WO2022210972A1 - 水硬性組成物用添加剤及びそれを用いた水硬性組成物 - Google Patents
水硬性組成物用添加剤及びそれを用いた水硬性組成物 Download PDFInfo
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- WO2022210972A1 WO2022210972A1 PCT/JP2022/016290 JP2022016290W WO2022210972A1 WO 2022210972 A1 WO2022210972 A1 WO 2022210972A1 JP 2022016290 W JP2022016290 W JP 2022016290W WO 2022210972 A1 WO2022210972 A1 WO 2022210972A1
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
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- C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
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- C04B24/06—Carboxylic acids; Salts, anhydrides or esters thereof containing hydroxy groups
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- C—CHEMISTRY; METALLURGY
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- 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
- C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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- 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
- C04B28/02—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 hydraulic cements other than calcium sulfates
Definitions
- the present invention relates to a hydraulic composition additive and a hydraulic composition using the same.
- Graphene sheets form a sheet-like structure in which carbon atoms are hexagonally bonded like a network.
- the thickness is extremely thin, about 1 nm, and it is light and has high strength. and has the advantage of high thermal conductivity.
- Non-Patent Document 1 it is known that adding several hundred grams of graphene sheets to 1 m 3 of concrete increases the strength by about two times.
- Non-Patent Document 1 has extremely poor production efficiency and is not suitable for efficiently and inexpensively producing large amounts of graphene.
- Non-Patent Document 1 there is a description that the manufacturing method has progressed by citing Non-Patent Document 2, which describes the original manufacturing method.
- Non-Patent Document 2 graphene is obtained by charging 50 mg / ml (5% by mass) of graphite, performing mixer treatment for a long time, and centrifuging. Only 1 to 10 ⁇ g/ml (0.0001 to 0.001%) can be obtained, and the absolute amount obtained and the yield from the original graphite are only about 0.01%, which is not sufficient.
- the step of centrifuging and collecting the supernatant is difficult to scale up.
- an object of the present invention is to provide an additive capable of improving the strength of a hydraulic composition in an efficient manner.
- the present inventors have found that by containing flaky carbon and an organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon, an efficient method found that the strength of the hydraulic composition can be improved.
- the inventors of the present invention have further studied based on this knowledge, and have completed the present invention. That is, the present invention includes the following configurations.
- Item 1 An additive for a hydraulic composition, comprising flaky carbon and an organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon.
- Section 2. The additive for hydraulic compositions according to Item 1, further comprising water.
- hydrophilic group is represented by general formulas (1) to (6):
- —OH in general formula (1) represents a hydroxyl group.
- the oxygen atom in general formula (2) represents an ether bond.
- General formula (5) represents an acid anhydride group.
- R 1 represents a divalent organic group.
- R2 represents a hydrogen atom or an alkyl group.
- X 1 denotes a hydrogen atom, alkali metal, NH4 or organic ammonium.
- X2 represents a hydrogen atom, alkali metal, NH4 , organic ammonium or alkyl group.
- Item 3 The additive for hydraulic compositions according to item 1 or 2, comprising at least one of the above.
- Section 4. The hydrophilic group according to any one of items 1 to 3, wherein the hydrophilic group includes at least one selected from the group consisting of an alcoholic hydroxyl group, —SO 3 Na, —COONa, —COOCH 3 , and a polyoxyethylene group. Additive for hydraulic compositions.
- Item 5 Any one of items 1 to 4, wherein the hydrophobic group comprises at least one selected from the group consisting of an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and a polyoxyalkylene group having 3 or more carbon atoms. Additive for hydraulic compositions as described.
- Item 6 The hydraulic composition according to any one of Items 1 to 5, wherein the hydrophobic group comprises an aryl group to which at least one oxygen atom is bound and/or an aryl group having two or more aromatic rings. Additive for
- the organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon is selected from the group consisting of an AE agent, a water reducing agent, a curing accelerator, an AE water reducing agent, a high performance water reducing agent, a high performance AE water reducing agent and a fluidizing agent.
- the additive for hydraulic composition according to any one of Items 1 to 6, which is at least one chemical admixture for concrete.
- Item 8. The additive for hydraulic composition according to any one of Items 1 to 7, wherein the carbon content of the flaky carbon is 95.0% by mass or more.
- Item 9 The additive for hydraulic compositions according to any one of Items 1 to 8, wherein the size of the flaky carbon is 0.1 to 30.0 ⁇ m.
- Item 10 The additive for hydraulic composition according to any one of Items 1 to 9, wherein the thickness of the flaky carbon is 0.335 to 100 nm.
- Item 11 The hydraulic property according to any one of Items 1 to 10, which contains 1 to 1000 parts by mass of an organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon with respect to 100 parts by mass of the flaky carbon. Additives for compositions.
- Item 12 A method for producing the additive for hydraulic compositions according to any one of Items 1 to 11, A carbonaceous material having a layered structure, a water-soluble compound having a hydrophobic group having a high affinity for carbon and a hydrophilic group, and a carbonaceous material dispersion containing a solvent are subjected to a pressure treatment of 30 MPa or more, By the pressure treatment, (i) colliding two or more of the carbonaceous material dispersions; At least one selected from the group consisting of (ii) colliding the carbonaceous material dispersion with a metal or ceramic material, and (iii) passing the carbonaceous material dispersion through a space having a cross-sectional area of 1 cm 2 or less.
- the production method wherein seeds are treated, the solvent contains water, and the content of the water is 70% by mass or more in the solvent.
- Item 13 A method for producing the additive for hydraulic compositions according to any one of Items 1 to 11, Between the rotating rotating disk and the disk installed substantially parallel to the rotating disk, installing a composition containing a carbonaceous material having a layered structure, a hydrophobic group having a high affinity for carbon, a water-soluble compound having a hydrophilic group, and a solvent; a step of applying shear to the carbonaceous material in the composition while adjusting the shortest distance between the rotating disk and the disk to be 200 ⁇ m or less, wherein the solvent contains water, and The production method, wherein the content of water is 70% by mass or more in the solvent.
- Item 14 The production method according to Item 12 or 13, wherein part or all of the solvent is removed after the pressure treatment or shear treatment.
- Item 15 A hydraulic composition comprising the additive for a hydraulic composition according to any one of Items 1 to 11 and a hydraulic component.
- Item 16 The hydraulic composition according to item 15, wherein the content of the hydraulic composition additive is 0.01 to 10 parts by mass with respect to 100 parts by mass of the hydraulic component.
- Item 17. A hydraulic composition according to Item 15 or 16, which is a cement hydration product.
- Item 18 A method for producing a hydraulic composition according to any one of Items 15 to 17, A manufacturing method comprising a step of mixing a hydraulic powder material and the additive for a hydraulic composition.
- Item 19 The manufacturing method according to Item 18, wherein in the mixing step, a concrete admixture is further mixed.
- the present invention it is possible to provide an additive capable of improving the strength of a hydraulic composition in an efficient manner.
- the present invention when compared with Non-Patent Document 1, when the charged graphite concentration is also 5% by mass, about 10000 times (with respect to the yield of 0.01%, the total amount used is 100%). It is possible to improve the strength of the hydraulic composition by a production method that is efficient in production, easy to scale up, and free from graphite loss.
- the additive for hydraulic composition of the present invention contains flaky carbon and an organic compound having a hydrophilic group and a hydrophobic group having a high affinity for carbon.
- Flaky Carbon functions as a strength improver.
- the flaky carbon preferably has a high carbon content from the viewpoint of improving the strength of the hydraulic composition.
- the carbon content of the flaky carbon is preferably 95.0% by mass or more, more preferably 97.0% by mass or more, and 97.5% by mass or more, assuming that the total amount of flaky carbon is 100% by mass. is more preferable, and 98.0% by mass or more is particularly preferable.
- the upper limit of the carbon content of the flaky carbon is not particularly limited, and is usually 100% by mass.
- the content of flaky carbon having a thickness of 0.335 to 20 nm is preferably 50% or more, more preferably 70% or more, and further preferably 80% or more, based on the total number of flaky carbon as 100%. preferable. That is, although flaky carbon having a large thickness may be included, the thickness of many flaky carbon is preferably 20 nm or less. The thickness of the flaky carbon is measured by observation with a transmission electron microscope (TEM).
- TEM transmission electron microscope
- flaky carbon having a layered structure in which 3 to 60 layers of graphene are laminated is more preferable.
- the content of flaky carbon having 1 to 60 layers is preferably 50% or more, more preferably 70% or more, and further preferably 80% or more, where the total number of flaky carbon is 100%. preferable.
- flaky carbon having a large thickness may be included, but the thickness of a large number of flaky carbon is preferably 60 layers or less. Note that the lamination of flaky carbon is calculated from the thickness measured by observation with a transmission electron microscope (TEM).
- TEM transmission electron microscope
- flaky carbon usually has a planar shape with many convex and reentrant angles, it is difficult to categorically define the size other than the thickness.
- the distance between the furthest convex corners in a piece of flaky carbon is defined as the size of that flaky carbon.
- the size of such flaky carbon is preferably 0.1 to 30.0 ⁇ m, more preferably 0.3 to 20.0 ⁇ m, even more preferably 0.5 to 15.0 ⁇ m.
- flaky carbon having such a size it is easy to further improve the strength improvement characteristics of the hydraulic composition.
- the size of the flaky carbon is measured by observation with a transmission electron microscope (TEM).
- the content of flaky carbon is not particularly limited, but from the viewpoint of strength improvement characteristics for the hydraulic composition, the total amount of the additive for hydraulic composition of the present invention is Based on 100% by mass, 1 to 50% by mass is preferable, 2 to 40% by mass is more preferable, and 2.5 to 30% by mass is even more preferable.
- (1-2) Organic compound having a hydrophilic group and a hydrophobic group with high affinity with carbon
- the graphene structure is maintained by using an organic compound having a hydrophilic group and a hydrophobic group with high affinity with carbon. It is possible to maintain the flaky carbon in the additive for hydraulic composition of the present invention in a uniformly dispersed state without aggregating the flaky carbon, and as a result, strengthen the strength improvement characteristics of the hydraulic composition. can do.
- An organic compound having a hydrophilic group and a hydrophobic group having a high affinity for carbon can also function as a dispersant for uniformly dispersing the flaky carbon.
- Such an organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon is not particularly limited, and various organic compounds (especially water-soluble compounds) that can function as a dispersant for flaky carbon. can be used.
- the hydrophobic group possessed by the organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon is not particularly limited, but an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a poly An oxyalkylene group and the like are preferred.
- An organic compound having a hydrophilic group and a hydrophobic group having a high affinity for carbon can contain one or more of such hydrophobic groups.
- the same hydrophobic groups may be used in a plurality, the same hydrophobic groups may be used in a plurality, or different hydrophobic groups may be used in a plurality.
- the alkyl group may be a straight-chain alkyl group or a branched-chain alkyl group, but from the viewpoint of affinity with carbon, a straight-chain alkyl group is preferable.
- the number of carbon atoms in the alkyl group is preferably 2 or more, more preferably 3 to 22, and even more preferably 4 to 18, from the viewpoint of affinity with carbon.
- alkyl groups examples include n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-undecyl group, n-dodecyl group (or n-lauryl group), n-tridecyl group, n-tetradecyl group (or n-myristyl group), n-pentadecyl group, n-hexadecyl group (or n-cetyl group), n-octadecyl group and the like.
- This alkyl group may or may not have a substituent.
- substituents include cycloalkyl groups, aryl groups, aralkyl groups and the like.
- cycloalkyl group and the aryl group those described later are exemplified.
- the aralkyl group as a substituent of the alkyl group is preferably an aralkyl group having 7 to 14 carbon atoms and having an aryl group and an alkyl group having 1 to 6 carbon atoms, and specifically, benzyl group, phenethyl group and the like. preferable.
- the substituent is not limited to the above, and may have a group derived from a fluorene structure (such as a fluorenyl group).
- a fluorene structure such as a fluorenyl group.
- a phenyl group or the like is preferable as a substituent, and when emphasizing compatibility with flaky carbon, strength improvement characteristics for hydraulic compositions, etc., a naphthyl group, fluorenyl group, or the like is used as a substituent. preferable.
- the alkenyl group preferably has 2 or more carbon atoms, more preferably 3 to 100 carbon atoms, and even more preferably 4 to 30 carbon atoms, from the viewpoint of affinity with carbon and water solubility.
- alkenyl groups include butenyl, hexenyl, octenyl, decenyl, dodecenyl, oleyl and linoleyl groups.
- This alkenyl group may or may not have a substituent.
- substituents include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and the like.
- the aralkyl group is exemplified by those mentioned above, and the cycloalkyl group and aryl group are exemplified below.
- the alkyl group as a substituent of the alkenyl group is preferably an alkyl group having 1 to 6 carbon atoms, and specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, A sec-butyl group, a tert-butyl group and the like are preferred.
- the substituent is not limited to the above, and may have a group derived from a fluorene structure (such as a fluorenyl group).
- a fluorene structure such as a fluorenyl group.
- a phenyl group or the like is preferable as a substituent, and when emphasizing compatibility with flaky carbon, strength improvement characteristics for hydraulic compositions, etc., a naphthyl group, fluorenyl group, or the like is used as a substituent. preferable.
- a cycloalkyl group having 5 to 10 carbon atoms is preferable, and specifically, a cyclopentyl group, a cyclohexyl group and the like are preferable.
- This cycloalkyl group may or may not have a substituent.
- substituents include alkyl groups, aryl groups, aralkyl groups, and the like.
- the alkyl group as a substituent of the cycloalkyl group is preferably an alkyl group having 1 to 6 carbon atoms, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group. , sec-butyl group, tert-butyl group and the like are preferred.
- Examples of the aryl group and aralkyl group as substituents of the cycloalkyl group include those exemplified above.
- the substituent is not limited to the above, and may have a group derived from a fluorene structure (such as a fluorenyl group).
- a fluorene structure such as a fluorenyl group.
- a phenyl group or the like is preferable as a substituent, and when emphasizing compatibility with flaky carbon, strength improvement characteristics for hydraulic compositions, etc., a naphthyl group, fluorenyl group, or the like is used as a substituent. preferable.
- aryl group an aryl group having 6 to 22 carbon atoms (especially 6 to 18) is preferable, and any of monocyclic aryl groups, condensed ring aryl groups and polycyclic aryl groups can be employed. Examples include phenyl group, naphthyl group, anthracenyl group, tetracenyl group, phenanthrenyl group, biphenyl group, terphenyl group, fluorenyl group, acenaphthenyl group, acenaphthylenyl group, pyrenyl group, chrysenyl group, triphenylenyl group and the like.
- This aryl group may or may not have a substituent.
- substituents include phenolic hydroxyl groups, alkyl groups, hydroxyalkyl groups, formylalkyl groups, cycloalkyl groups, aralkyl groups, alkoxy groups and the like.
- the alkyl group as a substituent of the aryl group is preferably an alkyl group having 1 to 6 carbon atoms, and specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, A sec-butyl group, a tert-butyl group and the like are preferred.
