcium phosphomolybdate, and aluminum phosphomolybdate.
  • polyamidine compound examples include acrylamide, acrylonitrile, N-vinylacrylamidine hydrochloride, N-vinylacrylamide, vinylamine hydrochloride, N-vinylformamide copolymer and the like.
  • ethyleneimine compounds include aminoethylene and dimethyleneimine. These substances forming the coating layer can be used singly or in combination of two or more.
  • the amorphous composition of the present invention contains the above inorganic fibers, and further contains, as appropriate, an inorganic powder containing Si, Al and / or Ca, an inorganic binder, and the like.
  • the inorganic powder may or may not be added. However, when it is added, it is desirable that the heat resistance of the inorganic powder is higher than that of the inorganic fiber in order to enhance fire resistance.
  • the inorganic powder is not particularly limited, but preferably has a melting point in an air atmosphere of 1100 ° C. or higher, more preferably 1300 ° C. or higher, and further preferably 1500 ° C. or higher.
  • a melting point in an air atmosphere 1100 ° C. or higher, more preferably 1300 ° C. or higher, and further preferably 1500 ° C. or higher.
  • clay minerals such as silica, alumina, mullite (silica 20 to 30% by weight, alumina 70 to 80% by weight), zircon, zirconia, kaolin and titania, calcia, magnesia or the like
  • An inorganic powder composed of two or more (mixtures) is used. Silica and alumina are preferred.
  • an inorganic powder containing no acicular crystal structure can be used.
  • the inorganic powder having an acicular crystal structure include one or more selected from wollastonite powder, sepiolite powder, attapulgide powder, and the like.
  • the inorganic binder examples include colloidal silica, alumina sol, zirconia sol, titania sol, and aluminum phosphate aqueous solution.
  • the inorganic binder may be a colloid such as colloidal silica, alumina sol, zirconia sol, titania sol, or a colloid in which these components are complexed, and is preferably colloidal silica.
  • the colloidal silica preferably has a pH of 8 or more, more preferably 9-11. If it is less than 8, there is a possibility that the paste does not have an appropriate viscosity.
  • colloidal silica When colloidal silica is included, the strength of the composition after heating increases. If too much is included, the amorphous composition may solidify.
  • the inorganic binder has a solid content of 1 to 30 parts by weight (preferably 1 to 25 parts by weight, more preferably 1 to 20 parts by weight) when the total weight of the inorganic fibers and the inorganic powder is 100 parts by weight. Further preferably 1 to 15 parts by weight, still more preferably 1 to 12 parts by weight, particularly preferably 2 to 10 parts by weight).
  • the inorganic fiber and the inorganic powder are blended so as to obtain desired heat resistance, density, and the like. When there are many inorganic fibers and there are few inorganic powders, a lightweight amorphous composition will be easy to be obtained. From the viewpoint of heat resistance, a suitable blending ratio of inorganic fiber: inorganic powder is shown below.
  • inorganic fiber: inorganic powder 100: 0 to 95: 5 and 80:20 to 10:90
  • inorganic fiber: inorganic powder 100: 0 to 95: 5 and 80:20 to 10:90
  • more preferably inorganic fiber: inorganic powder 100: 0 to 95: 5 and 75:25 to 10 : 90
  • most preferably inorganic fiber: Inorganic powder 100: 0 and 40:60 to 10:90.
  • 100: 0 to 90:10 and 70:30 to 10:90, more preferably 100: 0 to 90:10 and 65:35 to 10:90, more preferably inorganic fiber: inorganic powder 100: 0-95: 5 and 60: 40-10: 90.
  • the ratio of inorganic fiber: inorganic powder 100: 0 to 10:90 is set. be able to.
  • the ratio is preferably 70:30 to 10:90, more preferably 60:40 to 10:90.
  • the amount of inorganic fiber, inorganic powder, and inorganic binder may be adjusted so that the weight ratio of SiO 2 , CaO, Al 2 O 3 in the composition is in a range that does not melt in a desired use temperature range. .
  • the amorphous refractory of the present invention is suitably combined with inorganic fibers, inorganic powder, and an inorganic binder so that the obtained molded body preferably does not melt after heating at 1100 ° C. or the shrinkage ratio is less than 50%. More preferably, it is selected such that it does not melt after heating at 1200 ° C. or the shrinkage rate is less than 50%, and more preferably it does not melt after heating at 1300 ° C. or the shrinkage rate is less than 50%.
  • the shrinkage rate is preferably 30% or less, more preferably 20% or less, still more preferably 10% or less, and particularly preferably 5% or less.
  • the average particle size of the inorganic powder used in the composition of the present invention is usually 0.1 to 100 ⁇ m, preferably 0.2 to 50 ⁇ m, particularly preferably 0.2 to 10 ⁇ m.
  • the average particle size is less than 0.1 ⁇ m, separation becomes easy.
  • an average particle diameter exceeds 100 micrometers, it will become difficult to disperse
  • the amorphous composition of the present invention further contains a solvent.
  • the solvent is not particularly limited, and examples thereof include water and a polar organic solvent.
  • the polar organic solvent include monovalent alcohols such as ethanol and propanol, and divalent alcohols such as ethylene glycol. Among these, water is preferable in that there is no deterioration of the working environment and there is no burden on the environment.
  • the solvent is also included.
  • the compounding quantity is a compounding quantity of solid content.
  • the content of the solvent is usually 10 to 600 parts by weight (preferably 20 to 400 parts by weight) when the total content of inorganic fibers and inorganic powder is 100 parts by weight.
  • the fluidity can be adjusted, and the mechanical strength, particularly the bending strength, of the joint is increased. If the content is too high, the consistency of the amorphous composition will be high, so that the composition may drip during construction, and shrinkage of joints due to drying may increase.
