Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
  • C04B38/0051—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity
  • C04B38/0054—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity the pores being microsized or nanosized
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
  • C04B38/10—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by using foaming agents or by using mechanical means, e.g. adding preformed foam
  • C04B38/106—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by using foaming agents or by using mechanical means, e.g. adding preformed foam by adding preformed foams
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B28—WORKING CEMENT, CLAY, OR STONE
  • B28C—PREPARING CLAY; PRODUCING MIXTURES CONTAINING CLAY OR CEMENTITIOUS MATERIAL, e.g. PLASTER
  • B28C7/00—Controlling the operation of apparatus for producing mixtures of clay or cement with other substances; Supplying or proportioning the ingredients for mixing clay or cement with other substances; Discharging the mixture
  • B28C7/02—Controlling the operation of the mixing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B28—WORKING CEMENT, CLAY, OR STONE
  • B28C—PREPARING CLAY; PRODUCING MIXTURES CONTAINING CLAY OR CEMENTITIOUS MATERIAL, e.g. PLASTER
  • B28C7/00—Controlling the operation of apparatus for producing mixtures of clay or cement with other substances; Supplying or proportioning the ingredients for mixing clay or cement with other substances; Discharging the mixture
  • B28C7/04—Supplying or proportioning the ingredients
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/02—Alcohols; Phenols; Ethers
  • C04B24/023—Ethers
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/10—Carbohydrates or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/16—Sulfur-containing compounds
  • C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
  • C04B24/166—Macromolecular compounds comprising sulfonate or sulfate groups obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
  • C04B38/10—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by using foaming agents or by using mechanical means, e.g. adding preformed foam
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
  • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
  • C04B2103/302—Water reducers
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
  • C04B2103/40—Surface-active agents, dispersants
  • C04B2103/402—Surface-active agents, dispersants anionic
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
  • C04B2103/40—Surface-active agents, dispersants
  • C04B2103/406—Surface-active agents, dispersants non-ionic
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
  • C04B2111/00612—Uses not provided for elsewhere in C04B2111/00 as one or more layers of a layered structure
  • C04B2111/0062—Gypsum-paper board like materials
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
  • C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
  • C04B2201/30—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
  • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength

Definitions

• the present invention relates to a hardened gypsum body and a method for manufacturing the same.
• a hardened gypsum body used for gypsum boards and the like is made lighter by introducing air bubbles into a gypsum slurry containing gypsum and water.
• foam obtained by foaming a liquid composition containing a foaming agent composition and water is mixed with gypsum slurry, and the mixture is cured to produce a light-weight cured gypsum body with bubbles.
• Japanese Patent Application Publication No. 2004-508259 states that foaming agent-surfactant of 0.2 to 1.2 lb/msf, water of 650 to 1000 lb/msf, and ⁇ 1330 lb/msf (6.53 kg/m 2 )
• a gypsum board product made from a gypsum board product slurry containing stucco, having a thickness of 1/2 inch, having paper on the back and front sides, and having a total dry weight of ⁇ about 1275 lb/msf. discloses a gypsum board product in which the diameter of the bubbles within the gypsum board product is ⁇ 500 ⁇ m, and the gypsum board is disclosed to have sufficient strength and nail pull properties. Additionally, and in the Examples, 1/2 inch thick gypsum board was manufactured with dry weights of approximately 1235 and 1255 lb/msf (approximately 0.380 and 0.386 g/cm 3 ). This is disclosed.
• a cured gypsum body using gypsum as a hardening agent and containing air bubbles can reduce density and weight by containing air bubbles, but on the other hand, the weight reduction reduces strength.
• increasing the cell diameter can be considered to suppress the decrease in strength of the hardened gypsum body, but there is a limit to the increase in the cell diameter. Therefore, there is a need for a technology that controls the bubble diameter in the hardened gypsum body and achieves both weight reduction and strength.
• the present invention provides a hardened gypsum body containing air bubbles having the same density and the same average cell diameter, and which can increase the strength of the hardened gypsum body by controlling the coefficient of variation of the bubble diameter, and its production. provide a method.
• the present invention is a gypsum hardened body containing air bubbles,
• the density of the gypsum hardened body is 0.4 g/cm 3 or more and 0.8 g/cm 3 or less,
• the above-mentioned hardened gypsum body has an average cell diameter of 200 ⁇ m or more and 600 ⁇ m or less, and a coefficient of variation of the cell diameter of 0.30 or more and 0.48 or less.
• the present invention also relates to a method for producing a hardened gypsum body of the present invention, which includes the following steps 1, 2, and 3.
• ⁇ Step 1> A step of foaming a liquid composition containing a foaming agent composition containing a surfactant (hereinafter referred to as component (A)) and water to obtain foam.