- the hydroxyalkyl group as a substituent of the aryl group is preferably a hydroxyalkyl group having 1 to 6 carbon atoms, and specifically, a hydroxymethyl group (-CH 2 OH), a 2-hydroxyethyl group (-CH 2 CH 2 OH), 2-hydroxypropyl group (--CH 2 CHOHCH 3 ), 3-hydroxypropyl group (--CH 2 CH 2 CH 2 OH) and the like are preferred.
- the formylalkyl group as a substituent of the aryl group is preferably a formylalkyl group having 1 to 6 carbon atoms, and specifically, a formylmethyl group (-CH 2 CHO), a 2-formylethyl group (-CH 2 CH 2 CHO), 3-formylpropyl group (--CH 2 CH 2 CH 2 CHO) and the like are preferred.
- Examples of the cycloalkyl group and aralkyl group as substituents of the aryl group include those exemplified above.
- the alkoxy group as a substituent of the aryl group is preferably an alkoxy group having 1 to 6 carbon atoms, and specific examples thereof include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy and isobutyl. Oxy group, sec-butyloxy group, tert-butyloxy group and the like are preferred.
- the substituent is not limited to the above, and may have a group derived from a fluorene structure (such as a fluorenyl group).
- the aryl group mentioned above is an aryl group to which at least one oxygen atom is bonded (such as an aryl group to which a phenolic hydroxyl group is bonded), from the viewpoint of affinity with carbon, strength improvement properties for hydraulic compositions, and the like.
- aryl groups having two or more aromatic rings condensed aryl groups and polycyclic aryl groups, and the like are preferred.
- Polyoxyethylene groups are usually hydrophilic, but polyoxyalkylene groups with 3 or more carbon atoms, such as polyoxypropylene groups and polyoxybutylene groups, become more hydrophobic as the degree of polymerization increases, and function as hydrophobic groups.
- a polyoxypropylene group with a degree of polymerization of 4 or more and a polyoxybutylene group with a degree of polymerization of 3 or more are particularly preferable.
- the degree of polymerization of the polyoxyalkylene group portion having 3 or more carbon atoms is preferably 10,000 or less.
- polyoxyethylene-polyoxypropylene or polyoxyethylene-polyoxybutylene is used as an organic compound having a hydrophilic group and a hydrophobic group having a high affinity for carbon
- the polyoxypropylene group and the polyoxybutylene group are also It can function as a hydrophobic group.
- This polyoxyalkylene group having 3 or more carbon atoms may or may not have a substituent.
- substituents include alkyl groups, cycloalkyl groups, aralkyl groups, aryl groups, and the like.
- the alkyl group as a substituent of the polyoxyalkylene group having 3 or more carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n -butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like are preferred.
- Examples of the cycloalkyl group, aralkyl group and aryl group as substituents of the polyoxyalkylene group having 3 or more carbon atoms include those exemplified above.
- the substituent is not limited to the above, and may have a group derived from a fluorene structure (such as a fluorenyl group).
- a fluorene structure such as a fluorenyl group.
- a phenyl group or the like is preferable as a substituent, and when emphasizing compatibility with flaky carbon, strength improvement characteristics for hydraulic compositions, etc., a naphthyl group, fluorenyl group, or the like is used as a substituent. preferable.
- Such a hydrophobic group is preferably an aryl group or a polyoxyalkylene group having 3 or more carbon atoms, more preferably an aryl group, and at least More preferred are aryl groups with one oxygen atom (such as aryl groups with phenolic hydroxyl groups) and aryl groups with two or more aromatic rings (condensed aryl groups and polycyclic aryl groups).
- hydroxyphenyl group methoxyphenyl group, 3-hydroxypropylphenyl group, naphthyl group, hydroxynaphthyl group, anthracenyl group, hydroxyanthracenyl group, tetracenyl group, hydroxytetracenyl group, phenanthrenyl group, hydroxyphenyl group, nanthrenyl group, biphenyl group, hydroxybiphenyl group, terphenyl group, fluorenyl group, hydroxyfluorenyl group, acenaphthenyl group, acenaphthylenyl group, pyrenyl group, chrysenyl group, triphenylenyl group, polyoxypropylene group having a degree of polymerization of 4 or more, A polyoxybutylene group having a degree of polymerization of 3 or more is preferred.
- the hydrophilic group possessed by the organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon can increase the solubility in water of the organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon.
- the hydrophilic group possessed by the organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon can increase the solubility in water of the organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon.
- —OH in general formula (1) represents a hydroxyl group.
- the oxygen atom in general formula (2) represents an ether bond.
- General formula (5) represents an acid anhydride group.
- R 1 represents a divalent organic group.
- R2 represents a hydrogen atom or an alkyl group.
- X 1 denotes a hydrogen atom, alkali metal, NH4 or organic ammonium.
- X2 represents a hydrogen atom, alkali metal, NH4 , organic ammonium or alkyl group.
- a hydrophilic group represented by is preferred.
- An organic compound having a hydrophilic group and a hydrophobic group having a high affinity for carbon can contain one or more of such hydrophilic groups.
- hydrophilic groups when a plurality of hydrophilic groups are used, a plurality of the same hydrophilic groups may be used, a plurality of types of hydrophilic groups represented by the same general formula may be used, or hydrophilic groups represented by different general formulas may be used. A plurality of types of groups may be used.
- —OH represents a hydroxyl group, and from the viewpoint of hydrophilicity, it preferably represents an alcoholic hydroxyl group.
- the divalent organic group represented by R 1 is not particularly limited, and is preferably a divalent hydrocarbon group.
- divalent hydrocarbon groups include aliphatic hydrocarbon groups (alkylene groups (or alkylidene groups), cycloalkylene groups, alkylene (or alkylidene)-cycloalkylene groups, bi- or tricycloalkylene groups, etc.), aromatic hydrocarbons groups (arylene group, alkylene (or alkylidene)-arylene group, etc.) and the like.
- the alkylene group (or alkylidene group) represented by the group R 1 is preferably an alkylene group, more preferably a C 1-8 alkylene group, still more preferably a C 1-4 alkylene group, and a C 2 Particularly preferred are -4 alkylene groups, most preferred are C 2-3 alkylene groups. Specifically, methylene group, ethylene group, ethylidene group, trimethylene group, propylene group, propylidene group, tetramethylene group, ethylethylene group, butan-2-ylidene group, 1,2-dimethylethylene group, pentamethylene group, A pentane-2,3-diyl group and the like can be exemplified.
- the cycloalkylene group represented by R 1 is preferably a C 5-10 cycloalkylene group, more preferably a C 5-8 cycloalkylene group. Specific examples include a cyclopentylene group, a cyclohexylene group, a methylcyclohexylene group, a cycloheptylene group, and the like.
- the alkylene (or alkylidene)-cycloalkylene group represented by R 1 is preferably an alkylene-cycloalkylene group, more preferably a C 1-6 alkylene-C 5-10 cycloalkylene group, More preferred is a C 1-4 alkylene-C 5-8 cycloalkylene group.
- Specific examples include a methylene-cyclohexylene group, an ethylene-cyclohexylene group, an ethylene-methylcyclohexylene group, an ethylidene-cyclohexylene group, and the like.
- the bi- or tricycloalkylene group represented by group R 1 can be specifically exemplified by norbornane-diyl group and the like.
- the arylene group represented by group R 1 is preferably a C 6-10 arylene group. Specifically, a phenylene group, a naphthalenediyl group, and the like can be exemplified.
- the alkylene (or alkylidene)-arylene group represented by R 1 is preferably an alkylene-arylene group, more preferably a C 1-6 alkylene-C 6-20 arylene group, and a C 1- A 4 -alkylene-C 6-10 arylene group is more preferred, and a C 1-2 alkylene-phenylene group is particularly preferred.
- Specific examples include a methylene-phenylene group, an ethylene-phenylene group, an ethylene-methylphenylene group, an ethylidenephenylene group and the like.
- a divalent aliphatic hydrocarbon group particularly an alkylene group (eg, a C 1-4 alkylene group such as a methylene group, an ethylene group, etc.) is preferred.
- alkylene (or alkylidene)-cycloalkylene group and an alkylene (alkylidene)-arylene group are -R a -R b - (wherein R a is a separate oxygen atom in general formula (2). a bonded alkylene group or alkylidene group, and Rb represents a cycloalkylene group or arylene group).
- the hydrophilic group represented by the general formula (2) is not particularly limited, and for example, -C 2 H 4 O-, -C 3 H 6 O-, -CH 2 O- and the like can be used. . Those having a plurality (preferably 3 to 100) of these can also be preferably used, and for example, a trioxyethylene group, a tetraoxyethylene group, a polyoxymethylene group, a polyoxyethylene group and the like can be used. However, since the polyoxyalkylene group having 3 or more carbon atoms is a hydrophobic group as described above, when the number of carbon atoms in R 1 is 3 or more, the hydrophilic group represented by this general formula (2) is used alone. It is preferred to include (not repeat multiple times).
- hydrophilic group represented by the general formula (2) particularly a polyoxyethylene group
- it is particularly excellent in reinforcing properties such as strength improvement properties for hydraulic compositions.
- the alkali metal represented by X1 is not particularly limited, and includes sodium, potassium, lithium and the like.
- the organic ammonium represented by X1 is preferably a quaternary ammonium, and tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium and the like can be preferably used.
- the hydrophilic group represented by the general formula (3) is not particularly limited, but is, for example, -SO 3 -H + , -SO 3 -Na + , -SO 3 -K + , -SO 3 -Li + , -SO 3 - NH 4 + , -SO 3 - N(CH 3 ) 4 + , -SO 3 - N(C 2 H 5 ) 4 + , -SO 3 - N(C 3 H 7 ) 4 + , —SO 3 — N(C 4 H 9 ) 4 + and the like.
- Examples of the alkali metal and organic ammonium represented by X 2 in the general formula (4) include those exemplified above.
- the alkyl group represented by X 2 may be a straight-chain alkyl group or a branched-chain alkyl group.
- a linear alkyl group is preferred from the viewpoint of properties.
- the number of carbon atoms in the alkyl group is preferably 1 to 2 from the viewpoints of affinity with carbon, strength improvement properties for hydraulic compositions, and the like.
- the hydrophilic group represented by the general formula (4) is not particularly limited, but examples include -COOH, -COONa, -COOK, -COOLi, -COONH 4 , -COON(CH 3 ) 4 , -COON (C 2 H 5 ) 4 , —COON(C 3 H 7 ) 4 + , —COON(C 4 H 9 ) 4 + and the like.
- the group represented by general formula (5) represents an acid anhydride group.
- hydrophilic groups the general formula (1 ) to (5) are preferable, hydrophilic groups represented by general formulas (1) to (4) are more preferable, and general formulas (1), (3) and (4) are represented. Hydrophilic groups are more preferred. Specifically, alcoholic hydroxyl groups, ether groups, —SO 3 H, —SO 3 Na, —COOH, —COONa, —COOCH 3 , acid anhydride groups, polyoxyethylene groups, etc. are preferred, and alcoholic hydroxyl groups, ether groups, etc. are preferred. Group, —SO 3 H, —SO 3 Na, polyoxyethylene group and the like are more preferable, and alcoholic hydroxyl group, —SO 3 H, —SO 3 Na and the like are more preferable.
- the HLB value is From the viewpoint of the water solubility of organic compounds having hydrophobic groups that have a high affinity with carbon, the dispersibility of flaky carbon, and strengthening properties such as strength improvement properties for hydraulic compositions, 12 or more is preferable, and 13 to 19 are more. preferable.
- the hydrophobic groups are the same (when the affinity with the flaky carbon is about the same), the higher the HLB value, the better.
- the organic compound having a hydrophilic group that satisfies the above conditions and a hydrophobic group that has a high affinity for carbon is not particularly limited, but AE agents, water reducing agents, curing accelerators, AE water reducing agents, high performance water reducing agents, Examples include chemical admixtures for concrete such as high performance AE water reducing agents and fluidizing agents. From these, it can also be used individually and can also be used in combination of 2 or more type. These chemical admixtures conform to JIS A 6204.
- the AE agent is not particularly limited, but may be (special) anionic surfactants, alkyl ether-based anionic surfactants, (natural) resinate-based (special) anionic surfactants, or carboxylic acid-based anionic surfactants. , (modified) rosin anionic surfactant, natural resin acid/alkyl ether anionic surfactant, (special) nonionic surfactant, (special) anionic/nonionic surfactant, hydrocarbon sulfonate, Examples include imidazoline laurate derivatives, polyoxyethylene alkyl ether sulfates, and the like. These AE agents can be used alone or in combination of two or more. A complex consisting of two or more of these can also be used.
- the water reducing agent is not particularly limited, but standard water reducing agents include naphthalenesulfonic acid compounds, (modified) ligninsulfonic acid compounds, methylolmelamine condensates, polycarboxylic acid compounds, polycarboxylic acid ether compounds, and oxycarboxylic acid compounds.
- standard water reducing agents include formalin (high) condensates of naphthalenesulfonate, (modified) ligninsulfonic acid compounds, oxycarboxylic acid compounds, and the like. These water reducing agents can be used alone or in combination of two or more. A complex consisting of two or more of these can also be used.
- the curing accelerator is not particularly limited, but includes nitrogen-based inorganic salt compounds (nitrite compounds, nitrate compounds, etc.), calcium silicate hydrate, and the like. These curing accelerators can be used alone or in combination of two or more. A complex consisting of two or more of these can also be used.
- the AE water reducing agent is not particularly limited, but standard AE water reducing agents include (modified) ligninsulfonic acid compounds, (natural) resinate compounds, organic acid compounds, (special) ether compounds, polyether compounds, ( modified) polyol compounds, cellulose ether compounds, polycarboxylic acid compounds, polycarboxylic acid ether compounds, polycarboxylic acid polyether polymers, polyalkylene glycol compounds, polycarboxylic acid compounds, oxycarboxylic acid compounds, PAE compounds, etc.;
- Type AE water reducing agents include (modified) ligninsulfonic acid compounds, polycarboxylic acid compounds, hydroxycarboxylic acid compounds, oxycarboxylic acid compounds, organic acid compounds, glycitol compounds, natural resin acid compounds, polyether compounds, and (special) ether compounds.
- modified polyol compounds polyalkylene glycol compounds, polycarboxylic acid ether compounds, polycarboxylic acid polyether polymers, cellulose ether compounds, PAE compounds, etc.; system inorganic salt compounds (nitrite compounds, nitrate compounds, etc.), polycarboxylic acid compounds, organic acid compounds, polycarboxylic acid ether compounds, modified polyol compounds, rhodan compounds, amine compounds, and the like.
- the PAE compound means a dispersant composed of a predetermined polycondensation product, and the details thereof are also described in International Publication No. WO 2019/116425, so the description thereof is incorporated herein.
- These AE water reducing agents can be used alone or in combination of two or more. A complex consisting of two or more of these can also be used.
- the high-performance water reducing agent is not particularly limited, but naphthalenesulfonic acid compounds, naphthalenesulfonic acid formalin (high) condensates, polyether compounds, (modified) polyol compounds, carboxy group-containing polyether compounds, polyalkylene glycol compounds, Polycarboxylic acid compounds, polycarboxylic acid/(special) thickener complexes, polycarboxylic acid ether compounds, melamine sulfonic acid compounds, melamine sulfonic acid (high) condensate salts, aminosulfonic acid compounds, nitrogen-containing sulfonates, Amidosulfonic acid-modified melamine condensates, alkylallyl sulfonate (high) condensates, (modified) methylol melamine condensates, ester compounds, polycarboxylic acid ether compounds, PAE compounds and the like.