  • the amorphous composition of the present invention may contain an organic binder, an additive and the like in addition to the inorganic fiber, the inorganic powder, the inorganic binder, and the solvent.
  • “A chelating agent that does not contain metal ions” need not be included.
  • the organic binder include organic fiber, acrylic emulsion, starch, thickener and the like.
  • the organic binder has a solid content of, for example, 0.1 to 20 parts by weight (preferably 0.5 to 10 parts by weight, preferably 0.5 to 8 parts) when the inorganic fibers and the inorganic powder are combined to make 100 parts by weight. Parts by weight, more preferably 1 to 5 parts by weight).
  • organic fibers act as a protective film for inorganic fibers
  • the composition of the present invention does not need to contain organic fibers.
  • the organic fiber is not particularly limited and may be any of natural fiber or hydrophobic treated synthetic fiber. Examples of the natural fiber include pulp, cotton, hemp and the like. Examples of the synthetic fiber include vinylon and rayon. , Polypropylene, polyethylene and the like.
  • thickener examples include hydroxyethyl cellulose, sodium acrylate polymer, polyether polyol, acrylic polymer polyester amine, ethylene oxide, carboxymethyl cellulose (CMC) and the like.
  • the combined solid content of the inorganic binder and the organic binder is preferably 1 to 50 parts by weight, more preferably 1 to 30 parts by weight, The amount is preferably 1 to 20 parts by weight.
  • Hydrophobic treatment refers to treatment for improving the hydrophobicity of the fiber.
  • Examples of the hydrophobic treatment method include a method of coating the periphery of the fiber with a hydrophobic drug.
  • additives examples include a dispersant, a preservative, and a pH adjuster.
  • the preservative is not particularly limited, and examples thereof include an inorganic compound or an organic compound having a nitrogen atom or a sulfur atom.
  • the content of the preservative is not particularly limited, but the inorganic fiber and the inorganic powder are combined. The content is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight.
  • composition of the present invention does not need to contain a pH adjuster.
  • the pH adjuster include a buffer solution and an acid.
  • the buffer solution include a phthalate standard solution (Selensen buffer solution) that is a pH 4 standard solution, and a neutral phosphate standard solution that is a pH 7 standard solution, and examples of the acid include acetic acid and formic acid.
  • the pH is preferably about 4 to 8.5.
  • the dispersant is not particularly limited, and known ones can be used. Specific examples include carboxylic acids, polyhydric alcohols, amines, and the like.
  • the content of the dispersant is not particularly limited, but is 1 for 100 parts by weight of the solid content of the inorganic fiber and the inorganic powder. ⁇ 5 parts by weight is preferred.
  • the thickener is not particularly limited, and known ones can be used. Specific examples include hydroxyethyl cellulose, sodium acrylate polymer, polyether polyol, acrylic polymerized polyester polyester amine, ethylene oxide, and carboxymethyl cellulose (CMC).
  • the content of the thickener is not particularly limited, but the solid content is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the solid content of the inorganic fiber and the inorganic powder.
  • the amorphous composition according to the present invention can be produced by mixing and stirring each component.
  • the molded body according to the present invention can be obtained by molding an amorphous composition and drying / heating. Since the composition of the present invention is pasty (stucco), it can be applied with a trowel, hardened by hand, or sprayed with a pressure gun.
  • the molded product obtained from the amorphous composition of the present invention has excellent heat resistance, and preferably does not melt at 1100 ° C, more preferably 1300 ° C, and even more preferably 1500 ° C.
  • the molded body is obtained by forming an amorphous composition into a length of 160 ⁇ width of 40 ⁇ height of 40 mm in accordance with JIS R 2553 and heating and drying at 100 ° C. for 24 hours. It is preferable that the molded body does not melt when heated in a furnace at a predetermined temperature for 24 hours. “Melting” means that the heat shrinkage measured by the method of the example is 50% or more, or is vitrified or deformed clearly in appearance.
  • the density of the amorphous composition of the present invention after drying is usually 0.1 to 1.5 g / cm 3 .
  • the amorphous composition of the present invention has good practical properties in terms of long-term stability, bending strength, and heat shrinkage.
  • the amorphous composition of the present invention using Ca silicate fibers has a heat shrinkage ratio higher than that of an amorphous composition using ceramic fibers (containing 40 to 60% by weight of silica and 60 to 40% by weight of alumina) or Mg silicate fibers. Is small.
  • the heat shrinkage is preferably 10% or less, more preferably 5% or less, and particularly preferably 3% or less.
  • Example 1 [Manufacture of amorphous composition] Amorphous compositions 1 to 4 having the compositions shown in Table 1 were produced.
  • Inorganic fiber A contains 73 wt% of SiO 2 , 24 wt% of CaO, 0.3 wt% of MgO, and 2 wt% of Al 2 O 3 .
  • Colloidal silica (Snowtex 30, Nissan Chemical Industries, pH 9-10, 30% solids suspension) was used as the inorganic binder.
  • a thickener and an acrylic emulsion were used as the organic binder.
  • the amount of the inorganic fiber A and the inorganic powder is% by weight when the total of the inorganic fiber A and the inorganic powder is 100% by weight.
  • the amounts of the inorganic binder, the organic binder, and water are parts by weight when the total of the inorganic fibers A and the inorganic powder is 100 parts by weight.
  • the values of the inorganic binder and organic binder in the table are solid contents.
  • the densities after drying at 100 ° C. for 24 hours were 0.26 g / cm 3 , 0.44 g / cm 3 , 0.75 g / cm 3 , and 1.07 g / cm 3 , respectively, and there was no drying shrinkage.