• component (A) A step of foaming a liquid composition containing a foaming agent composition containing a surfactant (hereinafter referred to as component (A)) and water to obtain foam.
• component (A) A step of mixing the foam obtained in step 1 with a gypsum slurry containing gypsum and water to obtain a foam-containing gypsum slurry.
• ⁇ Step 3> After step 2, a step of molding and curing the aerated gypsum slurry.
• a hardened gypsum body containing air bubbles having the same density and the same average cell diameter can increase the strength of the hardened gypsum body by controlling the coefficient of variation of the bubble diameter, and A method of manufacturing the same is provided.
• the hardened gypsum body of the present invention and the method for producing the same are characterized in that the hardened gypsum body containing air bubbles has the same density and the same average cell size, and the gypsum hardened body contains air bubbles by controlling the coefficient of variation of the air bubble diameter.
• body strength can be increased is not necessarily clear, but it is presumed as follows. Conventionally, relatively large air bubbles have been introduced into a hardened gypsum body in order to improve the mechanical strength of the hardened gypsum body, as disclosed in, for example, a prior document (Japanese Patent Publication No. 2004-529050). Ta.
• JP-A-10-330174 in order to improve the adhesion to base paper and the strength of the cured gypsum, relatively large uniform air bubbles were scattered in the core.
• the present inventors have discovered that the strength of the hardened gypsum body can be increased by setting the coefficient of variation of the bubble diameter in the hardened gypsum body within a specific range. More specifically, the above-mentioned problem is solved by setting the coefficient of variation of the bubble diameter in the hardened gypsum body to 0.30 or more and 0.48 or less. The larger the coefficient of variation is, the larger the variation in bubble diameter is, and the smaller the coefficient of variation is, the smaller the variation in bubble diameter is.
• the hardened gypsum body contains coarse cells that cause intense stress concentration, resulting in the existence of locally weak points, which are destroyed and the strength is reduced.
• the diameter of the bubbles in the hardened gypsum body is uniform and the variation is too small, the distance between the bubbles becomes narrow and the bubbles in the hardened gypsum body become interconnected and act as coarse bubbles, resulting in severe stress concentration. , the strength decreases.
• the strength of the hardened gypsum body could be improved even in the hardened gypsum body. It is also estimated that by setting the average cell diameter within the specified range of the present invention, the strength of the hardened gypsum body can be maintained even if the density is reduced, making it possible to both reduce the weight and improve the strength of the hardened gypsum body. be done. Note that the present invention is not limited to the above expression mechanism.
• the hardened gypsum body as used in the present invention is obtained by drying and hardening a gypsum slurry containing air bubbles, gypsum, and water.
• the hardened gypsum body contains air bubbles.
• the density of the hardened gypsum body of the present invention is 0.4 g/cm 3 or more, preferably 0.5 g/cm 3 or more from the viewpoint of fire resistance, and 0.8 g/cm 3 or less, preferably from the viewpoint of handleability. is 0.75 g/cm 3 or less.
• the average cell diameter in the hardened gypsum body of the present invention is 200 ⁇ m or more, preferably 250 ⁇ m or more, more preferably 300 ⁇ m or more, still more preferably 400 ⁇ m or more, and even more preferably from the viewpoint of improving the strength of the hardened gypsum body at the same density. is 500 ⁇ m or more, and 600 ⁇ m or less, preferably 580 ⁇ m or less, from the viewpoint of improving the strength and cross-sectional appearance of the hardened gypsum body at the same density.
• the average cell diameter in the hardened gypsum body can be adjusted by selecting the type of surfactant (A) as the bubble component contained in the hardened gypsum body, or adding alcohol as the component (B) described below. .
• the average bubble diameter is calculated by preparing a hardened gypsum body containing bubbles, cutting out a cross section of the hardened body, observing the cross section with a digital microscope, and arbitrarily calculating the diameter of the cross section of 100 bubbles. Measured and calculated from the average value (arithmetic mean) of those values.
• the coefficient of variation of the bubble diameter is 0.30 or more, preferably 0.32 or more, more preferably 0.34 or more, from the viewpoint of improving base paper adhesion when making a gypsum board. From the viewpoint of improving the strength of the hardened gypsum body, it is 0.48 or less, preferably 0.45 or less, more preferably 0.43 or less, even more preferably 0.40 or less, even more preferably 0.38 or less, and more. More preferably, it is 0.36 or less.
• Adjustment of the coefficient of variation of the bubble diameter in a hardened gypsum body involves selecting the type of surfactant for component (A) as a bubble component contained in a hardened gypsum body, adjusting the viscosity of the gypsum slurry by using a water reducing agent, etc., and controlling foam and gypsum. Methods include selecting the stirring speed and stirring time for kneading the slurry.
• the hardened gypsum body of the present invention can be obtained by drying a gypsum slurry containing air bubbles, gypsum, and water.