- the PAE compound means a dispersant composed of a predetermined polycondensation product, and the details thereof are also described in International Publication No. WO 2019/116425, so the description thereof is incorporated herein.
- These superplasticizers can be used alone or in combination of two or more. A complex consisting of two or more of these can also be used.
- the high-performance AE water-reducing agent is not particularly limited, but standard high-performance AE water-reducing agents include (modified) ligninsulfonic acid compounds, aminosulfonic acid compounds, polycarboxylic acid compounds, polyether compounds, and carboxy group-containing polyethers. compounds, polyalkylene glycol compounds, ester compounds, PAE compounds, etc.; delayed high performance AE water reducing agents include (modified) ligninsulfonic acid compounds, polycarboxylic acid compounds, polycarboxylic acid ether compounds, polyether compounds, carboxy Group-containing polyether compounds, polyalkylene glycol compounds, PAE compounds and the like can be mentioned.
- the PAE compound means a dispersant composed of a predetermined polycondensation product, and the details thereof are also described in International Publication No. WO 2019/116425, so the description thereof is incorporated herein.
- These high performance AE water reducing agents can be used alone or in combination of two or more. A complex consisting of two or more of these can also be used.
- fluidizing agent there are no particular restrictions on the fluidizing agent, but standard fluidizing agents include melamine sulfonic acid compounds, alkylallyl sulfonic acid (high) condensates, (special) polycarboxylic acid compounds, polycarboxylic acid ether compounds, (special ) hydroxycarboxylic acid compounds, oxycarboxylic acid compounds, polyalkylene glycol compounds, and the like; and delay type fluidizing agents, such as polycarboxylic acid compounds and polycarboxylic acid ether compounds. These fluidizing agents can be used alone or in combination of two or more. A complex consisting of two or more of these can also be used.
- Examples of such organic compounds having a hydrophilic group and a hydrophobic group having a high affinity for carbon include Mighty AE-03, Mighty 100, Mighty 150, Mighty 150RX, Mighty 21HS, Mighty 21VS and Mighty manufactured by Kao Corporation.
- Tupole SSP-104 Tupole SSP-104H, Tupole HSP, Tupole EX, Tupole EX20, Tupole EX50, Tupole Tupole EX60, Tupole EX60T, Tupole EX60LB, Tupole LS-A, Tupole NR, Tupole NR20, Tupole EX50R, Tupole EX60R, Tupole EX60TR, Tupole EX60LBR, Tupole LS-AR, Tupole NZ , Tupole HP-8, Tupole HP-11, Tupole HP-11W , Tupole SR, Tupole HP-70, Tupole HP-70B, Tupole HF-70, Tupole HF-70R, Pole Fine MF, Pole Fine 510, Pole Fine SPA-2, High Fluid H; Nippon Sika ( Sikament Co., Ltd.
- Accelerate 100, Super Melamine; Lion Corporation Leopak G-100, Leopak G- 200, etc. can be used.
- These organic compounds having a hydrophilic group and a hydrophobic group having a high affinity for carbon can be used alone, or two or more of them can be used in combination. A complex consisting of two or more of these can also be used.
- the content of the organic compound having a hydrophilic group and a hydrophobic group with high affinity with carbon in the additive for hydraulic composition of the present invention is not particularly limited, but it has a hydrophilic group and a hydrophobic group with high affinity with carbon.
- the total amount of the additive for hydraulic compositions of the present invention is 100% by mass, and the amount is 0.1 to 50 mass. %, more preferably 0.2 to 40% by mass, even more preferably 0.3 to 30% by mass.
- the content of the organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon in the additive for hydraulic composition of the present invention is not particularly limited, but a hydrophilic group and a hydrophobic group having a high affinity with carbon 10 to 1000 parts by mass is preferable with respect to 100 parts by mass of flaky carbon, and 20 to 500 parts by mass, from the viewpoint of the water solubility of the organic compound having the parts is more preferred, and 30 to 300 parts by mass is even more preferred.
- the additive for a hydraulic composition of the present invention is applied to the surface of the flaky carbon with a hydrophilic group and an affinity with carbon. It has a structure coated with an organic compound having a highly hydrophobic group (Fig. 1).
- the additive for hydraulic composition of the present invention is an organic compound having a hydrophobic group having a high affinity with carbon. It has a structure in which flaky carbon is dispersed inside (Fig. 2).
- an organic compound having a hydrophilic group and a hydrophobic group that has a high affinity with carbon is interposed around the flaky carbon, thereby suppressing aggregation of the flaky carbon and improving the dispersibility of the flaky carbon. , it is possible to obtain a material capable of improving strength-enhancing properties for hydraulic compositions.
- the additive for hydraulic composition of the present invention contains other components.
- Such other components include, for example, carbon fiber (especially carbon nanofiber with a fiber diameter of 500 nm or less), activated carbon, carbon black (acetylene black, oil furnace black, etc.); black), vitreous carbon, carbon microcoils, fullerenes, biomass-based carbon materials (bagasse, sorghum, wood chips, sawdust, bamboo, tree bark, rice straw, rice husks, coffee grounds, used tea leaves, okara lees, rice bran, pulp waste, etc.
- Raw materials carbon fiber manufactured from lignin, etc.), cellulose nanofiber, boron nitride, molybdenum compounds (molybdenum disulfide, organic molybdenum, etc.), tungsten disulfide, melamine cyanurate, phthalocyanine, lead oxide, calcium fluoride, Layered minerals (mica, talc, etc.) and the like can also be used as long as they do not impair the effects of the present invention.
- the content of other components is small. It is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, based on 100% by mass as the total amount of the additive for hydraulic compositions of the present invention.
- the shape of the additive for hydraulic compositions of the present invention is not particularly limited, and examples thereof include a coating film, a sheet, and an aggregate. Moreover, without being limited to a solid, it may contain water to form an aqueous dispersion, which will be described later.
- the additive for hydraulic composition of the present invention is excellent in water solubility of organic compounds having hydrophilic groups and hydrophobic groups with high affinity with carbon, dispersibility of flaky carbon, and hydraulic composition. It is a material that can improve the strength improvement characteristics for objects.
- Such a hydraulic composition additive of the present invention is a material that can be added to a hydraulic composition to improve the strength after curing, and can be used for paste, mortar, concrete, and the like.
- the additive for hydraulic composition of the present invention contains, for example, water, and the content of water is 70% by mass or more in the solvent using a solvent.
- a carbonaceous material having a layered structure, a water-soluble compound having a hydrophobic group having a high affinity for carbon and a hydrophilic group, and a carbonaceous material dispersion containing a solvent are subjected to a pressure treatment of 30 MPa or more, By the pressure treatment, (i) colliding two or more of the carbonaceous material dispersions; At least one selected from the group consisting of (ii) colliding the carbonaceous material dispersion with a metal or ceramic material, and (iii) passing the carbonaceous material dispersion through a space having a cross-sectional area of 1 cm 2 or less.
- composition containing a carbonaceous material having a layered structure, a hydrophobic group having a high affinity for carbon, a water-soluble compound having a hydrophilic group, and a solvent is obtained by applying shear to the carbonaceous material in the composition while adjusting the shortest distance between the rotating disk and the disk to be 50 ⁇ m or less. can be manufactured.
- a dispersion flaky carbon dispersion
- an organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon and a solvent, flaky carbon, hydrophilic groups and affinity with carbon
- the above description can be adopted for the organic compound having a hydrophobic group with high affinity.
- the flaky carbon dispersion may also contain other components as described above, if necessary.
- This flaky carbon dispersion may be formed as a dispersion liquid, or may be formed as a coating film on a substrate.
- the solvent used for preparing the flaky carbon dispersion includes dispersibility of flaky carbon, strength improvement properties for the hydraulic composition, and the like. From this point of view, it is preferable to use water as the main solvent.
- the content of water in the solvent to be used is not particularly limited, but from the viewpoint of the dispersibility of flaky carbon, strength improvement properties for hydraulic compositions, etc., the total amount of the solvent is 100% by mass, and it is 70% by mass or more ( 70 to 100% by mass), more preferably 75 to 100% by mass.
- the solvent only water may be used, and the organic solvent may not necessarily be used.
- Monohydric alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol and tert-butyl alcohol;
- Organic solvents such as polyhydric alcohols; 2-methoxyethanol may also be used.
- the content of the organic solvent in the solvent to be used is the solubility of the organic compound having a hydrophilic group and a hydrophobic group with high affinity with carbon, the strength improvement characteristic for the hydraulic composition, etc., and the total amount of the solvent is 100% by mass. is preferably 30% by mass or less (0 to 30% by mass), more preferably 5 to 25% by mass.
- the content of the flaky carbon is not particularly limited, but from the viewpoint of easy composition of the additive for the hydraulic composition of the present invention, the total amount of the flaky carbon dispersion is 100% by mass. , preferably 30% by mass or less, more preferably 0.001 to 20% by mass, and even more preferably 0.1 to 10% by mass.
- the content of the organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon is not particularly limited, but from the viewpoint of easy composition of the durability improving agent of the present invention, the flaky carbon dispersion Taking the total amount as 100% by mass, it is preferably 0.01 to 50% by mass, more preferably 0.1 to 40% by mass, and even more preferably 0.5 to 30% by mass.
- the content of the organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon in the flaky carbon dispersion is not particularly limited, but it is easy to make the composition of the additive for the hydraulic composition of the present invention. From a viewpoint, it is preferably 10 to 1,000 parts by mass, more preferably 20 to 500 parts by mass, and even more preferably 30 to 300 parts by mass with respect to 100 parts by mass of flaky carbon.
- the content of the solvent is not particularly limited, but from the viewpoint of easy composition of the additive for the hydraulic composition of the present invention, the total amount of the flaky carbon dispersion is 100% by mass, 50 to 99.9998% by mass is preferred, 60 to 99.998 mass % is more preferred, and 70 to 99.98 mass % is even more preferred.
- the method for producing the flaky carbon dispersion is not particularly limited, and the solvent has a high affinity for flaky carbon and hydrophilic groups and carbon.
- An organic compound having a hydrophobic group can also be introduced.
- flaky carbon can be added to a dispersion of an organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon, or flaky carbon can be added to a dispersion having a hydrophilic group and a high affinity with carbon.
- Organic compounds with highly hydrophobic groups can also be introduced.
- flaky carbon and an organic compound having a hydrophilic group and a hydrophobic group having a high affinity for carbon can be added to the solvent at the same time.
- the rotating rotating disk and the rotating disk are installed substantially parallel to the rotating disk.
- a composition containing a carbonaceous material having a layered structure and an organic compound having a hydrophilic group and a hydrophobic group having a high affinity for carbon is placed between the rotating disc and the disc, and the shortest distance between the rotating disc and the disc. It is preferable to apply shear to the carbonaceous material in the composition while adjusting the distance to be 200 ⁇ m or less (grinding method).
- the flaky carbon dispersion is obtained by applying pressure of 30 MPa or more to a composition containing a carbonaceous material having a layered structure and an organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon. (High-pressure dispersion method).
- the flaky carbon maintaining the graphene structure is uniformly dispersed without aggregating (flaky carbon
- the flaky carbon can be obtained in the dispersion), the obtained flaky carbon is hardly broken, and the flaky carbon can be obtained in a short time, and the lumps that fail to peel off hardly remain.
- the organic compound having a hydrophilic group and a hydrophobic group having a high affinity for carbon can also function as a dispersant for uniformly dispersing the flaky carbon.
- the direction in which the force is applied is parallel to the surface direction of the carbonaceous material having a layered structure, and the treatment is performed in a narrow space.
- flaky carbon of a larger size for example, flaky carbon with a size of 1 ⁇ m or more
- the treatment is performed in a short time (with a small number of passes) with high peeling efficiency.
- thick lumps that fail to peel off are less likely to remain.
- the carbonaceous material having a layered structure is not particularly limited, and includes natural graphite, artificial graphite, expanded graphite, earthy graphite, graphite oxide and the like.
- Oxidized graphite may be graphite oxidized with one or more oxidizing agents such as sulfuric acid, nitric acid, potassium permanganate, and hydrogen peroxide.
- the graphite when obtaining graphite oxide by the Hammers method, the graphite is immersed in concentrated sulfuric acid, potassium permanganate is added to oxidize the graphite, and then the reactant is quenched with dilute sulfuric acid and/or hydrogen peroxide, After that, by washing with distilled water or the like, oxygen atoms are bonded to the carbon atoms and oxygen atoms are introduced between the layers to obtain graphite oxide.
- graphite oxide may be used when emphasis is placed on ease of manufacture.
- solvent molecules are easily inserted between the layers, it is easy to peel only in the layer direction, and the exfoliation efficiency and dispersibility are improved, so it is possible to shorten the treatment time. be.
- graphite oxide when graphite oxide is used, reduction treatment is required later, and from the viewpoint of maintaining the graphene structure, conductivity and strength, other materials (natural graphite, artificial graphite, expanded graphite, earthy graphite) is preferred.
- earthy graphite in order to further improve the dispersibility.
- other materials naturally graphite, artificial graphite, expanded graphite, graphite oxide
- crystallinity, purity and structure maintenance are preferable from the viewpoint of crystallinity, purity and structure maintenance.
- artificial graphite can be used when the crystallinity, strength, structure maintenance, etc. of the obtained flaky carbon are emphasized.
- the content of the carbonaceous material having a layered structure in the composition containing the carbonaceous material having a layered structure and the organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon is not particularly limited.
- the total amount of the composition used for producing the flaky carbon dispersion is 100% by mass, preferably 30% by mass or less, more preferably 0.001 to 20% by mass, and further 0.1 to 10% by mass. preferable.
- the thinner the content of the carbonaceous material having a layered structure the easier it is for flaky carbon to occur (delamination between layers). It tends to be easy to perform shearing treatment and the like while maintaining an appropriate viscosity.
- the content of the carbonaceous material having a layered structure in the flaky carbon dispersion is preferably within the above range.
- Organic Compound Having a Hydrophilic Group and a Hydrophobic Group Having a High Affinity with Carbon As the organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon, those mentioned above can be used.
- the content of the organic compound having a hydrophilic group and a hydrophobic group with high affinity with carbon in the composition used for producing the flaky carbon dispersion is not particularly limited, but the flaky carbon dispersion 0.01 to 50% by mass, more preferably 0.1 to 40% by mass, and even more preferably 0.5 to 30% by mass, when the total amount of the composition used for producing is 100% by mass.
- the content of the organic compound having a hydrophilic group and a hydrophobic group having a high affinity for carbon in the composition used for producing the flaky carbon dispersion is 100% of the carbonaceous material having a layered structure.
- the content of the organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon the thinner the content, the higher the content of the carbonaceous material having a relatively layered structure, and the strength of the hydraulic composition tends to be improved. At the same time, it is inexpensive and easy to process.
- flaky carbon tends to be obtained more efficiently because flaking (delamination) occurs more easily. Conversely, when the viscosity increases, the exfoliation efficiency may decrease.