  • the density was calculated according to JIS A 1116 by measuring the dimensional volume and weight.
  • Comparative Example 1 [Manufacture of amorphous composition] Amorphous compositions 1 ′ to 4 ′ having the compositions shown in Table 2 were produced. Specifically, the amorphous fibers 1 to 4 of the amorphous compositions 1 to 4 are changed to ceramic fibers (52% by weight of silica, 48% by weight of alumina) without using inorganic powder silica. 'Manufactured. For reference, the weight ratio of SiO 2 , CaO, Al 2 O 3 in the composition is shown in Table 7.
  • Example 1 The amorphous compositions 1 to 4 and 1 ′ to 4 ′ obtained in Example 1 and Comparative Example 1 were evaluated as follows. (1) Long-term stability The consistency, bending strength, and heat shrinkage ratio of the amorphous composition immediately after production, after storage for 3 months, and after storage for 6 months were measured by the following methods. The results are shown in Table 3. The amorphous compositions 1 to 4 obtained in Example 1 did not show any decrease in physical properties even after being stored for 6 months.
  • Example 2 Manufacture of amorphous composition
  • Amorphous compositions 10 to 20 were obtained in the same manner as in Example 1 except that the compositions shown in Table 6 were used.
  • the weight ratio of SiO 2 , CaO, Al 2 O 3 in the composition is shown in Table 7.
  • Evaluation example 2 [Evaluation of amorphous composition] About the amorphous compositions 10 to 20 obtained in Example 2, the heat shrinkage rate (%) when heated at 1100 ° C., 1200 ° C., 1300 ° C., 1400 ° C., and 1500 ° C. for 24 hours is the same as in Evaluation Example 1. And measured. In addition, when the heat shrinkage rate was 50% or more, or when it was vitrified or deformed clearly in appearance, it was defined as “melting”. The results are shown in Table 6.
  • Example 3 Manufacture of amorphous composition
  • Amorphous compositions 21 to 30 were obtained in the same manner as in Example 1 except for the compositions shown in Tables 8 and 9.
  • the amorphous composition of the present invention is in a paste form and can be used as a joint material, a repair material, and a heat insulating material.

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Abstract

被覆層で被覆されていない以下の組成の無機繊維、無機バインダー及び溶媒を含み、さらに無機粉体を含むことができ、前記無機繊維と前記無機粉体との割合が、無機繊維:無機粉体=100:0~10:90であり、pH調整剤と有機繊維は含まず、前記無機粉体を含むときは、前記無機粉体は針状結晶構造を含まない、ペースト状不定形組成物。[無機繊維の組成]SiO66~82重量%、CaO10~34重量%、MgO3重量%以下、Al5重量%以下、SiO、CaO、MgO、Alの合計98重量%以上

Description

不定形組成物
 本発明は、例えば、熱処理装置、工業窯炉内又は焼却炉内の目地材、特に、耐火タイル、断熱レンガ、鉄皮、モルタル耐火物等の隙間を埋める目地材として使用される不定形組成物に関し、より具体的には、特定の生体溶解性無機繊維を含む不定形組成物に関する。