• a foaming agent composition described below can be used, and the foaming agent composition includes a surfactant, a monohydric alcohol having 6 to 10 carbon atoms, and Examples include compositions containing nonionic compounds with a LogP of 0 or more and less than 2.0.
• the hardened gypsum body of the present invention preferably contains (A) a surfactant (hereinafter referred to as component (A)) and gypsum.
• the surfactant of component (A) is one type selected from (A1) anionic surfactant (hereinafter referred to as component (A1)) and (A2) nonionic surfactant (hereinafter referred to as component (A2)). The above can be mentioned.
• anionic surfactant as the component (A1) examples include sulfonic acid compounds, ether sulfate compounds, carboxylic acid compounds, phosphonic acid compounds, and phosphoric acid compounds having a hydrocarbon group having 8 to 18 carbon atoms.
• alkyl or alkenyl sulfates having an alkyl or alkenyl group
• alkyl or alkenyl sulfonic acids having an alkyl or alkenyl group
• olefin sulfonic acids polyoxyalkylene alkyl or alkenyl ether sulfates having an alkyl or alkenyl group, alkyl or alkenyl group-containing polyoxyalkylene alkyl or alkenyl ether carboxylic acids, and salts thereof.
• the salts of these anionic surfactants include one or more selected from alkali metal salts such as sodium salts and potassium salts, ammonium salts, and organic ammonium salts.
• Component (A1) is an alkyl group having 8 or more and 18 or less carbon atoms, from the viewpoint of increasing the cell diameter in the hardened gypsum body and reducing the amount of the foaming agent composition to be included in the gypsum slurry.
• an alkyl or alkenyl sulfate having an alkenyl group, or a salt thereof (hereinafter referred to as component (A11)) is preferable.
• Component (A11) has a carbon number of 8 or more, preferably 10 or more, from the viewpoint of increasing the cell diameter in the gypsum hardened body and reducing the amount of the foaming agent composition to be included in the gypsum slurry, and It has 18 or less, preferably 16 or less, more preferably 14 or less, even more preferably 12 or less alkyl or alkenyl groups, preferably alkyl groups.
• the salt of the component (A1) include one or more selected from alkali metal salts such as sodium salts and potassium salts, ammonium salts, and organic ammonium salts.
• the component (A11) includes octyl sulfate, decyl sulfate, dodecyl sulfate, tetradecyl sulfate, hexadecyl sulfate, octadecyl sulfate, 2-ethylhexyl sulfate, 2-propylheptyl sulfate, and
• One or more salts selected from these salts may be mentioned, and from the viewpoint of increasing the cell diameter in the hardened gypsum body and reducing the amount of the foaming agent composition to be included in the gypsum slurry, octyl sulfate, decyl sulfate, etc.
• It preferably contains one or more compounds selected from sulfate, dodecyl sulfate, tetradecyl sulfate, and salts thereof, and preferably contains one or more compounds selected from decyl sulfate, dodecyl sulfate, and salts thereof. It is more preferable to do so.
• the hardened gypsum body of the present invention contains, as the component (A11), an alkyl group having a carbon number of 10 or an alkenyl group, from the viewpoint of increasing the cell diameter in the hardened gypsum body and reducing the coefficient of variation of the cell size. It is preferable to contain an alkenyl sulfate or a salt thereof. (A11) The content of the alkyl or alkenyl sulfate having an alkyl group or alkenyl group having 10 carbon atoms or its salt in the component increases the cell diameter in the gypsum hardened body and reduces the coefficient of variation of the cell diameter.
• it is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, more preferably 90% by mass or more, and 100% by mass or less.
• nonionic surfactant as the component (A2) examples include alkylene oxide compounds and polyhydric alcohol compounds having a hydrocarbon group having 8 to 18 carbon atoms, such as alkyl monoglyceryl ether, polyoxyalkylene monoalkyl, or alkenyl Examples include one or more selected from ether, alkyl glycoside or alkyl polyglycoside (alkyl glycoside type nonionic surfactant), sorbitan type nonionic surfactant, aliphatic alkanolamide, fatty acid monoglyceride, and sucrose fatty acid ester.
• Component (A21) is an alkyl glycoside type nonionic surfactant from the viewpoint of reducing the coefficient of variation of the cell diameter in the gypsum hardened body and reducing the amount of the foaming agent composition to be included in the gypsum slurry. (hereinafter referred to as component (A21)) is preferred.
• component (A21) an alkyl glycoside type surfactant represented by the following general formula (A21) can be mentioned.
• R 1a is an alkyl group having 6 to 18 carbon atoms
• R 2a is an alkylene group having 2 to 4 carbon atoms
• G is a residue derived from a reducing sugar
• p is the average number of added moles of an oxyalkylene group. is a number from 0 to 10 indicating p R 2a may be the same or different.