- the content of the organic compound having a hydrophilic group and a hydrophobic group having a high affinity for carbon is within the above range. is preferred.
- a composition containing a carbonaceous material having a layered structure and an organic compound having a hydrophilic group and a hydrophobic group having a high affinity for carbon is used.
- a specific treatment from the viewpoint of exfoliation efficiency of the carbonaceous material having a layered structure, improvement in the strength of the obtained hydraulic composition, etc., a carbonaceous material having a layered structure, a hydrophilic group and carbon It is preferable to perform a specific treatment on the carbonaceous material dispersion containing an organic compound having a hydrophobic group that has a high affinity with .
- the carbonaceous material dispersion may be formed as a dispersion liquid, or may be formed as a coating film on a substrate.
- the solvent used to prepare the carbonaceous material dispersion (carbonaceous material dispersion or carbonaceous material coating film)
- the above-mentioned solvents can be adopted.
- the total amount of the solvent in the carbonaceous material dispersion is not particularly limited. From the viewpoint of efficiency, solubility of an organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon, etc., the total amount of the carbonaceous material dispersion is 100% by mass, and 50 to 99.9998% by mass is preferable, and 60 to 99% by mass. 0.998 mass % is more preferred, and 70 to 99.98 mass % is even more preferred.
- the carbonaceous material dispersion when a specific treatment is performed using a carbonaceous material dispersion using a solvent, the carbonaceous material dispersion has a layered structure of an organic compound dispersion having a hydrophilic group and a hydrophobic group having a high affinity with carbon. or an organic compound having a hydrophilic group and a hydrophobic group having a high affinity for carbon may be added to a carbonaceous material dispersion having a layered structure.
- a carbonaceous material having a layered structure and an organic compound having a hydrophilic group and a hydrophobic group having a high affinity for carbon may be introduced into the solvent at the same time.
- a composition containing a carbonaceous material having a layered structure and an organic compound having a hydrophilic group and a hydrophobic group having a high affinity for carbon may contain other ingredients.
- the finally obtained flaky carbon dispersion and the additive for the hydraulic composition can contain these other components.
- those mentioned above can be employed, and may be used within a range that does not impair the effects of the present invention.
- the content of other components is small. It is preferably 0.00001 to 5% by mass, more preferably 0.0001 to 2% by mass, based on 100% by mass as the total amount of the carbonaceous material dispersion.
- Shear treatment (grinding method)
- a carbonaceous material having a layered structure, a hydrophilic group and a carbon A composition containing an organic compound having a hydrophobic group that has a high affinity with is installed, and while adjusting the shortest distance between the rotating disk and the disk to be 200 ⁇ m or less, the carbonaceous material in the composition It is preferable to apply a shearing treatment.
- the carbonaceous material dispersion is placed between a rotating rotating disk and a disk installed substantially parallel to the rotating disk, It is preferable to apply shear to the carbonaceous material in the carbonaceous material dispersion while adjusting the shortest distance from the disc to 200 ⁇ m or less.
- the carbonaceous material having a layered structure is atomized by the shearing treatment, the graphene structure may not be maintained depending on the conditions, but the carbonaceous material having a layered structure is efficiently thinned. can reduce the processing time.
- the rotating disk and the disk are installed substantially parallel when performing such shearing treatment, they do not have to be strictly parallel.
- the angle between the axis perpendicular to the rotating disk and the axis perpendicular to the disk is preferably 10° or less, more preferably 5° or less. Most preferably, the axis perpendicular to the rotating disc and the axis perpendicular to the disc are strictly parallel.
- the shortest distance between the two surfaces when performing such a shearing treatment is not particularly limited as long as the carbonaceous material having a layered structure can be sufficiently thinned, but is preferably 200 ⁇ m or less, and 50 ⁇ m. The following is more preferable, and 30 ⁇ m or less is even more preferable.
- the shortest distance between the two surfaces when shearing is performed is the carbonaceous material having a layered structure from the shortest distance actually measured between the rotating disc and the hydrophilic group and carbon. means the distance excluding the thickness of the composition containing the organic compound having a high hydrophobic group.
- the fact that the measured shortest distance between the rotating disk and the disk is 0 ⁇ m means that the carbonaceous material having a layered structure and the hydrophilic group and the hydrophilic group and the carbon-affinity material are placed in close contact between the rotating disk and the disk.
- a composition containing an organic compound having a high hydrophobic group is placed, that is, a carbonaceous material having a layered structure and an organic compound having a hydrophilic group and a hydrophobic group having a high affinity for carbon are placed between the rotating discs It means that there is no space other than compounds.
- the rotating disk and the disk are installed substantially parallel, the distance between the rotating disk and the disk may vary depending on the location.
- the shortest distance between the rotating disc and the disc means the shortest distance between the rotating disc and the disc.
- the material to be processed may be sandwiched between the rotating disk and the disk, and the rotating disk and the disk are kept in contact, A carbonaceous material having a layered structure may be sandwiched between the rotating disk and the disk so as to widen.
- Such shearing treatment may be performed using a stone mill, vibratory mixer, spin coater, grinder, or the like, as long as there is a mechanism for rotating a plate-like object.
- the size of the rotating disc and disc that can be used at this time is not particularly limited, and is preferably 5 to 500 mm, more preferably 10 to 200 mm.
- the number of rotations of the rotating disk during the shearing treatment is not particularly limited, and is preferably within a range where the carbonaceous material having a layered structure can be sufficiently thinned, for example, preferably 1000 to 10000 ppm. , 1500 to 3000 ppm is more preferred.
- the carbonaceous material having a layered structure is brought into contact with the carbonaceous material having a layered structure, and the carbonaceous material having a layered structure and the carbonaceous material having a layered structure are contacted to form a layered structure on the carbonaceous material having a layered structure.
- Shear can be applied in a direction parallel to the graphene layers of the structured carbonaceous material.
- This shearing operation can be performed one or more times, preferably three or more times.
- the temperature at which the shearing treatment is performed is not particularly limited, and may be a temperature at which the carbonaceous material having a layered structure can be sufficiently thinned. obtain.
- the temperature at which the shear treatment is performed is preferably under conditions where the solubility of the organic compound having a hydrophilic group and a hydrophobic group with high affinity with carbon is high, and when the solubility increases at a higher temperature, a higher temperature is preferable, and has a cloud point. When using a water-soluble compound, it is preferable to keep the temperature below the cloud point.
- a stirring device, an ultrasonic dispersing device, etc. are used in order to bring the carbonaceous material having a layered structure into good contact with the organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon.
- the organic compound having a hydrophilic group and a hydrophobic group having a high affinity for carbon may be blended with the surface of the carbonaceous material having a layered structure by stirring in advance before preparing the composition.
- graphite oxide when used as the carbonaceous material having a layered structure, it exists as an oxide of flaky carbon in the sheared dispersion. Therefore, when graphite oxide is used as the carbonaceous material having a layered structure, it is preferable to perform a reduction treatment as a post-treatment.
- a reduction treatment various methods such as chemical reduction and electrochemical reduction can be employed, but chemical reduction is preferred. Among them, chemical reduction with reducing agents such as hydrazine and sodium borohydride is preferred.
- the amount of the reducing agent is preferably 1 to 1000 parts by mass, more preferably 20 to 500 parts by mass, and even more preferably 30 to 300 parts by mass with respect to 100 parts by mass of the flaky carbon oxide.
- the heating temperature is preferably 40 to 200°C, more preferably 50 to 150°C, even more preferably 60 to 120°C.
- the reduction time is preferably 10 minutes to 64 hours, more preferably 30 minutes to 48 hours, even more preferably 1 to 24 hours. However, it is preferably to the extent that the graphene structure is not destroyed excessively.
- the flaky carbon can be obtained as the flaky carbon dispersion described above.
- the flaky carbon dispersion also contains an organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon.
- This organic compound having a hydrophilic group and a hydrophobic group that has a high affinity with carbon can also be adsorbed on the surface of flaky carbon and isolated and dispersed flaky carbon at a high concentration in a solvent, so that flaky carbon dispersion It also functions as a dispersant in the body.
- an organic compound having a hydrophilic group and a hydrophobic group that has a high affinity with carbon is adsorbed on the surface of the flaky carbon.
- the weight loss in the range of 100 to 450° C. where the influence of adsorbed water can be eliminated is preferably 2.00 to 20.00% by mass, and 3.00 to 10.0%. 00% by mass is more preferable. This makes it particularly easy to improve the strength of the hydraulic composition.
- the organic compound having a hydrophilic group and a hydrophobic group having a high affinity for carbon can be used as a commercially available product, and is superior to conventional products in terms of both cost and dispersibility.
- the organic compound having a hydrophilic group and a hydrophobic group having a high affinity for carbon can impart sufficient strength to the hydraulic composition by remaining on the surface of the flaky carbon.
- an organic compound having a hydrophilic group and a hydrophobic group having a high affinity for carbon may exist in the vicinity of the flaky carbon without being adsorbed on the surface of the flaky carbon. Even if it is not adsorbed on the surface of the flaky carbon, it is present between the flaky carbon, making it easy to prevent strong agglomeration due to van der Waals forces between the flaky carbon, and promotes dispersion after addition to concrete. It's easy to do.
- the additive for the hydraulic composition is solid and includes other than the organic compound adsorbed on the surface of the flaky carbon, the effect of preventing the aggregation of the flaky carbon, the effect of promoting dispersion, and the interaction with the concrete via the organic matter.
- the organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon contained in the additive for hydraulic composition is 1 to 1000 parts by mass with respect to 100 parts by mass of flaky carbon. is preferred, and 10 to 200 parts by mass is more preferred.
- the plastic substrate is hydrolyzed during the reduction treatment, and when the reduction treatment is applied, the flaky carbon aggregates and cannot exist as a dispersion. Therefore, it was impossible to form a flaky carbon dispersion on a plastic substrate.
- a specific By performing the treatment it is also possible to form a flaky carbon dispersion on a substrate of plastic such as polyethylene terephthalate (PET) without undergoing hydrolysis.
- PET polyethylene terephthalate
- Pressure treatment (high pressure dispersion method)
- the composition containing the carbonaceous material having a layered structure and the organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon is subjected to a pressure of 30 MPa. It is preferable to perform the above pressure treatment.
- the carbonaceous material having a layered structure is atomized by the pressure treatment, the graphene structure may not be maintained depending on the conditions, but the carbonaceous material having a layered structure can be efficiently thinned. can be performed and the processing time can be reduced.
- the pressure level when performing such pressure treatment is not particularly limited as long as the carbonaceous material having a layered structure can be sufficiently thinned, but is preferably 30 MPa or more, and 50 to 400 MPa. is more preferable, and 100 to 300 MPa is even more preferable.
- Such pressure treatment can be performed using a high-pressure dispersion device, a supercritical water preparation device, or the like.
- a high-pressure dispersing device can disperse by applying mechanical pressure, and a supercritical water-producing device can raise the pressure of the system by heating water.
- Such pressurization causes, for example, (i) colliding two or more of the carbonaceous material dispersions; (ii) colliding the carbonaceous material dispersion with a metal or ceramic material (high-hardness material such as silicon carbide or alumina); (iii) A treatment such as passing the carbonaceous material dispersion through a space having a cross-sectional area of 1 cm 2 or less can be performed.
- the pressurizing conditions can be made stronger, the carbonaceous material having a layered structure can be thinned more efficiently, and the processing time can be further reduced. be able to. Moreover, according to the above (iii), the carbonaceous material having a layered structure can be thinned more appropriately while maintaining the graphene structure.
- This pressurizing operation can be performed once or more, preferably 10 times or more.
- the pressing temperature is not particularly limited, and may be a temperature at which the carbonaceous material having a layered structure can be sufficiently thinned. ⁇ 95°C.
- the temperature is preferably 0 to 100 ° C., and when pressure is generated by the supercritical state of water, 373 to 700 ° C. is preferable, and 380 to 450 ° C. is more preferable. preferable.
- an ultrasonic dispersion treatment as a preliminary treatment (pretreatment) to atomize the carbonaceous material having a layered structure. This can have effects such as clogging prevention.
- the output power when performing ultrasonic dispersion treatment it should be stronger than the ultrasonic dispersion treatment (about 40 to 50 W) that is usually performed from the viewpoint of thinning the carbonaceous material having a layered structure. is preferred.
- the output of the ultrasonic dispersion treatment is preferably 100 W or more, more preferably 300 to 20000 W, even more preferably 400 to 18000 W.
- the ultrasonic dispersion temperature is not particularly limited, and may be a temperature at which the carbonaceous material having a layered structure can be sufficiently thinned.
- the ultrasonic dispersion time is not particularly limited, and may be set to a time sufficient to thin the carbonaceous material having a layered structure, and may be 1 to 600 minutes, particularly 3 to 120 minutes.
- dispersion treatment using other dispersing devices such as normal mechanical stirring, dispersing treatment using an emulsifying device, dispersing treatment using a bead mill, etc. may be used in combination.
- graphite oxide when used as the carbonaceous material having a layered structure, it exists as an oxide of flaky carbon in the pressure-treated dispersion. Therefore, when graphite oxide is used as the carbonaceous material having a layered structure, it is preferable to perform a reduction treatment as a post-treatment.
- a reduction treatment various methods such as chemical reduction and electrochemical reduction can be employed, but chemical reduction is preferred. Among them, chemical reduction with reducing agents such as hydrazine and sodium borohydride is preferred.
- the amount of the reducing agent is preferably 1 to 1000 parts by mass, more preferably 10 to 500 parts by mass, and even more preferably 50 to 300 parts by mass with respect to 100 parts by mass of the flaky carbon oxide.
- the heating temperature is preferably 40 to 200°C, more preferably 50 to 150°C, even more preferably 60 to 120°C.
- the reduction time is preferably 10 minutes to 64 hours, more preferably 30 minutes to 48 hours, even more preferably 1 to 24 hours. However, it is preferably to the extent that the graphene structure is not destroyed excessively.
- the additive for hydraulic composition of the present invention is obtained by removing the solvent from the flaky carbon dispersion, if necessary. can be done.
- a method of concentrating the flaky carbon dispersion In order to remove the solvent, there is a method of concentrating the flaky carbon dispersion. It can be carried out by a method of recovering the heat conductive material of the present invention by solid-liquid separation.
- a method for solid-liquid separation for example, a method commonly used for solid-liquid separation, for example, a method of filtering using a filter paper, a glass filter, etc.; a method of filtering after centrifugation; The method can be exemplified.
- the drying method is not particularly limited, and for example, a method of drying at about 50 to 200° C. for about 1 to 24 hours using a hot air dryer or the like can be exemplified.
- the above flaky carbon dispersion from which the solvent has been removed can be used if necessary, but if necessary, an organic compound having a hydrophilic group and a hydrophobic group with high affinity for carbon It can also be removed.
- a chemical admixture which will be described later, can be added again to obtain the additive for the hydraulic composition of the present invention.
- a water-soluble compound having a hydrophobic group that has a high affinity for carbon and a hydrophilic group can be removed by washing the flaky carbon composition with water, an organic solvent, or the like. The washing treatment can be removed by washing with dilute acid or dilute alkali in addition to water and organic solvent.