 従来、不定形組成物は、ガラス繊維、グラスウール、セラミックウール、ロックウール、アルミナ質繊維、ジルコニア質繊維、シリカ・アルミナ質繊維等の無機繊維を、強化繊維として含有していた。不定形組成物は、例えば、鏝塗り、スプレー塗り又は注入施工等により、タイル等の隙間に挿入され、目地を形成する。その際、不定形組成物に含有されている無機繊維は粉塵となって空気中に飛散し、作業者が該粉塵を吸入することとなる。無機繊維は、人に吸入されて肺に侵入すると健康被害が懸念されるため、現在、無機繊維として生体溶解性繊維を用いる不定形組成物が開発されている(例えば、特許文献1~5)。
特開2006-306713号公報 特開2006-282404号公報 特開2005-281079号公報 特表2002-524384号公報 国際公開第2011/083696号パンフレット
 不定形組成物は、通常、製造後保管される。上述したように炉の補修や目地の形成等に塗布や埋め込まれた後、乾燥する。その後、炉において高温に晒される。従って、保管、使用時のペーストの状態のとき、設備等に施工して乾燥した後、さらに設備等の加熱時に、それぞれ以下の実用特性が求められる。
 ペースト時には、ちょう度(粘性)が適切であって施工性に優れること、長期安定性を有する(保管性に優れる)ことである。乾燥後は、乾燥収縮が少なく形状の変化が少ないこと、乾燥強度が高いことである。加熱時は、加熱収縮率が小さく耐熱性、熱伝導率に優れることである。例えば、1100℃加熱後の加熱収縮率が50%未満、もしくは外観上で明らかなガラス化、変形等がないことが実用上好ましい。
 本発明者らは、耐火性、生体溶解性に優れる新規な生体溶解性繊維を開発した(特願2011-59354)。本発明は、このような耐火性、生体溶解性に優れる生体溶解性繊維を含む、実用特性を有する不定形組成物を提供することをその目的の一つとする。
 本発明によれば、以下の不定形組成物が提供される。
1.被覆層で被覆されていない以下の組成の無機繊維、無機バインダー及び溶媒を含み、
 さらに無機粉体を含むことができ、
 前記無機繊維と前記無機粉体との割合が、無機繊維:無機粉体=100:0~10:90であり、
 pH調整剤と有機繊維は含まず、
 前記無機粉体を含むときは、前記無機粉体は針状結晶構造を含まない、ペースト状不定形組成物。
[無機繊維の組成]
 SiO 66~82重量%
 CaO 10~34重量%
 MgO 3重量%以下
 Al 5重量%以下
 SiO、CaO、MgO、Alの合計 98重量%以上
2.前記無機粉体を含む1記載の不定形組成物。
3.前記無機粉体が、大気雰囲気中で1500℃以上の融点を有する2記載の不定形組成物。
4.前記無機粉体が、シリカ、アルミナ、ムライト、ジルコン、ジルコニア、チタニア、粘土鉱物、カルシア及びマグネシアから選択される1種又は2種以上からなる2記載の不定形組成物。
5.前記無機バインダーがコロイドを含む1~4のいずれか記載の不定形組成物。
6.前記コロイドがコロイダルシリカである5記載の不定形組成物。
7.前記コロイダルシリカのpHが9~11である6記載の不定形組成物。
8.前記無機バインダーが、コロイダルシリカ、アルミナゾル、ジルコニアゾル、チタニアゾル及びリン酸アルミニウム水溶液から選択される1種又は2種以上からなる1~4のいずれか記載の不定形組成物。
9.前記無機バインダーが、前記無機繊維と前記無機粉体の合計を100重量部としたときに、固形分として1~30重量部含まれる1~8のいずれか記載の不定形組成物。
10.さらに有機バインダーを含む1~9のいずれか記載の不定形組成物。
11.前記有機バインダーがアクリルエマルジョン、澱粉及び増粘剤から選択される1種又は2種以上からなる10記載の不定形組成物。
12.前記有機バインダーが、前記無機繊維と前記無機粉体の合計を100重量部としたときに、固形分として0.1~20重量部含まれている10又は11記載の不定形組成物。
13.金属イオンを含まないキレート剤は含まない1~12のいずれか記載の不定形組成物。
14.1~13のいずれか記載の不定形組成物が乾燥した成形物。
 本発明によれば、耐火性、生体溶解性に優れる生体溶解性繊維を含む、実用特性を有する不定形組成物を提供することができる。
 本発明の不定形組成物は、強化繊維として耐火性、生体溶解性に優れる特定の生体溶解性繊維を含む。
 生体溶解性繊維は、MgOを多く含むMgシリケート繊維と、CaOを多く含むCaシリケート繊維に大別できるが、本発明では、Caシリケート繊維を用いる。生体溶解性繊維は水に溶けやすいため、通常組成物に含まれる水に溶解し、含有成分が溶出する。それが組成物中の他の成分や、塗布される被対象物等と反応し不都合をもたらす恐れがある。従って、水に溶けにくいセラミックス繊維を含む組成物は生体溶解性繊維を含む組成物と異なる挙動を示す場合があり、また、生体溶解性繊維の中でも、Mgシリケート繊維を含む組成物とCaシリケート繊維を含む組成物は溶出する成分の種類や量が異なるため、異なる挙動を示す場合がある。
 不定形組成物に、Mgシリケート繊維を用いるときは、必要な強度を確保するために、バインダーとして有機繊維を添加するが、Caシリケート繊維は有機繊維の添加は必要ではない。また、Mgシリケート繊維を用いるときは、pH調整剤(リン酸緩衝液、ホウ酸緩衝液等の緩衝溶液や、酢酸等の酸)の添加が必要である。pH調整剤を添加しないと、保管中に固化する恐れがあり、乾燥収縮が大きくなる。しかし、Caシリケート繊維はpH調整剤の添加は必要ではない。さらに、Mgシリケート繊維を用いるときは、繊維の表面をリン酸塩等で被覆しないと保管中に溶解するが、Caシリケート繊維は被覆は必要ではない。
 本発明で用いるCaシリケート繊維は以下の組成を有する。
 SiO 66~82重量%(例えば、66~75重量%未満、68~80重量%、70~80重量%、71~75重量%未満、71~80重量%又は71~76重量%、とできる)
 CaO 10~34重量%(例えば、20~30重量%又は21~26重量%とできる)