• q is a number from 1 to 3 indicating the average degree of condensation of G.
• the number of carbon atoms in R 1a is preferably from the viewpoint of reducing the coefficient of variation of the bubble diameter in the hardened gypsum body and improving the foaming properties of the foaming agent composition contained in the gypsum slurry. is 8 or more, more preferably 10 or more, and preferably 14 or less, more preferably 12 or less.
• R 2a is preferably an ethylene group or a propylene group, more preferably an ethylene group.
• p is preferably 5 or less, more preferably 2 or less, and may be 0.
• q is preferably 2.5 or less, more preferably 2 or less.
• G includes residues derived from monosaccharides such as glucose, galactose, xylose, mannose, lyxose, arabinose, fructose, or mixtures thereof, and disaccharides or more include maltose, xylobiose, isomaltose, cellobiose, gentibiose, and lactose. , sucrose, nigerose, turanose, raffinose, gentianose, menditose, or a mixture thereof.
• preferred raw materials are glucose and fructose as monosaccharides, and maltose and sucrose as disaccharides or more, from the viewpoint of availability.
• the gypsum used can be high-quality neutralized gypsum, phosphogypsum which is a by-product of phosphoric acid, flue gas desulfurization gypsum generated in thermal power generation, natural gypsum containing various impurities or clay, or mixtures thereof. I can do it.
• the clay contained in gypsum is mainly composed of hydrated silicate minerals with a layered structure (hereinafter referred to as clay minerals).
• the clay minerals contained in this clay as fine grains include kaolin minerals (kaolin minerals).
• serpentine lizardite, antigorite, chrysotile
• mica clay minerals illite, sericite, glauconite, celadonite
• chlorite vermiculite
• smectite montmorillonite, beidellite, nontronite, saponite, hectorite
• Examples of gypsum include one or more types selected from anhydrite and hemihydrate.
• natural gypsum or chemical gypsum such as neutralized gypsum or by-product gypsum can be used alone, or a mixture of two or more thereof can be used.
• main chemical gypsum include phosphate gypsum, hydrofluoric gypsum, titanium gypsum, and flue gas desulfurization gypsum.
• the raw material gypsum may include recycled gypsum.
• the recycled gypsum may be any recycled gypsum recovered from waste gypsum boards generated in-house by gypsum board manufacturers, waste gypsum boards generated during new construction and demolition, and the like.
• the present invention can be suitably used with any of these raw gypsums, and excellent effects can be obtained even with gypsums blended in various proportions.
• the hardened gypsum body of the present invention has a water/gypsum ratio that improves the fluidity of the gypsum slurry, increases the average cell diameter of the hardened gypsum body, reduces the coefficient of variation of the cell diameter, and improves the strength.
• a water/gypsum ratio that improves the fluidity of the gypsum slurry, increases the average cell diameter of the hardened gypsum body, reduces the coefficient of variation of the cell diameter, and improves the strength.
• the content is preferably 100% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less.
• the water/gypsum ratio is the mass percentage (mass %) of water and gypsum in the hardened gypsum body, and is calculated as water/gypsum ⁇ 100.
• the water/gypsum ratio may be the mass percentage of water and gypsum in the gypsum slurry before hardening of the gypsum hardened body.
• component (A) is preferably 0.001 part by mass or more, more preferably 0.004 part by mass, from the viewpoint of reducing the density of the hardened gypsum body, based on 100 parts by mass of gypsum. Above, more preferably 0.01 part by mass or more, and from the viewpoint of improving the strength of the gypsum hardened body, preferably 0.1 part by mass or less, more preferably 0.06 part by mass or less, still more preferably 0.03 part by mass. Contains less than 1 part.
• the mass of component (A1) shall be defined using a value converted to sodium salt.
• the content of the component (A) may be the content in the gypsum slurry before hardening of the gypsum hardened body.
• the component (A1) is preferably 0% from the viewpoint of reducing the density of the hardened gypsum body based on 100 parts by mass of the gypsum. 0.001 parts by mass or more, more preferably 0.004 parts by mass or more, even more preferably 0.01 parts by mass or more, and from the viewpoint of improving the strength of the hardened gypsum, preferably 0.1 parts by mass or less, more preferably The content is 0.06 parts by mass or less, more preferably 0.03 parts by mass or less.
• the content of the component (A1) may be the content in the gypsum slurry before curing of the gypsum hardened body.
• the amount of the component (A11) is preferably 0.0% based on 100 parts by mass of the gypsum from the viewpoint of reducing the density of the cured body.
• the content of the above component (A11) may be the content in the gypsum slurry before hardening of the gypsum hardened body.