- the water-soluble compound having a hydrophobic group having a high affinity for carbon and a hydrophilic group is an organic ammonium salt
- heat treatment at 150 to 400°C, preferably 200 to 350°C will decompose the organic ammonium salt.
- a water-soluble compound having a hydrophobic group having a high affinity for carbon and a hydrophilic group can also be removed by heat treatment.
- the water-soluble compound having a hydrophobic group and a hydrophilic group, which have a high affinity for carbon, used in the present invention does not form a chemical bond with the flaky carbon, and its molecular weight is small, so its adsorptive power is weaker than that of conventional products. . Therefore, the water-soluble compound used in the present invention has the advantage of being easier to remove from the flaky carbon composition than the conventional product.
- the washing for removing the water-soluble compound having a hydrophobic group with a high affinity for carbon and a hydrophilic group can be performed by bringing the flaky carbon composition into contact with a washing liquid.
- a washing liquid water, various organic solvents, and the like can be used as long as they can dissolve a water-soluble compound having a hydrophobic group having a high affinity for carbon and a hydrophilic group.
- organic solvents include alcohols such as methanol, ethanol, and isopropyl alcohol (IPA) (especially alcohols having 1 to 6 carbon atoms), acetone, N-methylpyrrolidone, dimethylformamide, and the like. These may be used alone or in combination of two or more.
- an organic solvent that evaporates from the flaky carbon composition in a short time after washing is preferred.
- the organic solvent include those having a boiling point of about 50 to 250° C., particularly about 60 to 200° C. at normal pressure, such as methanol, ethanol, acetone, N-methylpyrrolidone, and dimethylformamide.
- the flaky carbon composition is contacted with a dilute acid or dilute alkali for washing to remove a water-soluble compound having a hydrophobic group with a high affinity for carbon and a hydrophilic group, and then You may carry out by washing with water.
- the dilute acid is preferably 0.1-5% hydrochloric acid
- the dilute alkali is preferably 0.1-3% aqueous ammonia.
- the cleaning liquid and the flaky carbon composition should be brought into contact.
- the immersion time is preferably within 30 minutes, more preferably within 20 minutes, in order to maintain the shape of the flaky carbon composition.
- the amount of the cleaning liquid used is not particularly limited as long as it is an effective amount for cleaning, and can be appropriately selected from a wide range. Good results are obtained when about 1000 to 5000 parts by weight are used.
- Hydraulic Composition contains the additive for hydraulic compositions of the present invention.
- the configuration other than the additive for hydraulic compositions of the present invention can be the same as that of conventional hydraulic compositions.
- the hydraulic composition of the present invention preferably contains the additive for hydraulic compositions of the present invention and a hydraulic component (hydraulic powder, etc.).
- the hydraulic component is not particularly limited, and for example, cement can be used, including Portland cement and mixed cement. Known or commercially available products can be used for these cements. These hydraulic components (hydraulic powder, etc.) can be used alone or in combination of two or more.
- the content of the hydraulic component is not particularly limited. It is preferably 200 to 2,000 kg/m 3 , more preferably 240 to 1,500 kg/m 3 per 1 m 3 of material.
- the content of the additive for hydraulic compositions of the present invention is determined from the viewpoint of filling property, fluidity, strength after curing, etc. It is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 1 part by mass, based on 100 parts by mass.
- the content of water is 5 parts per 100 parts by mass of the hydraulic component (hydraulic powder, etc.) from the viewpoint of filling properties, fluidity, strength after curing, etc. 80 parts by mass is preferable, and 10 to 70 parts by mass is more preferable.
- the additive for hydraulic composition of the present invention contains water, addition of water so that the total with water in the additive for hydraulic composition of the present invention is within the above range. It is preferable to adjust the amount.
- the hydraulic composition of the present invention further contains aggregates (silica sand, river sand, land sand, mountain sand) in addition to the above-described additives for hydraulic compositions of the present invention and hydraulic components (hydraulic powder, etc.). , sea sand, blast furnace slag fine aggregate, stone powder, silica fume, fly ash, natural zeolite, synthetic zeolite, pumice stone, fine aggregate such as kaolin; coarse aggregate such as blast furnace slag coarse aggregate) and water.
- aggregates sica sand, river sand, land sand, mountain sand
- hydraulic components hydraulic powder, etc.
- the additive for hydraulic composition of the present invention contains the above-mentioned organic compound having a hydrophilic group and a hydrophobic group having a high affinity with carbon, addition of a chemical admixture is not necessarily essential. However, from the viewpoint of filling property, fluidity, etc., a chemical admixture may be further included.
- the chemical admixture is not particularly limited, but those conventionally used in hydraulic compositions can be used. Those described in the organic compound having can be used. At this time, the same type of organic compound as the organic compound having a hydrophilic group and a hydrophobic group having a high affinity for carbon contained in the additive for hydraulic composition of the present invention can be used, or a different type can be used. You can also
- the amount used is appropriately selected from the viewpoint of filling properties, fluidity, strength after curing, etc., and may be used within a range that does not impair the effects of the present invention. It is preferably 0.0005 to 10 parts by mass, more preferably 0.001 to 6 parts by mass, per 100 parts by mass of the component (hydraulic powder, etc.).
- the hydraulic composition of the present invention can also contain swelling agents, foaming agents, foaming agents, waterproofing agents, and the like, as long as they do not impair the effects of the present invention.
- the method for producing the hydraulic composition of the present invention does not differ from the conventional one except that the additive for hydraulic compositions of the present invention is used, and it can be produced according to a conventional method. Also, the method for curing the hydraulic composition of the present invention is not different from the conventional method, and can be carried out according to the conventional method.
- the chemical admixture is supplied as an aqueous solution, and the concentration varies depending on the product. Since the ratio of graphene to dispersant is generally discussed in terms of mass ratio to solid matter, the concentration was measured. The results are as follows. Master Pozzolith No.
- Example 1 Dispersibility of flaky carbon dispersion
- Example 1-1 A mixture was obtained by mixing and stirring 500 g of natural graphite (manufactured by Ito Graphite Industry Co., Ltd.), 250 g of polyoxyethylene naphthalyl ether (molecular weight: 1200 to 1300) and 9250 g of water. This mixture was sheared once at 1700 rpm using a ceramic grinder with a radius of 300 mm. The shortest distance of the ceramic grinder was about 10 ⁇ m.
- Example 1-2 In Example 1-1, Master Pozzolith No. 2 was applied to the obtained flaky carbon dispersion. A flaky carbon dispersion having the composition shown in Table 1 was produced in the same manner, except that 12 g of Master Polyheed 15S (manufactured by BASF Japan Ltd.) was added instead of 70 (manufactured by BASF Japan Ltd.). .
- Example 1-3 Master Pozzolith No. 70 (manufactured by BASF Japan Ltd.) 12 g was diluted with 24 g of water and added to the flaky carbon dispersion obtained in Example 1-1. A flaky carbon dispersion was produced. As a result, the solid content concentration of the chemical admixture was adjusted to the same level as in Example 2.
- Examples 1-4 From the flaky carbon dispersion liquid obtained in Example 1-1, 0.2 g of flaky carbon, 9.8 g of water and Master Pozzolith No. 70 (manufactured by BASF Japan Ltd.) 1.2 g of a flaky carbon dispersion was taken out, and 30 g of water and Master Pozzolith No. 2 were added thereto. 3.6 g of 70 (manufactured by BASF Japan Ltd.) was added to prepare a flaky carbon dispersion having the composition shown in Table 1. This composition corresponds to 125 g of flaky carbon/m 3 of concrete in the tests described below.
- Examples 1-5 A dispersion consisting of 0.2 g of flaky carbon, 9.8 g of water, and 1.2 g of Master Polyheed 15S (manufactured by BASF Japan Ltd.) was taken out from the flaky carbon dispersion obtained in Example 1-2. , and 30 g of water and 3.6 g of Master Polyheed 15S (manufactured by BASF Japan Ltd.) were added thereto to produce a flaky carbon dispersion having the composition shown in Table 1. This composition corresponds to 125 g of flaky carbon/m 3 of concrete in the tests described below.
- Example 1-6 The dispersion obtained in Example 1-4 was diluted with water so that the concentration of flaky carbon in water was 0.005% by mass, and a flaky carbon dispersion having the composition shown in Table 1 was produced. In the previous report, there are cases where the dispersibility is improved when the concentration in water is less than 0.01% by mass, so this was carried out.
- Test Example 1 Dispersibility After standing the dispersibility of the dispersions obtained in Examples 1 to 6, the dispersibility was visually observed for the presence or absence of precipitates, etc. A: Dispersed even 10 minutes after the end of the dispersing treatment. B: It was evaluated that a suspended substance was generated immediately after the end of the dispersing treatment. Table 1 shows the results. As a result, all of Examples 1-1 to 1-6 were excellent in dispersibility, and among them, Examples 1-1, 1-3 and 1-4 were particularly excellent in dispersibility.
- Example 2 Mortar (Part 1)
- Example 2-1 1000 g of natural graphite (manufactured by Ito Graphite Industry Co., Ltd.), 100 g of polyoxyethylene naphthalyl ether (molecular weight: 1200 to 1300) and 18900 g of water were mixed and stirred to obtain a mixture. This mixture was sheared once at 1700 rpm using a ceramic grinder with a radius of 300 mm. The shortest distance of the ceramic grinder was about 10 ⁇ m.
- the flake-like carbon had a flake size of 1 to 20 ⁇ m.
- JIS R5201 Physical Test Method for Cement
- the inclusion of 0.73 g of flaky carbon means that the cement amount is 307 kg/concrete m 3 with a design standard strength of 24 N/mm 2 and a blend of 24-12-20 N. On the assumption that 500 g of flaky carbon is put in, the amount of cement in the mortar of this example is 450 g.
- Example 2-2 A mixture was obtained by mixing and stirring 500 g of natural graphite (manufactured by Ito Graphite Industry Co., Ltd.), 250 g of polyoxyethylene naphthalyl ether (molecular weight: 1200 to 1300) and 9250 g of water. This mixture was sheared once at 1700 rpm using a ceramic grinder with a radius of 300 mm. The shortest distance of the ceramic grinder was about 10 ⁇ m.
- the flake-like carbon had a flake size of 1 to 20 ⁇ m.
- JIS R5201 Physical Test Method for Cement
- the inclusion of 0.73 g of flaky carbon means that the cement amount is 307 kg/concrete m 3 with a design standard strength of 24 N/mm 2 and a blend of 24-12-20 N. On the assumption that 500 g of flaky carbon is put in, the amount of cement in the mortar of this example is 450 g.
- Example 2-3 A mixture was obtained by mixing and stirring 80 g of natural graphite (manufactured by Ito Graphite Industry Co., Ltd.), 480 g of Master Polyheed 15S (manufactured by BASF Japan Ltd.) and 3440 g of water. This mixture was sheared twice at 1700 rpm using a ceramic grinder with a radius of 300 mm. The shortest distance of the ceramic grinder was about 10 ⁇ m.
- the flake-like carbon had a flake size of 1 to 20 ⁇ m.
- JIS R5201 Physical Test Method for Cement
- the inclusion of 0.73 g of flaky carbon means that the cement amount is 307 kg/concrete m 3 with a design standard strength of 24 N/mm 2 and a blend of 24-12-20 N. It was calculated from the fact that the amount of cement was 450 g on the assumption that 500 g of flaky carbon was put in.
- Test Example 2 Fresh Properties of Mortar The mortars obtained in Examples 2-1 to 2-3 were removed from the mold one day after production, and the setting and hardening conditions were visually observed. As a result, no abnormality was observed in any of Examples 2-1 to 2-3.
- Test Example 3 Change over time of slump flow For Examples 2-1 to 2-3, two batches of mortar were produced, and after combining the samples for each of Examples 2-1 to 2-3, cement 5 stroke flow was measured in accordance with the physical test method (JIS R5201). Table 2 shows the results.
- Example 3 Concrete
- the base concrete is mixed with a design standard strength of about 24 N/mm 2 , and 305 kg/m 3 of ordinary Portland cement (manufactured by Sumitomo Osaka Cement Co., Ltd.) and 997 kg/m 3 of Nishijima crushed stone as coarse aggregate per 1 m 3 of concrete. 3. 569 kg/m 3 of Ibigawa river sand as fine aggregate, 246 kg/m 3 of crushed sand from Ibaraki as fine aggregate, and 3.0 kg/m of Master Polyheed 15S (manufactured by BASF Japan Ltd.) as chemical admixture.
- Example 3-1 750 g of natural graphite (manufactured by Ito Graphite Industry Co., Ltd.), 375 g of polyoxyethylene naphthalyl ether (molecular weight: 1200 to 1300) and 13875 g of water were mixed and stirred to obtain a mixture. This mixture was sheared once at 1700 rpm using a ceramic grinder with a radius of 300 mm. The shortest distance of the ceramic grinder was about 10 ⁇ m.
- the flake-like carbon had a flake size of 1 to 20 ⁇ m.
- Example 3-1 When producing kneading water, 0.2418 kg of the obtained flaky carbon dispersion was added, and the concrete of Example 3-1 was prepared in the same manner as in Comparative Example 3-1, except that the amount of water was adjusted. manufactured. Thus, the amount of flaky carbon added is 350 g/m 3 of concrete.
- Example 3-2 750 g of natural graphite (manufactured by Ito Graphite Industry Co., Ltd.), 375 g of polyoxyethylene naphthalyl ether (molecular weight: 1200 to 1300) and 13875 g of water were mixed and stirred to obtain a mixture. This mixture was sheared five times at 1700 rpm using a ceramic grinder with a radius of 300 mm. The shortest distance of the ceramic grinder was about 10 ⁇ m.
- the flake-like carbon had a flake size of 1 to 15 ⁇ m.
- Example 3-2 When producing kneading water, 0.2356 kg of the obtained flaky carbon dispersion was added, and the concrete of Example 3-2 was prepared in the same manner as in Comparative Example 3-1 except that the amount of water was adjusted. manufactured. Thus, the amount of flaky carbon added is 350 g/m 3 of concrete.
- Example 3-3 When producing kneading water, 0.4836 kg of the flaky carbon dispersion obtained in Example 3-1 was added, and the amount of water was adjusted in the same manner as in Comparative Example 3-1. 3-3 concretes were produced. Accordingly, the amount of flaky carbon added is 700 g/m 3 of concrete.
- Example 3-4 When producing kneading water, 0.4712 kg of the flaky carbon dispersion obtained in Example 3-2 was added, and the amount of water was adjusted in the same manner as in Comparative Example 3-1. 3-4 concretes were produced. Accordingly, the amount of flaky carbon added is 700 g/m 3 of concrete.
- Test Example 5 Fresh Properties of Concrete
- the slump of the concrete obtained in Examples 3-1 to 3-4 and Comparative Example 3-1 conforms to JIS A1101, after the completion of kneading, 30 minutes and 60 minutes after pouring water. Measurement was performed later, and the air content was measured after kneading was completed in accordance with JIS A1128. Also, the concrete temperature (room temperature 20° C.) was measured at the same time as the slump measurement. Table 4 shows the results.