 MgO 3重量%以下(例えば、1重量%以下とできる)
 Al 5重量%以下(例えば3.5重量%以下又は3重量%以下とできる。また、1重量%以上又は2重量%以上とできる)
 他の酸化物 2重量%未満
 SiOが上記範囲であると耐熱性に優れる。CaOとMgOが上記範囲であると加熱前後の生体溶解性に優れる。
 Al含有量は、例えば、3.4重量%以下又は3.0重量%以下とできる。また、1.1重量%以上又は2.0重量%以上とできる。好ましくは0~3重量%、より好ましくは1~3重量%である。この範囲でAlを含むと強度が高くなる。
 上記の無機繊維は、他の酸化物として、アルカリ金属酸化物(KO、NaO等)、Fe、ZrO、P、B、TiO、MnO、R(RはSc,La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu,Y又はこれらの混合物から選択される)等を1以上含んでもよく、含まなくてもよい。他の酸化物は、それぞれ、0.2重量%以下又は0.1重量%以下としてよい。アルカリ金属酸化物は各酸化物を0.2重量%以下としてもよく、アルカリ金属酸化物の合計を0.2重量%以下としてもよい。
 また、生体溶解性繊維は、SiO、CaO、MgO、Alの合計を98重量%超又は99重量%超としてよい。
 生体溶解性無機繊維は、例えば、40℃における生理食塩水溶解率が1%以上の無機繊維である。
 生理食塩水溶解率は、例えば、次のようにして測定される。すなわち、先ず、無機繊維を200メッシュ以下に粉砕して調製された試料1g及び生理食塩水150mLを三角フラスコ(容積300mL)に入れ、40℃のインキュベーターに設置する。次に、三角フラスコに、毎分120回転の水平振動を50時間継続して加える。その後、ろ過により得られた濾液に含有されている各元素の濃度(mg/L)をICP発光分析装置により測定する。そして、測定された各元素の濃度と、溶解前の無機繊維における各元素の含有量(重量%)と、に基づいて、生理食塩水溶解率(%)を算出する。すなわち、例えば、測定元素が、ケイ素(Si)、マグネシウム(Mg)、カルシウム(Ca)及びアルミニウム(Al)である場合には、次の式により、生理食塩水溶解率C(%)を算出する;C(%)=[ろ液量(L)×(a1+a2+a3+a4)×100]/[溶解前の無機繊維の重量(mg)×(b1+b2+b3+b4)/100]。この式において、a1、a2、a3及びa4は、それぞれ測定されたケイ素、マグネシウム、カルシウム及びアルミニウムの濃度(mg/L)であり、b1、b2、b3及びb4は、それぞれ溶解前の無機繊維におけるケイ素、マグネシウム、カルシウム及びアルミニウムの含有量(重量%)である。
 さらに、本発明に用いる繊維は、界面活性剤、分散剤で前処理されていてもよい。前処理すると表面が滑らかになり、他の成分と混ぜて組成物を製造するとき折れ難く、長い状態で組成物に含まれる。その結果、施工性の向上や強度が高まり、収縮が少なくなる。さらに、耐湿性が改善され、保管安定性が良くなる。
 無機繊維は、強度の観点から、平均繊維径は通常1~50μm、好ましくは2~10μm、特に好ましくは2~5μmであり、平均繊維長は通常1~200mm、好ましくは2~50mmである。
 また、無機繊維に含まれる粒径45μm以上のショットの量を10重量%超えとしてもよい。ショットの量を減らす処理では繊維長が短くなりすぎて加熱収縮、強度等に影響を及ぼす恐れがあるためである。
 本発明の不定形組成物に含まれる無機繊維の表面は被覆層で被覆される必要はない。無機繊維の表面に被覆層を形成する物質としては、リン酸塩、モリブデン化合物、ポリアミジン化合物、エチレンイミン化合物等が挙げられる。リン酸塩としては、トリポリリン酸アルミニウム、トリポリリン酸ニ水素アルミニウム、メタリン酸アルミニウム、リン酸亜鉛、リン酸カルシウム等が挙げられる。モリブデン化合物としては、モリブデン酸亜鉛、モリブデン酸アルミニウム、モリブデン酸カルシウム、リンモリブデン酸カルシウム、リンモリブデン酸アルミニウム等が挙げられる。ポリアミジン化合物としては、アクリルアミド、アクリロニトリル、N-ビニルアクリルアミジン塩酸塩、N-ビニルアクリルアミド、ビニルアミン塩酸塩、N-ビニルホルムアミド共重合体等が挙げられる。エチレンイミン化合物としては、アミノエチレン、ジメチレンイミン等が挙げられる。これら被覆層を形成する物質は、1種単独又は2種以上を組み合わせて用いることができる。
 本発明の不定形組成物は、上記無機繊維を含み、さらに、適宜、Si,Al及び/又はCaを含む無機粉体や無機バインダー等を含む。無機粉体は添加してもしなくてもよいが、添加する場合は、耐火性を高めるために、無機粉体の耐熱性は、無機繊維より高いものが望まれる。
 無機粉体は、特に限定されないが、好ましくは1100℃以上、より好ましくは1300℃以上、さらに好ましくは1500℃以上の大気雰囲気中での融点を有する。
 具体的には、例えば、シリカ、アルミナ、ムライト(シリカ20~30重量%、アルミナ70~80重量%)、ジルコン、ジルコニア、カオリン、チタニア等の粘土鉱物、カルシア、マグネシアから選択される1種又は2種以上(混合物)からなる無機粉体を用いる。好ましくはシリカ、アルミナである。
 本発明では、針状結晶構造を含まない無機粉体を用いることができる。針状結晶構造を有する無機粉末として、ワラストナイト粉末、セピオライト粉末、アタパルジャイド粉末等から選ばれる1種以上を挙げることができる。
 無機バインダーとしては、コロイダルシリカ、アルミナゾル、ジルコニアゾル、チタニアゾル、リン酸アルミニウム水溶液等が挙げられる。
 無機バインダーは、コロイダルシリカ、アルミナゾル、ジルコニアゾル、チタニアゾル、またはそれら成分が複合化されたコロイド等のコロイドでよく、好ましくはコロイダルシリカである。コロイダルシリカは、pHは8以上が好ましく、9~11がより好ましい。8未満であると適度の粘度を有するペーストにならない恐れがある。コロイダルシリカを含むと加熱後の組成物の強度が高まる。多く含みすぎると不定形組成物が固化する恐れがある。