• the component (A2) is preferably 0% from the viewpoint of reducing the density of the hardened gypsum body based on 100 parts by mass of the gypsum. 0.0001 parts by mass or more, more preferably 0.0005 parts by mass or more, still more preferably 0.001 parts by mass or more, and from the viewpoint of reducing the coefficient of variation of the bubble diameter in the hardened gypsum body and improving the strength. is contained in an amount of 0.01 part by mass or less, more preferably 0.006 part by mass or less, still more preferably 0.003 part by mass or less.
• the content of the component (A2) may be the content in the gypsum slurry before curing of the gypsum hardened body.
• the hardened gypsum body of the present invention further includes component (B) from the viewpoint of improving the rapid foaming properties and foam stability of the foaming agent composition contained in the gypsum slurry and increasing the cell diameter in the hardened gypsum body.
• component (B) a monohydric alcohol having 6 or more and 10 or less carbon atoms.
• the number of carbon atoms in component (B) is 6 or more and 10 or less, preferably 8, from the viewpoint of improving the rapid foaming properties and foam stability of the foaming agent composition contained in the gypsum slurry.
• Component (B) is a straight-chain or branched hydrocarbon group, preferably a straight-chain or branched alkyl group, from the viewpoint of improving the rapid foaming properties and foam stability of the foaming agent composition to be contained in the gypsum slurry. , more preferably a monohydric alcohol having a straight-chain alkyl group.
• Component (B) specifically includes one or more selected from hexanol, octanol, decanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol, and 2-propylheptanol.
• Component (B) is preferably selected from octanol and decanol from the viewpoint of improving the rapid foaming properties and foam stability of the foaming agent composition to be included in the gypsum slurry and increasing the cell diameter in the hardened gypsum body. It is preferable to contain one or more types of octanol, more preferably octanol.
• the content of one or more selected from octanol and decanol in component (B) is preferably 80% by mass or more, more preferably 90% by mass or more, and preferably 100% by mass or less, substantially 100% by mass. % is more preferable. Further, the content of octanol in component (B) is preferably 80% by mass or more, more preferably 90% by mass or more, and preferably 100% by mass or less, and even more preferably substantially 100% by mass.
• the hardened gypsum body of the present invention improves the rapid foaming properties and foam stability of the foaming agent composition containing component (B) in the gypsum slurry, increases the cell diameter in the hardened gypsum body, and From the viewpoint of reducing the density of the cured body, preferably 0.00005 parts by mass or more, more preferably 0.0001 parts by mass or more, still more preferably 0.0005 parts by mass or more, even more preferably, based on 100 parts by mass of gypsum.
• the content is 0.001 parts by mass or more, and from the viewpoint of reducing odor, preferably 0.01 parts by mass or less, more preferably 0.005 parts by mass or less, still more preferably 0.003 parts by mass or less.
• the content of the component (B) may be the content in the gypsum slurry before hardening of the gypsum hardened body.
• the hardened gypsum body of the present invention further contains a nonionic compound having a LogP of 0 or more and less than 2.0 as component (C) from the viewpoint of suppressing separation of the foaming agent composition contained in the gypsum slurry. I can do it. However, compounds corresponding to component (B) are excluded from component (C).
• the LogP of component (C) is 0 or more, preferably 0.4 or more, more preferably 0.8 or more, still more preferably 1. It is 0 or more and less than 2.0, preferably 1.5 or less, more preferably 1.0 or less.
• the logP value is a coefficient indicating the affinity of an organic compound for water and 1-octanol.
• the 1-octanol/water partition coefficient P is a distribution equilibrium when a trace amount of a compound is dissolved as a solute in a two-liquid phase solvent of 1-octanol and water, and is the ratio of the equilibrium concentrations of the compound in each solvent. It is common to express them in the form of their logarithm logP to the base 10.
• the logP values of many compounds have been reported, and many values can be referenced in databases available from Daylight Chemical Information Systems, Inc. (Daylight CIS) and the like.
• ClogP Calculated logP
• This ClogP value can be used in place of the actually measured logP value when selecting a compound. In the present invention, if there is an actual measured value of logP, it is used, and if there is no measured value, the ClogP value calculated by the program CLOGP v4.01 is used.
• nonionic compound of component (C) examples include one or more selected from alcohol (excluding component (B)), glycol ether, and aldehyde.
• the logP of these nonionic compounds needs to satisfy the above range.
• the alcohol is preferably a monohydric alcohol, such as 1-propanol (logP: 0.25), 2-propanol (LogP: 0.05), 1-butanol (logP: 0.88), or 2-butanol (LogP: 0.61), 2-methyl-1-propanol (LogP: 0.76), 2-methyl-2-propanol (LogP: 0.35), 1-pentanol (LogP: 1.51), 2-pen Tanol (LogP: 1.19), 3-pentanol (LogP: 1.21), 2-methyl-1-butanol (logP: 1.29), 2-methyl-2-butanol (LogP: 0.89) , 3-methyl-2-butanol (LogP: 1.28), 3-methyl-1-butanol (LogP: 1.16), and cyclopentanol (LogP: 0.71). It will be done.