- Test Example 6 Compressive Strength Test and Static Modulus of Elasticity Test A steel mold (100 mm in diameter ⁇ 200 mm) was used to prepare 12 test pieces per compound after kneading was completed. On the next day, all the specimens were removed from the molds and cured in water at 20°C until they reach a predetermined material age. At the time of demolding, the state of setting and hardening at 1 day of material age was checked in the same manner as in Test Example 2, and no abnormalities were found.
- Example 4 Mortar (Part 2)
- Comparative Example 4-1 4.40 g of Master Polyheed 15S (manufactured by BASF Japan Ltd.) and 220.6 g of water were mixed to obtain kneaded water.
- Example 4-1 500 g of natural graphite (manufactured by Ito Graphite Industry Co., Ltd.), 250 g of carboxymethyl cellulose sodium salt (manufactured by Sigma-Aldrich) and 9250 g of water were mixed and stirred to obtain a mixture. This mixture was sheared once at 1700 rpm using a ceramic grinder with a radius of 300 mm. The shortest distance of the ceramic grinder was about 10 ⁇ m.
- the flake-like carbon had a flake size of 1 to 20 ⁇ m.
- Example 4-2 A mixture was obtained by mixing and stirring 500 g of natural graphite (manufactured by Ito Graphite Industry Co., Ltd.), 1428 g of Master Polyheed 15S (manufactured by BASF Japan Ltd.) and 8070 g of water. This mixture was sheared once at 1700 rpm using a ceramic grinder with a radius of 300 mm. The shortest distance of the ceramic grinder was about 10 ⁇ m.
- the flake-like carbon had a flake size of 1 to 20 ⁇ m.
- Example 4-3 A mixture was obtained by mixing and stirring 500 g of natural graphite (manufactured by Ito Graphite Industry Co., Ltd.), 1428 g of Master Polyheed 15S (manufactured by BASF Japan Ltd.) and 8070 g of water. This mixture was sheared five times at 1700 rpm using a ceramic grinder with a radius of 300 mm. The shortest distance of the ceramic grinder was about 10 ⁇ m.
- the flake-like carbon had a flake size of 1 to 15 ⁇ m.
- Example 4-4 A mixture was obtained by mixing and stirring 500 g of natural graphite (manufactured by Ito Graphite Industry Co., Ltd.), 2857 g of Master Polyheed 15S (manufactured by BASF Japan Ltd.) and 8070 g of water. This mixture was sheared once at 1700 rpm using a ceramic grinder with a radius of 300 mm. The shortest distance of the ceramic grinder was about 10 ⁇ m.
- the flake-like carbon had a flake size of 1 to 20 ⁇ m.
- Example 4-5 A mixture was obtained by mixing and stirring 500 g of natural graphite (manufactured by Ito Graphite Industry Co., Ltd.), 2125 g of Master Polyheed 15S (manufactured by BASF Japan Ltd.) and 8070 g of water. This mixture was sheared five times at 1700 rpm using a ceramic grinder with a radius of 300 mm. The shortest distance of the ceramic grinder was about 10 ⁇ m.
- the flake-like carbon had a flake size of 1 to 15 ⁇ m.
- Test Example 7 Mortar flow test For Comparative Example 4-1 and Examples 4-1 to 4-5, two batches of mortar were produced for each of Comparative Example 4-1 and Examples 4-1 to 4-5. After combining the samples into one, the 15-stroke flow was measured in accordance with the cement physical test method (JIS R5201). Table 5 shows the results.
- Test Example 8 Mortar air content Two batches of mortar were produced, and the samples of each of Comparative Example 4-1 and Examples 4-1 to 4-5 were combined into one, and then the polymer cement mortar test method ( According to JIS A1171), the amount of air was measured after kneading. Table 5 shows the results.
- Test Example 9 Compressive strength test When the flow value of the mortar falls within the range of 240 ⁇ 40 mm and the air content falls within the range of 10.5 ⁇ 1.5%, a simple steel formwork with a diameter of 50 mm ⁇ 100 mm is used to divide the specimen into 1 Nine tubes were produced per formulation.
- the mold was filled with mortar in two layers, and each layer was poked eight times using a ramming rod. Next, the weight of the test piece after molding was measured one by one, and it was confirmed that the standard value was 370 g or more (excluding the weight of the formwork).
- the addition of the flaky carbon dispersion increased the compressive strength compared to the base concrete, and a maximum strength improvement of 28.4% was observed at the age of 28 days.
- Example 5 Mortar (Part 3)
- Comparative Example 5-1 12.375 g of Master Glenium SP8SB (manufactured by BASF Japan Ltd.) and 212.625 g of water were mixed to obtain kneaded water.
- Example 5-1 250 g of natural graphite (manufactured by Fuji Graphite Industries Co., Ltd.), 2989 g of master glenium SP8SB (manufactured by BASF Japan Ltd.) and 1761 g of water were mixed and stirred to obtain a mixture. This mixture was sheared 5 times at 1700 rpm using a ceramic grinder with a radius of 300 mm. The shortest distance of the ceramic grinder was about 10 ⁇ m.
- the flake-like carbon had a flake size of 1 to 15 ⁇ m.
- Comparative Example 5-2 7.875 g of Master Ease 3030 (manufactured by BASF Japan Ltd.) and 217.125 g of water were mixed to obtain kneaded water.
- Example 5-2 250 g of natural graphite (manufactured by Fuji Graphite Industries Co., Ltd.), 1902 g of Master Ease 3030 (manufactured by BASF Japan Ltd.), and 2848 g of water were mixed and stirred to obtain a mixture. This mixture was sheared five times at 1700 rpm using a ceramic grinder with a radius of 300 mm. The shortest distance of the ceramic grinder was about 10 ⁇ m.
- the flake-like carbon had a flake size of 1 to 20 ⁇ m.
- Example 5-3 250 g of natural graphite (manufactured by Fuji Graphite Industries Co., Ltd.), 1359 g of Mighty 3000S (manufactured by Kao Corporation) and 3391 g of water were mixed and stirred to obtain a mixture. This mixture was sheared five times at 1700 rpm using a ceramic grinder with a radius of 300 mm. The shortest distance of the ceramic grinder was about 10 ⁇ m.
- the flake-like carbon had a flake size of 1 to 20 ⁇ m.
- Comparative Example 5-4 7.875 g of Mighty 3000H (manufactured by Kao Corporation) and 217.125 g of water were mixed to obtain kneaded water.
- Example 5-4 250 g of natural graphite (manufactured by Fuji Graphite Industries Co., Ltd.), 1902 g of Mighty 3000H (manufactured by Kao Corporation), and 2848 g of water were mixed and stirred to obtain a mixed liquid. This mixture was sheared five times at 1700 rpm using a ceramic grinder with a radius of 300 mm. The shortest distance of the ceramic grinder was about 10 ⁇ m.
- the flake-like carbon had a flake size of 1 to 15 ⁇ m.
- Comparative Example 5-5 4.725 g of Master Polyheed 15S (manufactured by BASF Japan Ltd.) and 220.275 g of water were mixed to obtain kneaded water.
- Example 5-5 250 g of natural graphite (manufactured by Fuji Graphite Industries Co., Ltd.), 1141 g of Master Polyheed 15S (manufactured by BASF Japan Ltd.) and 3609 g of water were mixed and stirred to obtain a mixture. This mixture was sheared five times at 1700 rpm using a ceramic grinder with a radius of 300 mm. The shortest distance of the ceramic grinder was about 10 ⁇ m.
- the flake-like carbon had a flake size of 1 to 25 ⁇ m.
- Test Example 10 Mortar Flow Test For Comparative Examples 5-1 to 5-5 and Examples 5-1 to 5-5, two batches of mortar were produced, and Comparative Examples 5-1 to 5-5 and implementation After combining the samples for each of Examples 5-1 to 5-5, 15-stroke flow was measured according to the cement physical test method (JIS R5201). Table 6 shows the results.
- Test Example 11 Compressive strength test When the flow value of the mortar fell within the range of ⁇ 40 mm of the flow value of the comparative example, 3 specimens were produced per formulation using a simple steel formwork with a diameter of 50 mm ⁇ 100 mm. .
- Example 5-1 is Comparative Example 5-1
- Example 5-2 is Comparative Example 5-2
- Example 5-3 is Comparative Example 5-3
- Example 5-4 is Comparative Example 5-4 and Example 5-5 were compared with Comparative Example 5-5, respectively.
- the mold was filled with mortar in two layers, and each layer was poked eight times using a ramming rod. Next, the weight of the test piece after molding was measured one by one, and it was confirmed that the standard value was 370 g or more (excluding the weight of the formwork).
- the specimen was allowed to stand still in a test room at 20 ⁇ 2°C, and after confirming that there was no curing failure at 7 days of material age, it was removed from the mold. After demolding, the specimen was placed in a water tank at 20 ⁇ 1° C. and cured in water until it reached a predetermined material age.
- the addition of the flaky carbon dispersion increased the compressive strength compared to the base concrete, and a maximum strength improvement of 89.9% was observed at the age of 28 days.
- Comparative Example 6-1 7.875 g of Master Glenium SP8SV (manufactured by BASF Japan Ltd.) and 217.125 g of water were mixed to obtain kneaded water.
- Example 6-1 250 g of natural graphite (manufactured by Ito Graphite Industry Co., Ltd.), 1902 g of master glenium SP8SV (manufactured by BASF Japan Ltd.) and 2848 g of water were mixed and stirred to obtain a mixture. This mixture was sheared five times at 1700 rpm using a ceramic grinder with a radius of 300 mm. The shortest distance of the ceramic grinder was about 10 ⁇ m.
- the flake-like carbon had a flake size of 1 to 15 ⁇ m.
- Comparative Example 6-2 12.375 g of Master Glenium SP8SB (manufactured by BASF Japan Ltd.) and 212.625 g of water were mixed to obtain kneaded water.
- Example 6-2 250 g of natural graphite (manufactured by Ito Graphite Industry Co., Ltd.), 2989 g of master glenium SP8SB (manufactured by BASF Japan Ltd.) and 1761 g of water were mixed and stirred to obtain a mixture. This mixture was sheared five times at 1700 rpm using a ceramic grinder with a radius of 300 mm. The shortest distance of the ceramic grinder was about 10 ⁇ m.
- the flake-like carbon had a flake size of 1 to 15 ⁇ m.
- Comparative Example 6-3 5.625 g of Mighty 3000S (manufactured by Kao Corporation) and 219.375 g of water were mixed to obtain kneaded water.
- Example 6-3 250 g of natural graphite (manufactured by Ito Graphite Industry Co., Ltd.), 1359 g of Mighty 3000S (manufactured by Kao Corporation), and 3391 g of water were mixed and stirred to obtain a mixture. This mixture was sheared five times at 1700 rpm using a ceramic grinder with a radius of 300 mm. The shortest distance of the ceramic grinder was about 10 ⁇ m.
- the flake-like carbon had a flake size of 1 to 25 ⁇ m.
- Comparative Example 6-4 4.725 g of Master Polyheed 15S (manufactured by BASF Japan Ltd.) and 220.275 g of water were mixed to obtain kneaded water.
- Example 6-4 250 g of natural graphite (manufactured by Ito Graphite Industry Co., Ltd.), 1141 g of Master Polyheed 15S (manufactured by BASF Japan Ltd.) and 3609 g of water were mixed and stirred to obtain a mixture. This mixture was sheared five times at 1700 rpm using a ceramic grinder with a radius of 300 mm. The shortest distance of the ceramic grinder was about 10 ⁇ m.
- the flake-like carbon had a flake size of 1 to 20 ⁇ m.
- Test Example 12 Mortar flow test For Comparative Examples 6-1 to 6-5 and Examples 6-1 to 6-5, two batches of mortar were produced and Comparative Examples 6-1 to 6-5 and Examples were prepared. After combining the samples every 6-1 to 6-5, the 15-stroke flow was measured according to the cement physical test method (JIS R5201). Table 7 shows the results.
- Test Example 13 Compressive strength test When the flow value of the mortar fell within the range of ⁇ 40 mm of the flow value of the comparative example, 3 specimens were produced per formulation using a simple steel formwork with a diameter of 50 mm ⁇ 100 mm. .
- Example 6-1 is Comparative Example 6-1
- Example 6-2 is Comparative Example 6-2
- Example 6-3 is Comparative Example 6-3
- Example 6-4 is Comparative Example 6-4.
- Example 6-5 were compared with Comparative Example 6-5, respectively.
- the mold was filled with mortar in two layers, and each layer was poked eight times using a ramming rod. Next, the weight of the test piece after molding was measured one by one, and it was confirmed that the standard value was 370 g or more (excluding the weight of the formwork).
- the addition of the flaky carbon dispersion increased the compressive strength compared to the base concrete, and a maximum strength improvement of 74.1% was observed at the age of 28 days.
- Comparative Example 7-1 0.151 kg of Master Polyheed 15S (manufactured by BASF Japan Ltd.) and 7.74 kg of water were mixed to obtain kneaded water.
- Example 7-1 250 g of natural graphite (manufactured by Ito Graphite Industry Co., Ltd.), 1141 g of Master Polyheed 15S (manufactured by BASF Japan Ltd.) and 3609 g of water were mixed and stirred to obtain a mixture. This mixture was sheared twice at 1700 rpm using a ceramic grinder with a radius of 300 mm. The shortest distance of the ceramic grinder was about 10 ⁇ m.
- the flake-like carbon had a flake size of 1 to 20 ⁇ m.
- Test Example 14 Fresh Properties of Concrete For Comparative Example 7-1 and Example 7-1, concrete was produced, and the fresh properties were measured according to JIS A1101 for slump and JIS A1128 for air content. Table 8 shows the results.
- Test Example 15 Compressive Strength Test According to the description of JIS A4308 "Ready Mixed Concrete”, when the concrete slump falls within the range of 12.0 ⁇ 2.5 cm and the air content falls within the range of 4.5 ⁇ 1.5%. , JIS A1132 "How to make concrete strength test specimens", three specimens each having a diameter of 100 mm x 200 mm were prepared for each composition.
- the addition of the flaky carbon dispersion increased the compressive strength compared to the base concrete, and a maximum strength improvement of 23.1% was observed at the age of 28 days.
- Test Example 16 Bending Strength Test According to the description of JIS A4308 "Ready Mixed Concrete", when the concrete slump fell within the range of 120 ⁇ 2.5 cm and the air content was within the range of 4.5 ⁇ 1.5%, JIS Three specimens of 100 mm ⁇ 100 mm ⁇ 400 mm were prepared for each formulation in accordance with A1132 “Manufacturing of Specimens for Concrete Strength Test”.
- the formwork was filled with concrete in two layers, each layer of 1000 mm2 was poked with a ram, and a metal spatula was used to poke along the side and end faces of the formwork. Spating was carried out with a hammer, and molding was carried out by tapping the side of the mold with a wooden mallet.
- the addition of the flaky carbon dispersion increased the bending strength compared to the base concrete, and a maximum strength improvement of 6.63% was observed at the age of 28 days.