 無機バインダーは、無機繊維と無機粉体とを合わせた重量を100重量部としたとき、固形分含量で1~30重量部(好ましくは1~25重量部、より好ましくは1~20重量部、さらに好ましくは1~15重量部、さらにより好ましくは1~12重量部、特に好ましくは2~10重量部)含むことができる。無機繊維と無機粉体は、所望する耐熱性、密度等になるように配合する。無機繊維が多く、無機粉体が少ないと軽量な不定形組成物が得られやすい。
 耐熱性の観点から無機繊維:無機粉体の好適な配合比を以下に示す。
 無機粉体を含む場合であって、無機バインダーとしてコロイダルシリカ、無機粉体としてアルミナを選択した場合は、無機繊維:無機粉体=100:0~10:90の割合とすることができる。好ましくは、無機繊維:無機粉体=100:0~95:5および80:20~10:90、さらに好ましくは、無機繊維:無機粉体=100:0~95:5および75:25~10:90、より好ましくは、100:0および70:30~10:90、さらにより好ましくは、無機繊維:無機粉体=100:0および65:35~10:90、もっとも好ましくは、無機繊維:無機粉体=100:0および40:60~10:90である。
 無機粉体を含む場合であって、無機バインダーとしてコロイダルシリカ、無機粉体としてムライトを選択した場合は、無機繊維:無機粉体=100:0~10:90の割合とすることができる。好ましくは、100:0~90:10および70:30~10:90、さらに好ましくは100:0~90:10および65:35~10:90、より好ましくは無機繊維:無機粉体=100:0~95:5および60:40~10:90である。
 無機粉体を含む場合であって、無機バインダーとしてコロイダルシリカ、無機粉体としてカオリンを選択した場合は、無機繊維:無機粉体=100:0~10:90の割合とすることができる。好ましくは、無機繊維:無機粉体=100:0~80:20および60:40~10:90、さらに好ましくは100:0~80:10および50:50~10:90、より好ましくは無機繊維:無機粉体=100:0~85:15および50:50~10:90、さらにより好ましくは100:0~90:10および40:60~10:90である。
 無機粉体を含む場合であって、無機バインダーとしてコロイダルシリカ、無機粉体としてシリカを選択した場合は、無機繊維:無機粉体=100:0~10:90である。
 無機粉体を含む場合であって、無機バインダーとしてコロイダルシリカ、無機粉体としてジルコン、ジルコニア、チタニアの1以上を選択した場合は、無機繊維:無機粉体=100:0~10:90である。
 無機粉体を含む場合であって、無機バインダーとしてコロイダルシリカ、無機粉体としてカルシア、マグネシアの1以上を選択した場合は、無機繊維:無機粉体=100:0~10:90の割合とすることができる。好ましくは70:30~10:90、より好ましくは60:40~10:90である。
 組成物におけるSiO、CaO、Alの重量比が、例えば、所望する使用温度域で溶融しない範囲となるように、無機繊維、無機粉体、無機バインダーの量を調整してもよい。
 本発明の不定形耐火物は、得られる成形体が、好ましくは1100℃加熱後に溶融しない又は収縮率が50%未満となるよう無機繊維、無機粉体、無機バインダーを適宜組み合わせる。より好ましくは1200℃加熱後に溶融しない又は収縮率が50%未満、さらに好ましくは1300℃加熱後に溶融しない又は収縮率が50%未満となるよう選択する。収縮率は、好ましくは30%以下、より好ましくは20%以下、さらに好ましくは10%以下、特に好ましくは5%以下である。
 本発明の組成物に用いる無機粉体の平均粒子径は、通常0.1~100μm、好ましくは0.2~50μm、特に好ましくは0.2~10μmである。平均粒子径が0.1μm未満だと、分離し易くなる。また、平均粒子径が、100μmを超えると、均一に分散し難くなる。
 本発明の不定形組成物は、さらに溶媒を含む。
 溶媒としては、特に制限されないが、水及び極性有機溶媒が挙げられ、極性有機溶媒としては、エタノール、プロパノール等の1価のアルコール類、エチレングリコール等の2価のアルコール類が挙げられる。これらのうち、水が、作業環境の悪化がなく、環境への負荷がない点で好ましい。懸濁液や分散液等として成分を配合するときは、その溶媒も含まれる。尚、固体を懸濁液や分散液等として配合するとき、その配合量は固形分の配合量である。
 溶媒の含有量は、無機繊維と無機粉体を合わせた含量を100重量部としたとき、通常10~600重量部(好ましくは20~400重量部)である。溶媒を含むことにより、流動性を調節でき、目地の機械的強度、特に曲げ強度が高まる。含有量が多すぎると不定形組成物のちょう度が高くなるので施工時に組成物がたれ、また、乾燥による目地の収縮が大きくなる恐れがある。
 本発明の不定形組成物は、前記無機繊維、無機粉体、無機バインダー、溶媒の他に有機バインダー、添加剤等を含むことができる。「金属イオンを含まないキレート剤」は含む必要はない。
 有機バインダーとしては、有機繊維、アクリルエマルジョン、澱粉、増粘剤等が挙げられる。
 有機バインダーは、無機繊維と無機粉体を合わせて100重量部としたとき、例えば固形分含量を0.1~20重量部(好ましくは0.5~10重量部、好ましくは0.5~8重量部、さらに好ましくは1~5重量部)含むことができる。
 有機繊維は無機繊維の保護膜として作用するが、本発明の組成物は有機繊維を含む必要はない。有機繊維としては、特に制限されず、天然繊維又は疎水処理された合成繊維のいずれであってもよく、天然繊維としては、パルプ、綿、麻等が挙げられ、合成繊維としては、ビニロン、レーヨン、ポリプロピレン、ポリエチレン等が挙げられる。
 増粘剤としてヒドロキシエチルセルロース、アクリル酸ナトリウム重合物、ポリエーテルポリオール、アクリル系高分子ポリエステルアミン、エチレンオキサイド、カルボキシルメチルセルロース(CMC)等が挙げられる。