• 1-propanol logP: 0.25
• 2-propanol LogP: 0.05
• 1-butanol logP: 0.88
• glycol ethers having a hydrocarbon group having 7 or less carbon atoms are preferred, such as diethylene glycol monobutyl ether (logP: 0.56), ethylene glycol monobutyl ether (logP: 0.81), ethylene glycol monophenyl ether (logP : 1.16), triethylene glycol monobutyl ether (logP: 0.02), and propylene glycol monobutyl ether (logP: 1.15).
• aldehydes examples include butanal (logP: 0.88), pentanal (logP: 1.31), hexanal (logP: 1.78), benzaldehyde (logP: 1.48), and cinnamaldehyde (logP: 1.9).
• Components (C) other than alcohol, glycol ether, and aldehyde include butyl lactate (logP: 0.8), dimethyl ether (logP: 0.1), diethyl ether (logP: 0.89), and diisopropyl ether (logP: 1.52), tetrahydrofuran (logP: 0.46), propanoic acid (logP: 0.33), butanoic acid (logP: 0.79), pentanoic acid (logP: 1.39), hexanoic acid (logP: 1 .92), and benzoic acid (logP: 1.87).
• component (C) is preferably 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-1-butanol, One or more selected from benzaldehyde, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, and diethylene glycol monobutyl ether, more preferably one selected from 1-butanol, 2-methyl-1-butanol, diethylene glycol monobutyl ether, and benzaldehyde. More than a species.
• the cured gypsum body of the present invention preferably contains component (C) of 0.0001 parts by mass or more, based on 100 parts by mass of gypsum, from the viewpoint of suppressing separation of the foaming agent composition contained in the gypsum slurry.
• component (C) 0.0005 parts by mass or more, more preferably 0.001 parts by mass or more, and from the viewpoint of economic efficiency, preferably 0.01 parts by mass or less, more preferably 0.007 parts by mass or less, still more preferably 0. Contains .005 parts by mass or less.
• the content of the component (C) may be the content in the gypsum slurry before curing of the gypsum hardened body.
• the hardened gypsum body of the present invention can contain additives used for gypsum boards and the like.
• additives include water reducers, antifoaming agents, foam stabilizers, curing accelerators, curing modifiers, water repellents, adhesives, and retardants, and reinforcing fibers such as glass fibers, carbon fibers, and waste paper. , virgin pulp, etc., or together with lightweight aggregates such as pearlite, foamed steel, etc., to produce gypsum board.
• water reducing agent examples include one or more selected from naphthalene sulfonic acid polymers, polycarboxylic acid polymers, melamine sulfonic acid polymers, and phosphoric acid ester polymers, preferably naphthalene sulfonic acid polymers. It is one or more selected from polymers and polycarboxylic acid polymers.
• the hardening accelerator examples include one or more selected from dihydrate gypsum and potassium sulfate.
• the cured gypsum body of the present invention can be suitably used for gypsum boards, fireproof materials, etc.
• the present invention provides a method for producing a hardened gypsum body of the present invention, which includes the following steps 1, 2, and 3.
• ⁇ Step 1> (A) Foaming is achieved by foaming a liquid composition containing a foaming agent composition (hereinafter referred to as the foaming agent composition of the present invention) containing a surfactant (hereinafter referred to as component (A)) and water.
• component (A) a surfactant
• the process of obtaining ⁇ Step 2> A step of mixing the foam obtained in step 1 with a gypsum slurry containing gypsum and water to obtain a foam-containing gypsum slurry.
• ⁇ Step 3> After step 2, a step of molding and curing the aerated gypsum slurry.
• the hardened gypsum body of the present invention can be manufactured by this manufacturing method.
• the embodiments described for the hardened gypsum body of the present invention can be applied as appropriate.
• Step 1 is a step of foaming a liquid composition containing the foaming agent composition according to the present invention and water to obtain foam.
• the foaming agent composition according to the present invention contains a surfactant as component (A).
• Component (A) is the same as the component (A) described for the hardened gypsum product of the present invention, and its preferred embodiments are also the same.
• the foaming agent composition according to the present invention preferably contains component (A) in an amount of 5% by mass or more, from the viewpoint of reducing the density of the gypsum hardened body and reducing the amount of the foaming agent composition added.
• component (A) preferably contains component (A) in an amount of 5% by mass or more, from the viewpoint of reducing the density of the gypsum hardened body and reducing the amount of the foaming agent composition added.
• the content is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, even more preferably 35% by mass or less.
• component (A1) is used to reduce the density of the hardened gypsum body, and the amount of the foaming agent composition added is From the viewpoint of reducing From the viewpoint of improving the strength of the cured product and suppressing separation of the foaming agent composition, preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, even more preferably 35% by mass or less. Contains less than % by mass.