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Abstract
Description
で表される少なくとも1種を含む、項1又は2に記載の水硬性組成物用添加剤。
層状構造を有する炭素質材料、炭素と親和性の高い疎水基と、親水基とを有する水溶性化合物、及び溶媒を含有する炭素質材料分散体に対して、30MPa以上の加圧処理を行い、該加圧処理により、
(i)2個以上の前記炭素質材料分散体同士を衝突させること、
(ii)前記炭素質材料分散体と金属又はセラミックス材料とを衝突させること、及び
(iii)前記炭素質材料分散体を断面積1cm2以下の空間を通過させること
よりなる群から選ばれる少なくとも1種の処理を行い、前記溶媒が水を含有し、且つ、該水の含有量が、前記溶媒中の70質量%以上である、製造方法。
回転する回転盤と、前記回転盤と略平行に設置された盤との間に、
層状構造を有する炭素質材料と、炭素と親和性の高い疎水基と、親水基とを有する水溶性化合物と、溶媒とを含む組成物を設置し、
前記回転盤と前記盤との最短距離が200μm以下となるように調整しながら、前記組成物中の炭素質材料に対してせん断を加える工程
を備え、前記溶媒が水を含有し、且つ、該水の含有量が、前記溶媒中の70質量%以上である、製造方法。
水硬性粉体材料と、前記水硬性組成物用添加剤とを混合する工程
を備える、製造方法。
本発明の水硬性組成物用添加剤は、薄片状カーボンと、親水基及び炭素と親和性の高い疎水基を有する有機化合物とを含有する。
薄片状カーボンは、強度向上剤として機能する。
本発明においては、親水基及び炭素と親和性の高い疎水基を有する有機化合物を使用することにより、グラフェン構造を維持した薄片状カーボンが凝集することなく、本発明の水硬性組成物用添加剤中の薄片状カーボンを均一分散した状態で維持することができ、この結果、水硬性組成物に対する強度向上特性を強化することができる。なお、親水基及び炭素と親和性の高い疎水基を有する有機化合物は、薄片状カーボンを均一分散させるための分散剤としても機能し得る。
で表される親水基が好ましい。親水基及び炭素と親和性の高い疎水基を有する有機化合物は、このような親水基を、1種又は2種以上含むことができる。また、複数の親水基を使用する場合には、同じ親水基を複数用いてもよいし、同じ一般式で表される親水基を複数種用いてもよいし、異なる一般式で表される親水基を複数種用いてもよい。
本発明の水硬性組成物用添加剤において、薄片状カーボン、並びに親水基及び炭素と親和性の高い疎水基を有する有機化合物以外にも、他の成分を含ませてもよい。このような他の成分としては、例えば、カーボンファイバー(特に繊維径500nm以下のカーボンナノファイバー)、活性炭、カーボンブラック(アセチレンブラック、オイルファーネスブラック等;特に導電性が高く、比表面積が大きいケッチェンブラック)、ガラス状カーボン、カーボンマイクロコイル、フラーレン、バイオマス系炭素材料(バガス、ソルガム、木くず、おがくず、竹、木皮、稲ワラ、籾殻、コーヒーかす、茶殻、おからかす、米糠、パルプくず等を原料としたもの;リグニンから製造したカーボンファイバー等)、セルロースナノファイバー、窒化ホウ素、モリブデン化合物(二硫化モリブデン、有機モリブデン等)、二硫化タングステン、メラミンシアヌレート、フタロシアニン、酸化鉛、フッ化カルシウム、層状鉱物(マイカ、タルク等)等を、本発明の効果を損なわない範囲で使用することもできる。
本発明の水硬性組成物用添加剤は、例えば、水を含有し、且つ、水の含有量が、溶媒中の70質量%以上含有する溶媒を用いて、
層状構造を有する炭素質材料、炭素と親和性の高い疎水基と、親水基とを有する水溶性化合物、及び溶媒を含有する炭素質材料分散体に対して、30MPa以上の加圧処理を行い、該加圧処理により、
(i)2個以上の前記炭素質材料分散体同士を衝突させること、
(ii)前記炭素質材料分散体と金属又はセラミックス材料とを衝突させること、及び
(iii)前記炭素質材料分散体を断面積1cm2以下の空間を通過させること
よりなる群から選ばれる少なくとも1種の処理を行ったり、或いは、
回転する回転盤と、前記回転盤と略平行に設置された盤との間に、
層状構造を有する炭素質材料と、炭素と親和性の高い疎水基と、親水基とを有する水溶性化合物と、溶媒とを含む組成物を設置し、
前記回転盤と前記盤との最短距離が50μm以下となるように調整しながら、前記組成物中の炭素質材料に対してせん断を加えたりすること
により、本発明の水硬性組成物用添加剤を製造することができる。
薄片状カーボンと、前記親水基及び炭素と親和性の高い疎水基を有する有機化合物と、溶媒とを含有する分散体(薄片状カーボン分散体)において、薄片状カーボンと、親水基及び炭素と親和性の高い疎水基を有する有機化合物については、上記した説明を採用することができる。また、薄片状カーボン分散体には、必要に応じて、上記した他の成分を含ませることもできる。
本発明において、上記薄片状カーボン分散体の製造方法は、特に制限されず、溶媒に対して薄片状カーボン及び親水基及び炭素と親和性の高い疎水基を有する有機化合物を投入することもできる。具体的には、親水基及び炭素と親和性の高い疎水基を有する有機化合物の分散体に薄片状カーボンを投入することもできるし、薄片状カーボンの分散体に親水基及び炭素と親和性の高い疎水基を有する有機化合物を投入することもできる。また、溶媒中に、薄片状カーボン及び親水基及び炭素と親和性の高い疎水基を有する有機化合物を同時に投入することもできる。
層状構造を有する炭素質材料としては、特に制限はないが、天然黒鉛、人造黒鉛、膨張黒鉛、土状黒鉛、酸化黒鉛等が挙げられる。酸化黒鉛とは、例えば、硫酸、硝酸、過マンガン酸カリウム、過酸化水素等の1種以上の酸化剤により酸化された黒鉛が使用され得る。例えば、ハマーズ法により酸化黒鉛を得る場合には、黒鉛を濃硫酸中に浸し、過マンガン酸カリウムを加えて黒鉛を酸化させた後、反応物を希硫酸及び/又は過酸化水素でクエンチし、その後、蒸留水で洗浄すること等により、炭素原子に酸素原子が結合し、層間に酸素原子が導入されて酸化黒鉛を得ることができる。
親水基及び炭素と親和性の高い疎水基を有する有機化合物としては、上記したものを採用できる。
上記した薄片状カーボン分散体の製造方法においては、上記のとおり、層状構造を有する炭素質材料と、親水基及び炭素と親和性の高い疎水基を有する有機化合物とを含む組成物を用いて、特定の処理を行うことが好ましいが、層状構造を有する炭素質材料の薄片化効率、得られる水硬性組成物の強度向上等の観点から、層状構造を有する炭素質材料と、親水基及び炭素と親和性の高い疎水基を有する有機化合物とを含む炭素質材料分散体に対して、特定の処理を行うことが好ましい。
本発明において、層状構造を有する炭素質材料と、親水基及び炭素と親和性の高い疎水基を有する有機化合物とを含む組成物(例えば、炭素質材料分散体等)には、他の成分を含ませてもよい。これにより、最終的に得られる薄片状カーボン分散体や水硬性組成物用添加剤中にも、これら他の成分を含ませることができる。このような他の成分としては、上記したものを採用でき、本発明の効果を損なわない範囲で使用してもよい。
本発明では、磨砕法を採用する場合、上記のとおり、回転する回転盤と、前記回転盤と略平行に設置された盤との間に、層状構造を有する炭素質材料と、親水基及び炭素と親和性の高い疎水基を有する有機化合物とを含む組成物を設置し、前記回転盤と前記盤との最短距離が200μm以下となるように調整しながら、前記組成物中の炭素質材料に対してせん断を加える処理を行うことが好ましい。なお、炭素質材料分散体を使用する場合には、回転する回転盤と、前記回転盤と略平行に設置された盤との間に、炭素質材料分散体を設置し、前記回転盤と前記盤との最短距離が200μm以下となるように調整しながら、前記炭素質材料分散体中の炭素質材料に対してせん断を加える処理を行うことが好ましい。
本発明では、高圧分散法を採用する場合、上記のとおり、層状構造を有する炭素質材料と、親水基及び炭素と親和性の高い疎水基を有する有機化合物とを含む組成物に対して、30MPa以上の加圧処理を行うことが好ましい。
(i)2個以上の前記炭素質材料分散体同士を衝突させること、
(ii)前記炭素質材料分散体と金属又はセラミックス材料(炭化ケイ素、アルミナ等高硬度の材料)とを衝突させること、
(iii)前記炭素質材料分散体を断面積1cm2以下の空間を通過させること
等の処理を行い得る。
本発明の水硬性組成物用添加剤は、上記の薄片状カーボン分散体から必要に応じて溶媒を除去することで得ることができる。
本発明の水硬性組成物は、上記した本発明の水硬性組成物用添加剤を含有する。本発明の水硬性組成物において、本発明の水硬性組成物用添加剤以外の構成は、従来の水硬性組成物と同様とすることができる。
マスターポゾリスNo.70(BASFジャパン(株)製;リグニンスルホン酸とポリオールとの複合体):40.21質量%
マスターポリヒード15S(BASFジャパン(株)製;リグニンスルホン酸とポリカルボン酸エーテルとの複合体):16.37質量%
マスターグレニウムSP8SB(BASFジャパン(株)製;ポリカルボン酸エーテル系化 合物と分子内架橋ポリマーの 複合体):17.92質量%
マスターグレニウムSP8SV(BASFジャパン(株)製;ポリカルボン酸エーテル系化合物):17.81質量%
マスターイース3030(BASFジャパン(株)製;PAE化合物):23.21質量%
マイテイ3000S(花王(株)製;ポリエーテル系ポリカルボン酸化合物):20.96質量%
マイテイ3000H(花王(株)製;ポリエーテル系ポリカルボン酸化合物):24.47質量%。
実施例1-1
500gの天然黒鉛(伊藤黒鉛工業(株)製)とポリオキシエチレンナフタリルエーテル(分子量1200~1300)250gと水9250gを混合して攪拌することで、混合液を得た。この混合液を半径300mmのセラミックグラインダーを用いて、1700rpmでせん断処理を1回施した。なお、セラミックグラインダーの最短距離は、約10μmであった。
実施例1-1において、得られた薄片状カーボン分散液に対して、マスターポゾリスNo.70(BASFジャパン(株)製)の代わりに、マスターポリヒード15S(BASFジャパン(株)製)を12g添加すること以外は同様に、表1に示す組成の薄片状カーボン分散液を製造した。
マスターポゾリスNo.70(BASFジャパン(株)製)12gを、水24gで希釈し、実施例1-1において、得られた薄片状カーボン分散液に対して添加したこと以外は同様に、表1に示す組成の薄片状カーボン分散液を製造した。これにより、化学混和剤の固形分濃度を、実施例2と同程度になるように調整した。
実施例1-1で得られた薄片状カーボン分散液から、薄片状カーボン0.2g、水9.8g及びマスターポゾリスNo.70(BASFジャパン(株)製)1.2gからなる薄片状カーボン分散液を取り出し、そこに水30g及びマスターポゾリスNo.70(BASFジャパン(株)製)3.6gを添加し、表1に示す組成の薄片状カーボン分散液を製造した。この組成は、後述の試験において、薄片状カーボン125g/コンクリートm3に相当する。
実施例1-2で得られた薄片状カーボン分散液から、薄片状カーボン0.2g、水9.8g及びマスターポリヒード15S(BASFジャパン(株)製)1.2gからなる分散液を取り出し、そこに水30g及びマスターポリヒード15S(BASFジャパン(株)製)3.6gを添加し、表1に示す組成の薄片状カーボン分散液を製造した。この組成は、後述の試験において、薄片状カーボン125g/コンクリートm3に相当する。
実施例1-4で得られた分散液を、薄片状カーボンの水に対する濃度が0.005質量%となるように水で希釈し、表1に示す組成の薄片状カーボン分散液を製造した。既報において、水に対する濃度が0.01質量%を下回ると分散性が向上する事例が存在するため実施した。
実施例1~6で得られた分散液の分散性を静置した後に、分散性を目視で沈殿状態の有無等を観察し、
A:分散処理の終了後10分経過後も分散している
B:分散処理の終了直後から、懸濁状の物質が発生する
として評価した。結果を表1に示す。この結果、実施例1-1~1-6のいずれも分散性に優れており、なかでも、実施例1-1、1-3及び1-4が、特に分散性に優れていた。
実施例2-1
1000gの天然黒鉛(伊藤黒鉛工業(株)製)とポリオキシエチレンナフタリルエーテル(分子量1200~1300)100gと水18900gを混合して攪拌することで、混合液を得た。この混合液を半径300mmのセラミックグラインダーを用いて、1700rpmでせん断処理を1回施した。なお、セラミックグラインダーの最短距離は、約10μmであった。
500gの天然黒鉛(伊藤黒鉛工業(株)製)とポリオキシエチレンナフタリルエーテル(分子量1200~1300)250gと水9250gを混合して攪拌することで、混合液を得た。この混合液を半径300mmのセラミックグラインダーを用いて、1700rpmでせん断処理を1回施した。なお、セラミックグラインダーの最短距離は、約10μmであった。
80gの天然黒鉛(伊藤黒鉛工業(株)製)とマスターポリヒード15S(BASFジャパン(株)製)480gと水3440gを混合して攪拌することで、混合液を得た。この混合液を半径300mmのセラミックグラインダーを用いて、1700rpmでせん断処理を2回施した。なお、セラミックグラインダーの最短距離は、約10μmであった。
実施例2-1~2-3で得られたモルタルを製造1日後にモールドから脱型し、凝結・硬化状況を目視で確認した。この結果、実施例2-1~2-3のいずれにおいても、異常は見られなかった。
実施例2-1~2-3について、各2バッチ分のモルタルを製造し実施例2-1~2-3毎に試料を1つに合わせた後、セメントの物理試験方法(JIS R5201)に準拠して、5打フローを計測した。結果を表2に示す。
比較例3-1
ベースコンクリートの配合として、設計基準強度24N/mm2程度とし、コンクリート1m3あたり、普通ポルトランドセメント(住友大阪セメント(株)製)を305kg/m3、粗骨材として西島産砕石を997kg/m3、細骨材として揖斐川産川砂を569kg/m3、細骨材として茨木産砕砂を246kg/m3、化学混和剤としてマスターポリヒード15S(BASFジャパン(株)製)を3.0kg/m3、水を168kg/m3とし、水/セメント比(W/C)を55質量%、細骨材率(s/a)を45.0%、目標スランプを12cm、目標空気量を4.5質量%の配合に対し、コンクリートの練り混ぜ量が35Lとなる数量に対して、以下のように調製した。
750gの天然黒鉛(伊藤黒鉛工業(株)製)とポリオキシエチレンナフタリルエーテル(分子量1200~1300)375gと水13875gを混合して攪拌することで、混合液を得た。この混合液を半径300mmのセラミックグラインダーを用いて、1700rpmでせん断処理を1回施した。なお、セラミックグラインダーの最短距離は、約10μmであった。
750gの天然黒鉛(伊藤黒鉛工業(株)製)とポリオキシエチレンナフタリルエーテル(分子量1200~1300)375gと水13875gを混合して攪拌することで、混合液を得た。この混合液を半径300mmのセラミックグラインダーを用いて、1700rpmでせん断処理を5回施した。なお、セラミックグラインダーの最短距離は、約10μmであった。