 上記無機繊維と無機粉体との合計を100重量部とした場合に、無機バインダーと有機バインダーは合わせた固形分含量は、好ましくは1~50重量部、より好ましくは1~30重量部、さらに好ましくは1~20重量部である。
 無機繊維は、ある程度の疎水性を持たせることが、無機繊維を水中に投入した際、急激に沈むことなく、ある程度の時間浮遊することになり、互いのあるいは他の混合材料との混合性がよくなる点で好ましい。疎水処理とは、繊維の疎水性を向上させる処理のことを指し、疎水処理の方法としては、例えば、繊維の周りを疎水性の薬剤でコーティングする方法が挙げられる。
 添加剤としては、分散剤、防腐剤、pH調整剤等を挙げることができる。
 防腐剤としては、特に制限されないが、例えば、窒素原子又は硫黄原子を有する無機化合物又は有機化合物等が挙げられ、防腐剤の含有量は、特に制限されないが、無機繊維と無機粉体を合わせた含量100重量部に対して0.1~5重量部が好ましい。
 尚、本発明の組成物は、pH調整剤を含む必要はない。pH調整剤としては、例えば緩衝溶液又は酸が挙げられる。緩衝溶液としては、pH4標準溶液であるフタール酸塩標準溶液(セーレンセン緩衝液)、pH7標準溶液である中性リン酸塩標準溶液が挙げられ、酸としては、酢酸、蟻酸等が挙げられる。pHは4~8.5程度が好ましい。
 分散剤としては、特に制限されず、公知のものが使用できる。具体的には、カルボン酸類、多価アルコール、アミン類等が挙げられ、分散剤の含有量は、特に制限されないが、無機繊維と無機粉体を合わせた固形分含量100重量部に対して1~5重量部が好ましい。
 増粘剤としては、特に制限されず、公知のものが使用できる。具体的には、ヒドロキシエチルセルロース、アクリル酸ナトリウム重合物、ポリエーテルポリオール、アクリル系重合高分子ポリエステルアミン、エチレンオキサイド、カルボキシルメチルセルロース(CMC)等が挙げられる。増粘剤の含有量は、特に制限されないが、無機繊維と無機粉体を合わせた固形分含量100重量部に対して固形分含量0.1~20重量部が好ましい。
 本発明に係る不定形組成物は、各成分を混合・撹拌して製造できる。本発明に係る成形体は、不定形組成物を成形し乾燥/加熱して得ることができる。本発明の組成物はペースト状(漆喰)であるため、こてで塗ったり、手で固めたり、圧力銃で散布できる。
 本発明の不定形組成物から得られる成形体は耐熱性に優れ、好ましくは1100℃、より好ましくは1300℃、さらに好ましくは1500℃で溶融しない。具体的には、成形体は、不定形組成物を、JIS R 2553に準じ、長さ160×幅40×高さ40mmに成形し、100℃で24時間加熱乾燥して得る。この成形体を、炉中、所定温度で24時間加熱したとき、溶融しないことが好ましい。「溶融」とは、実施例の方法で測定する加熱収縮率が50%以上、もしくは外観上で明らかなガラス化、変形することである。
 本発明の不定形組成物の乾燥した後の密度は、通常0.1~1.5g/cmである。
 本発明の不定形組成物は、長期安定性、曲げ強度、加熱収縮率の点から、良好な実用特性を有する。
 特に、Caシリケート繊維を用いた本発明の不定形組成物は、セラミックス繊維(シリカ40~60重量%、アルミナ60~40重量%含有)やMgシリケート繊維を用いた不定形組成物より加熱収縮率が小さい。加熱収縮率は好ましくは10%以下、より好ましくは5%以下、特に好ましくは3%以下である。
実施例1
[不定形組成物の製造]
 表1に示す組成の不定形組成物1~4を製造した。
 無機繊維AはSiOを73重量%、CaOを24重量%、MgOを0.3重量%、Alを2重量%含む。
 無機バインダーとしてコロイダルシリカ(スノーテックス30、日産化学工業社製、pH9~10、固形分が30%の懸濁液)を用いた。
 有機バインダーとして増粘剤及びアクリルエマルジョンを用いた。
 表1において、無機繊維Aと無機粉末の量は、無機繊維Aと無機粉末の合計を100重量%としたときの重量%である。
 無機バインダー、有機バインダー、水の量は、無機繊維Aと無機粉末の合計を100重量部としたときの重量部である。表中の無機バインダー、有機バインダーの値は固形分量である。
 100℃24時間乾燥した後の密度は、それぞれ0.26g/cm、0.44g/cm、0.75g/cm、1.07g/cmであり、乾燥収縮はなかった。密度はJIS A 1116に準じ、寸法体積及び重量を測定して算出した。
Figure JPOXMLDOC01-appb-T000001
比較例1
[不定形組成物の製造]
 表2に示す組成の不定形組成物1’~4’を製造した。具体的には、不定形組成物1~4の無機繊維Aをセラミック繊維(シリカ52重量%、アルミナ48重量%)に変えて、無機粉末シリカを用いずに、不定形組成物1’~4’を製造した。
 参考として、組成物におけるSiO、CaO、Alの重量比を表7に示す。
Figure JPOXMLDOC01-appb-T000002
評価例1
 実施例1と比較例1で得られた不定形組成物1~4,1’~4’について以下の評価をした。
(1)長期安定性
 製造直後、3カ月保管後、6カ月保管後の不定形組成物について、以下の方法で、ちょう度、曲げ強度、加熱収縮率を測定した。結果を表3に示す。実施例1で得られた不定形組成物1~4は6カ月保管しても物性に低下は見られなかった。
(i)ちょう度
 JIS K 2220に準じ、ちょう度計を用いて測定した。金属カップには内径100mm、内高50mmのものを、円錐には円錐Aを使用した。
(ii)曲げ強度
 不定形組成物を、長さ160×幅40×高さ40mmに成形し、100℃で24時間加熱乾燥して断熱材を得た。
 この断熱材を1100℃で24時間加熱し、加熱後の断熱材の曲げ強度を求めた。曲げ強度は、3点曲げ強度試験機(テンシロン)を用いて、破断荷重を測定し、次式により算出した。
曲げ強度(MPa)={3×最大荷重(N)×支持ロールの中心距離(mm)}/{2×断熱材の幅(mm)×(断熱材の厚さ(mm))
(iii)加熱収縮率