• component (A11) may be added to reduce the density of the cured product and the amount of the foaming agent composition added may be reduced.
• component (A11) may be added to reduce the density of the cured product and the amount of the foaming agent composition added may be reduced.
• the amount preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 25% by mass or more, and
• it is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass.
• the content is more preferably 35% by mass or less.
• the foaming agent composition comprises reducing the density of the hardened gypsum body by adding the component (A2), and the amount of the foaming agent composition added. From the viewpoint of reducing and from the viewpoint of suppressing separation of the foaming agent composition, preferably 10% by mass or less, more preferably 7% by mass or less, still more preferably 4% by mass or less, even more preferably 3% by mass or less. , more preferably 2.5% by mass or less.
• the foaming agent composition according to the present invention may further contain a monohydric alcohol having 6 to 10 carbon atoms as the component (B) from the viewpoint of reducing the amount of the foaming agent composition added.
• Component (B) is the same as the component (B) described for the hardened gypsum product of the present invention, and its preferred embodiments are also the same.
• component (B) is used to increase the cell diameter in the hardened gypsum product and reduce the density of the hardened gypsum product.
• component (B) is used to increase the cell diameter in the hardened gypsum product and reduce the density of the hardened gypsum product.
• component (B) is used to increase the cell diameter in the hardened gypsum product and reduce the density of the hardened gypsum product.
• component (B) is used to increase the cell diameter in the hardened gypsum product and reduce the density of the hardened gypsum product.
• the foaming agent composition according to the present invention further contains a nonionic compound having a LogP of 0 or more and less than 2.0 (provided that (B) (excluding compounds that fall under the category of ingredients).
• Component (C) is the same as the component (C) described for the hardened gypsum product of the present invention, and its preferred embodiments are also the same.
• the component (C) is preferably 2% by mass or more, more preferably 3% by mass or more, from the viewpoint of suppressing separation of the foaming agent composition. At least 4% by mass, more preferably at least 4% by mass, and from the viewpoint of reducing the amount of foaming agent composition added, preferably at most 20% by mass, more preferably at most 15% by mass, even more preferably at most 10% by mass. , more preferably 6% by mass or less, even more preferably 5% by mass or less.
• the foaming agent composition according to the present invention contains water.
• the foaming agent composition according to the present invention contains water preferably at least 10% by mass, more preferably at least 20% by mass, even more preferably at least 30% by mass, even more preferably at least 40% by mass, even more preferably
• the content is 50% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less.
• the foaming agent composition according to the present invention includes, as other components, a thickener, a chelating agent, a heavy metal scavenger, a rust preventive agent, a preservative, a coloring agent, a fragrance, an antifoaming agent, a flocculant, a water-soluble polymer, etc. can be contained. These are those that do not fall under the (A) component, (B) component, and (C) component.
• step 1 a liquid composition containing a foaming agent composition according to the present invention and water is foamed to obtain foam.
• the foaming ratio of the liquid composition is preferably 3 times or more, more preferably 5 times or more, even more preferably 7 times or more from the economical viewpoint, and from the viewpoint of kneading of the gypsum slurry and foam, it is preferable. is 20 times or less, more preferably 15 times or less, even more preferably 10 times or less.
• step 2 the foam obtained in step 1 is mixed with a gypsum slurry containing gypsum and water to obtain a foam-containing gypsum slurry.
• the gypsum slurry preferably contains a water reducing agent from the viewpoint of adjusting the viscosity of the gypsum slurry and controlling the coefficient of variation of the bubble diameter in the hardened gypsum body.
• the water reducing agent include one or more selected from naphthalene sulfonic acid polymers, polycarboxylic acid polymers, melamine sulfonic acid polymers, and phosphoric acid ester polymers, preferably naphthalene sulfonic acid polymers.
• the gypsum slurry may contain a hardening accelerator.
• the hardening accelerator include one or more selected from dihydrate gypsum and potassium sulfate.
• foam is added to the gypsum slurry in an amount of preferably 50% by volume or more, more preferably 75% by volume or more, still more preferably 100% by volume or more, from the viewpoint of reducing the weight of the hardened product. From the viewpoint of improving strength, it is preferably mixed in an amount of 200% by volume or less, more preferably 150% by volume or less, still more preferably 100% by volume or less. In this production method, admixtures known in the art can be mixed in step 1 and/or step 2.
• step 2 the mixing amounts of the (A) component, (A1) component, (A2) component, (B) component, and (C) component in the bubble-containing gypsum slurry are the same as each component described in the hardened gypsum product of the present invention.
• the content can be replaced with the mixing amount and applied as appropriate.
• the water/gypsum ratio in the aerated gypsum slurry is the same as the water/gypsum ratio range described for the cured gypsum body of the present invention.