練り混ぜ水を製造する際に、実施例3-1で得られた薄片状カーボン分散液を0.4836kg添加し、水の量を調整すること以外は比較例3-1と同様に、実施例3-3のコンクリートを製造した。これにより、薄片状カーボンの添加量は、700g/コンクリートm3である。
練り混ぜ水を製造する際に、実施例3-2で得られた薄片状カーボン分散液を0.4712kg添加し、水の量を調整すること以外は比較例3-1と同様に、実施例3-4のコンクリートを製造した。これにより、薄片状カーボンの添加量は、700g/コンクリートm3である。
実施例3-1~3-4及び比較例3-1で得られたコンクリートのスランプは、JIS A1101に準拠し、練り混ぜ終了後、注水30分後及び60分後に計測を行い、空気量はJIS A1128に準拠し、練り混ぜ終了後に計測を行った。また、スランプ計測時に合わせてコンクリート温度(室温20℃)を計測した。結果を表4に示す。
鋼製型枠(直径100mm×200mm)を用いて、練り混ぜ終了後に1配合当たり12本作製した。翌日、全ての供試体を脱型し、所定材齢まで20℃で水中養生を行った。脱型時に材齢1日の凝結・硬化状況を試験例2と同様に確認したところ、いずれも異常がなかった。
比較例4-1
マスターポリヒード15S(BASFジャパン(株)製)4.40gと、水220.6gとを混合して練り混ぜ水を得た。
500gの天然黒鉛(伊藤黒鉛工業(株)製)とカルボキシメチルセルロースナトリウム塩250g(シグマアルドリッチ製)と水9250gを混合して攪拌することで、混合液を得た。この混合液を半径300mmのセラミックグラインダーを用いて、1700rpmでせん断処理を1回施した。なお、セラミックグラインダーの最短距離は、約10μmであった。
500gの天然黒鉛(伊藤黒鉛工業(株)製)とマスターポリヒード15S(BASFジャパン(株)製)1428gと水8070gを混合して攪拌することで、混合液を得た。この混合液を半径300mmのセラミックグラインダーを用いて、1700rpmでせん断処理を1回施した。なお、セラミックグラインダーの最短距離は、約10μmであった。
500gの天然黒鉛(伊藤黒鉛工業(株)製)とマスターポリヒード15S(BASFジャパン(株)製)1428gと水8070gを混合して攪拌することで、混合液を得た。この混合液を半径300mmのセラミックグラインダーを用いて、1700rpmでせん断処理を5回施した。なお、セラミックグラインダーの最短距離は、約10μmであった。
500gの天然黒鉛(伊藤黒鉛工業(株)製)とマスターポリヒード15S(BASFジャパン(株)製)2857gと水8070gを混合して攪拌することで、混合液を得た。この混合液を半径300mmのセラミックグラインダーを用いて、1700rpmでせん断処理を1回施した。なお、セラミックグラインダーの最短距離は、約10μmであった。
500gの天然黒鉛(伊藤黒鉛工業(株)製)とマスターポリヒード15S(BASFジャパン(株)製)2125gと水8070gを混合して攪拌することで、混合液を得た。この混合液を半径300mmのセラミックグラインダーを用いて、1700rpmでせん断処理を5回施した。なお、セラミックグラインダーの最短距離は、約10μmであった。
比較例4-1、実施例4-1~4-5について、各2バッチ分のモルタルを製造し比較例4-1、実施例4-1~4-5毎に試料を1つに合わせた後、セメントの物理試験方法(JIS R5201)に準拠して、15打フローを計測した。結果を表5に示す。
各2バッチ分のモルタルを製造し比較例4-1、実施例4-1~4-5毎に試料を1つに合わせた後、ポリマーセメントモルタルの試験方法(JIS A1171)に準拠し、練り混ぜ終了後に空気量を計測した。結果を表5に示す。
モルタルのフロー値が240±40mm且つ空気量が10.5±1.5%の範囲内に収まったとき簡易鋼製型枠直径50mm×100mmを用いて供試体を1配合当たり9本作製した。
比較例5-1
マスターグレニウムSP8SB(BASFジャパン(株)製)12.375gと、水212.625gとを混合して練り混ぜ水を得た。
250gの天然黒鉛(富士黒鉛工業(株)製)とマスターグレニウムSP8SB(BASFジャパン(株)製)2989gと水1761gを混合して攪拌することで、混合液を得た。この混合液を半径300mmのセラミックグラインダーを用いて、1700rpmでせん断処理を5回施した。なお、セラミックグラインダーの最短距離は、約10μmであった。
マスターイース3030(BASFジャパン(株)製)7.875gと、水217.125gとを混合して練り混ぜ水を得た。
250gの天然黒鉛(富士黒鉛工業(株)製)とマスターイース3030(BASFジャパン(株)製)1902gと水2848gを混合して攪拌することで、混合液を得た。この混合液を半径300mmのセラミックグラインダーを用いて、1700rpmでせん断処理を5回施した。なお、セラミックグラインダーの最短距離は、約10μmであった。
マイテイ3000S(花王(株)製)5.625gと、水219.375gとを混合して練り混ぜ水を得た。
250gの天然黒鉛(富士黒鉛工業(株)製)とマイテイ3000S(花王(株)製)1359gと水3391gを混合して攪拌することで、混合液を得た。この混合液を半径300mmのセラミックグラインダーを用いて、1700rpmでせん断処理を5回施した。なお、セラミックグラインダーの最短距離は、約10μmであった。
マイテイ3000H(花王(株)製)7.875gと、水217.125gとを混合して練り混ぜ水を得た。
250gの天然黒鉛(富士黒鉛工業(株)製)とマイテイ3000H(花王(株)製)1902gと水2848gを混合して攪拌することで、混合液を得た。この混合液を半径300mmのセラミックグラインダーを用いて、1700rpmでせん断処理を5回施した。なお、セラミックグラインダーの最短距離は、約10μmであった。
マスターポリヒード15S(BASFジャパン(株)製)4.725gと、水220.275gとを混合して練り混ぜ水を得た。
250gの天然黒鉛(富士黒鉛工業(株)製)とマスターポリヒード15S(BASFジャパン(株)製)1141gと水3609gを混合して攪拌することで、混合液を得た。この混合液を半径300mmのセラミックグラインダーを用いて、1700rpmでせん断処理を5回施した。なお、セラミックグラインダーの最短距離は、約10μmであった。
比較例5-1~5-5及び実施例5-1~5-5について、各2バッチ分のモルタルを製造し、比較例5-1~5-5及び実施例5-1~5-5毎に試料を1つに合わせた後、セメントの物理試験方法(JIS R5201)に準拠して、15打フローを計測した。結果を表6に示す。
モルタルのフロー値が比較例のフロー値の±40mmの範囲内に収まったとき、簡易鋼製型枠直径50mm×100mmを用いて供試体を1配合当たり3本作製した。実施例5-1は比較例5-1と、実施例5-2は比較例5-2と、実施例5-3は比較例5-3と、実施例5-4は比較例5-4と、実施例5-5は比較例5-5と、それぞれ対比した。
マスターグレニウムSP8SV(BASFジャパン(株)製)7.875gと、水217.125gとを混合して練り混ぜ水を得た。
250gの天然黒鉛(伊藤黒鉛工業(株)製)とマスターグレニウムSP8SV(BASFジャパン(株)製)1902gと水2848gを混合して攪拌することで、混合液を得た。この混合液を半径300mmのセラミックグラインダーを用いて、1700rpmでせん断処理を5回施した。なお、セラミックグラインダーの最短距離は、約10μmであった。
マスターグレニウムSP8SB(BASFジャパン(株)製)12.375gと、水212.625gとを混合して練り混ぜ水を得た。
250gの天然黒鉛(伊藤黒鉛工業(株)製)とマスターグレニウムSP8SB(BASFジャパン(株)製)2989gと水1761gを混合して攪拌することで、混合液を得た。この混合液を半径300mmのセラミックグラインダーを用いて、1700rpmでせん断処理を5回施した。なお、セラミックグラインダーの最短距離は、約10μmであった。
マイテイ3000S(花王(株)製)5.625gと、水219.375gとを混合して練り混ぜ水を得た。
250gの天然黒鉛(伊藤黒鉛工業(株)製)とマイテイ3000S(花王(株)製)1359gと水3391gを混合して攪拌することで、混合液を得た。この混合液を半径300mmのセラミックグラインダーを用いて、1700rpmでせん断処理を5回施した。なお、セラミックグラインダーの最短距離は、約10μmであった。
マスターポリヒード15S(BASFジャパン(株)製)4.725gと、水220.275gとを混合して練り混ぜ水を得た。
250gの天然黒鉛(伊藤黒鉛工業(株)製)とマスターポリヒード15S(BASFジャパン(株)製)1141gと水3609gを混合して攪拌することで、混合液を得た。この混合液を半径300mmのセラミックグラインダーを用いて、1700rpmでせん断処理を5回施した。なお、セラミックグラインダーの最短距離は、約10μmであった。
比較例6-1~6-5及び実施例6-1~6-5について、各2バッチ分のモルタルを製造し比較例6-1~6-5及び実施例6-1~6-5毎に試料を1つに合わせた後、セメントの物理試験方法(JIS R5201)に準拠して、15打フローを計測した。結果を表7に示す。
モルタルのフロー値が比較例のフロー値の±40mmの範囲内に収まったとき、簡易鋼製型枠直径50mm×100mmを用いて供試体を1配合当たり3本作製した。実施例6-1は比較例6-1と、実施例6-2は比較例6-2と、実施例6-3は比較例6-3と、実施例6-4は比較例6-4と、実施例6-5は比較例6-5と、それぞれ対比した。
マスターポリヒード15S(BASFジャパン(株)製)0.151kgと、水7.74kgとを混合して練り混ぜ水を得た。
250gの天然黒鉛(伊藤黒鉛工業(株)製)とマスターポリヒード15S(BASFジャパン(株)製)1141gと水3609gを混合して攪拌することで、混合液を得た。この混合液を半径300mmのセラミックグラインダーを用いて、1700rpmでせん断処理を2回施した。なお、セラミックグラインダーの最短距離は、約10μmであった。
比較例7-1及び実施例7-1について、コンクリートを製造し、スランプはJIS A1101、空気量はJIS A1128に準拠して、フレッシュ性状を計測した。結果を表8に示す。
JIS A4308「レディーミクストコンクリート」の記載に準拠し、コンクリートのスランプが12.0±2.5cm且つ空気量が4.5±1.5%の範囲内に収まったとき、JIS A1132「コンクリートの強度試験用供試体の作り方」に準拠し、直径100mm×200mmの供試体を1配合当たり3本作製した。
JIS A4308「レディーミクストコンクリート」の記載に準拠し、コンクリートのスランプが120±2.5cm且つ空気量が4.5±1.5%の範囲内に収まったとき、JIS A1132「コンクリートの強度試験用供試体の作り方」に準拠し、100mm×100mm×400mmの供試体を1配合当たり3本作製した。
Claims (19)
- 薄片状カーボンと、親水基及び炭素と親和性の高い疎水基を有する有機化合物とを含有する、水硬性組成物用添加剤。
- さらに、水を含有する、請求項1に記載の水硬性組成物用添加剤。
- 前記親水基が、アルコール性水酸基、-SO3Na、-COONa、-COOCH3、及びポリオキシエチレン基よりなる群から選ばれる少なくとも1種を含む、請求項1~3のいずれか1項に記載の水硬性組成物用添加剤。
- 前記疎水基が、アルキル基、アルケニル基、シクロアルキル基、アリール基、及び炭素数3以上のポリオキシアルキレン基よりなる群から選ばれる少なくとも1種を含む、請求項1~4のいずれか1項に記載の水硬性組成物用添加剤。
- 前記疎水基が、少なくとも1つの酸素原子が結合しているアリール基、及び/又は2個以上の芳香環を有するアリール基を含む、請求項1~5のいずれか1項に記載の水硬性組成物用添加剤。
- 親水基及び炭素と親和性の高い疎水基を有する有機化合物が、AE剤、減水剤、硬化促進剤、AE減水剤、高性能減水剤、高性能AE減水剤及び流動化剤よりなる群から選ばれる少なくとも1種のコンクリート用化学混和剤である、請求項1~6のいずれか1項に記載の水硬性組成物用添加剤。
- 前記薄片状カーボンの炭素含有率が95.0質量%以上である、請求項1~7のいずれか1項に記載の水硬性組成物用添加剤。
- 前記薄片状カーボンの大きさが0.1~30.0μmである、請求項1~8のいずれか1項に記載の水硬性組成物用添加剤。
- 前記薄片状カーボンの厚みが0.335~100nmである、請求項1~9のいずれか1項に記載の水硬性組成物用添加剤。
- 前記薄片状カーボン100質量部に対して、前記親水基及び炭素と親和性の高い疎水基を有する有機化合物を1~1000質量部含有する、請求項1~10のいずれか1項に記載の水硬性組成物用添加剤。
- 請求項1~11のいずれか1項に記載の水硬性組成物用添加剤の製造方法であって、
層状構造を有する炭素質材料、炭素と親和性の高い疎水基と、親水基とを有する水溶性化合物、及び溶媒を含有する炭素質材料分散体に対して、30MPa以上の加圧処理を行い、該加圧処理により、
(i)2個以上の前記炭素質材料分散体同士を衝突させること、
(ii)前記炭素質材料分散体と金属又はセラミックス材料とを衝突させること、及び
(iii)前記炭素質材料分散体を断面積1cm2以下の空間を通過させること
よりなる群から選ばれる少なくとも1種の処理を行い、前記溶媒が水を含有し、且つ、該水の含有量が、前記溶媒中の70質量%以上である、製造方法。 - 請求項1~11のいずれか1項に記載の水硬性組成物用添加剤の製造方法であって、
回転する回転盤と、前記回転盤と略平行に設置された盤との間に、
層状構造を有する炭素質材料と、炭素と親和性の高い疎水基と、親水基とを有する水溶性化合物と、溶媒とを含む組成物を設置し、
前記回転盤と前記盤との最短距離が200μm以下となるように調整しながら、前記組成物中の炭素質材料に対してせん断を加える工程
を備え、前記溶媒が水を含有し、且つ、該水の含有量が、前記溶媒中の70質量%以上である、製造方法。 - 前記加圧処理又はせん断処理の後、溶媒の一部又は全部を除去する、請求項12又は13に記載の製造方法。
- 請求項1~11のいずれか1項に記載の水硬性組成物用添加剤と、水硬性成分とを含有する、水硬性組成物。
- 前記水硬性組成物用添加剤の含有量が、前記水硬性成分100質量部に対して、0.01~1質量部である、請求項15に記載の水硬性組成物。
- セメント水和生成物である、請求項15又は16に記載の水硬性組成物。
- 請求項15~17のいずれか1項に記載の水硬性組成物の製造方法であって、
水硬性粉体材料と、前記水硬性組成物用添加剤とを混合する工程
を備える、製造方法。 - 前記混合工程において、さらに、コンクリート用混和剤を混合する、請求項18に記載の製造方法。
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