 不定形組成物を、JIS R 2553に準じ、長さ160×幅40×高さ40mmに成形し、100℃で24時間加熱乾燥して断熱材を得た。
 この断熱材を、電気炉中1300℃で24時間加熱し、加熱後の断熱材の長さを測定した。加熱収縮率は、加熱前の断熱材の長さをXmm、加熱後の長さをYmmとし、次式により求めた。
加熱収縮率(%)={(X-Y)/X}×100
Figure JPOXMLDOC01-appb-T000003
(2)加熱収縮率
 製造直後の不定形組成物について、1100℃,1200℃及び1300℃で、24時間加熱した後の収縮率(%)を、上記(1)(iii)と同様にして測定した。5回測定した平均値を、表4に示す。不定形組成物1~4は不定形組成物1’~4’より収縮率が少ないことが分かる。
Figure JPOXMLDOC01-appb-T000004
(3)曲げ強度
 製造直後の不定形組成物について、1100℃,1200℃及び1300℃で、24時間加熱した後の曲げ強度(Mpa)を、上記(1)(ii)と同様にして測定した。5回測定した平均値を、表5に示す。不定形組成物1~4の曲げ強度は不定形組成物1’~4’とほぼ同じであった。
Figure JPOXMLDOC01-appb-T000005
実施例2
[不定形組成物の製造]
 表6の組成である他は実施例1と同様にして、不定形組成物10~20を得た。参考として、組成物におけるSiO、CaO、Alの重量比を表7に示す。
評価例2
[不定形組成物の評価]
 実施例2で得られた不定形組成物10~20について、1100℃,1200℃,1300℃,1400℃,1500℃で24時間加熱したときの、加熱収縮率(%)を評価例1と同様にして測定した。尚、加熱収縮率が50%以上、もしくは外観上で明らかなガラス化、変形したとき「溶融」とした。結果を表6に示す。
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
実施例3
[不定形組成物の製造]
 表8,9の組成である他は実施例1と同様にして、不定形組成物21~30を得た。
評価例3
[不定形組成物の評価]
 実施例3で得られた不定形組成物21~30について、1300℃で24時間加熱したときの、加熱収縮率(%)を評価例1と同様にして測定した。結果を表8,9に示す。
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
 本発明の不定形組成物は、ペースト状であり、目地材、補修材、断熱材として使用できる。
 上記に本発明の実施形態及び/又は実施例を幾つか詳細に説明したが、当業者は、本発明の新規な教示及び効果から実質的に離れることなく、これら例示である実施形態及び/又は実施例に多くの変更を加えることが容易である。従って、これらの多くの変更は本発明の範囲に含まれる。
 この明細書に記載の文献及び本願のパリ優先の基礎となる日本出願明細書の内容を全てここに援用する。

Claims (14)

  1.  被覆層で被覆されていない以下の組成の無機繊維、無機バインダー及び溶媒を含み、
     さらに無機粉体を含むことができ、
     前記無機繊維と前記無機粉体との割合が、無機繊維:無機粉体=100:0~10:90であり、
     pH調整剤と有機繊維は含まず、
     前記無機粉体を含むときは、前記無機粉体は針状結晶構造を含まない、ペースト状不定形組成物。
    [無機繊維の組成]
     SiO 66~82重量%
     CaO 10~34重量%
     MgO 3重量%以下
     Al 5重量%以下
     SiO、CaO、MgO、Alの合計 98重量%以上
  2.  前記無機粉体を含む請求項1記載の不定形組成物。
  3.  前記無機粉体が、大気雰囲気中で1500℃以上の融点を有する請求項2記載の不定形組成物。
  4.  前記無機粉体が、シリカ、アルミナ、ムライト、ジルコン、ジルコニア、チタニア、粘土鉱物、カルシア及びマグネシアから選択される1種又は2種以上からなる請求項2記載の不定形組成物。
  5.  前記無機バインダーがコロイドを含む請求項1~4のいずれか記載の不定形組成物。
  6.  前記コロイドがコロイダルシリカである請求項5記載の不定形組成物。
  7.  前記コロイダルシリカのpHが9~11である請求項6記載の不定形組成物。
  8.  前記無機バインダーが、コロイダルシリカ、アルミナゾル、ジルコニアゾル、チタニアゾル及びリン酸アルミニウム水溶液から選択される1種又は2種以上からなる請求項1~4のいずれか記載の不定形組成物。
  9.  前記無機バインダーが、前記無機繊維と前記無機粉体の合計を100重量部としたときに、固形分として1~30重量部含まれる請求項1~8のいずれか記載の不定形組成物。
  10.  さらに有機バインダーを含む請求項1~9のいずれか記載の不定形組成物。
  11.  前記有機バインダーがアクリルエマルジョン、澱粉及び増粘剤から選択される1種又は2種以上からなる請求項10記載の不定形組成物。
  12.  前記有機バインダーが、前記無機繊維と前記無機粉体の合計を100重量部としたときに、固形分として0.1~20重量部含まれている請求項10又は11記載の不定形組成物。
  13.  金属イオンを含まないキレート剤は含まない請求項1~12のいずれか記載の不定形組成物。
  14.  請求項1~13のいずれか記載の不定形組成物が乾燥した成形物。
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US20140378596A1 (en) 2014-12-25
JP2013112600A (ja) 2013-06-10
EP2786976A1 (en) 2014-10-08
EP2786976A4 (en) 2014-12-10
CN103958440B (zh) 2016-03-09
JP5022512B1 (ja) 2012-09-12

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