• the temperature of the foam and gypsum slurry used for mixing is preferably 15°C or higher and 40°C or lower, respectively.
• the kneading speed of the foam and the gypsum slurry is preferably 250 rpm or more, more preferably 250 rpm or more, from the viewpoint of increasing the bubble diameter in the hardened gypsum body, reducing the coefficient of variation, and improving kneading properties.
• the speed is 500 rpm or more, more preferably 750 rpm or more, even more preferably 1000 rpm or more, and from the viewpoint of suppressing defoaming, preferably 2000 rpm or less, more preferably 1800 rpm or less.
• the kneading time of the foam and the gypsum slurry is preferably 1 second or more, more preferably from the viewpoint of increasing the bubble diameter in the hardened gypsum body, reducing the coefficient of variation, and improving kneading properties. is 3 seconds or more, more preferably 5 seconds or more, and from the viewpoint of suppressing defoaming, is preferably 60 seconds or less, more preferably 30 seconds or less, still more preferably 20 seconds or less.
• Methods of mixing foam and gypsum slurry are well known, such as those described in U.S. Pat. No. 4,518,652, U.S. Pat. be able to.
• Step 3 After step 2, the following step 3 is further performed to produce a hardened gypsum body.
• Step 3 After Step 2, the step of molding and curing the aerated gypsum slurry. Molding and curing can be performed by known methods. For example, gypsum boards, fireproof materials, etc. can be manufactured by referring to ⁇ Gypsum Board Manufacturing'' described in ⁇ Gypsum Lime Handbook'' (edited by the Gypsum and Lime Society), pages 322 to 324.
• Examples 1 to 3 and Comparative Examples 1 to 2 (1) Preparation of foaming agent composition
• the foaming agent composition shown in Table 1 was prepared by the following method. Each raw material listed in Table 1 was added at a predetermined ratio to a total of 30 g in a 50 mL screw tube, and stirred at 1000 rpm for 3 hours using a stirrer to prepare a foaming agent composition. When the solution viscosity was high and the stirring efficiency was poor, heating was performed at 40° C. as appropriate.
• the mixture was kneaded at high speed for 30 seconds to obtain a gypsum slurry containing air bubbles. Note that the water/gypsum ratio in the gypsum slurry was 75% by mass. The temperature of both the foam and the gypsum slurry used for kneading was 20°C.
• the cross section was observed with a digital microscope, the diameters of 100 bubble cross sections were arbitrarily measured, and the average bubble diameter was calculated from the arithmetic mean of these values. Note that when measuring the diameter of a bubble cross section, if the bubble cross section is circular, the diameter is taken as the diameter, if the bubble cross section is elliptical, the long axis is taken as the diameter, and if the bubble cross section is irregular, the longest part is taken as the diameter. Tables 2 and 3 show the results of the average cell diameter in the hardened gypsum body. The coefficient of variation of the bubble diameter in the obtained gypsum hardened body was calculated from the following formula (1) using the standard deviation of the 100 bubble diameters measured in the above procedure and the average bubble diameter.
• Tables 2 and 3 show the results of the coefficient of variation of the bubble diameter in the hardened gypsum body.
• Bubble diameter variation coefficient Bubble diameter standard deviation ⁇ Average bubble diameter ...
• Tables 2 and 3 show the densities of the stone hardened bodies obtained.
• the hardened gypsum bodies in Tables 2 and 3 had specimen densities of 0.51 g/cm 3 and 0.73 g/cm 3 , respectively. It can be seen that even if the specimen density and average cell diameter of the hardened gypsum body are approximately the same, the compression hardness is improved by setting the value of the coefficient of variation of the bubble diameter of the hardened gypsum body within the range of the present invention.
• Examples 4 to 10 and Comparative Example 3 The foaming agent compositions listed in Table 1 and water were mixed in proportions to give the concentrations listed in Table 4 to prepare diluted aqueous solutions of the foaming agent compositions. Then, a gypsum slurry was prepared in the same manner as in (2) Preparation of a gypsum slurry, except that the conditions for preparing the gypsum slurry as shown in Table 4 were changed.
• NSF naphthalene sulfonic acid formaldehyde condensate salt
• PCE polycarboxylic acid ether-based high performance water reducing agent
• potassium sulfate is a hardening accelerator (does not contribute to improving compressive strength), and was added at the same time as dihydrate gypsum.
• the compressive strength of the hardened gypsum bodies in Table 4 tends to decrease as the specimen density of the gypsum hardened body decreases, so the test results are listed in descending order of specimen density so that the compressive strength can be compared between hardened gypsum bodies with similar densities. I sorted things first. A comparison of hardened gypsum specimens with similar densities shows that the compressive strength is improved by setting the values of the average cell diameter and the coefficient of variation of the cell diameter of the hardened gypsum material within the range of the present invention.

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