EP3086892A1 - Système bicomposant notamment destiné à la formation d'un adhésif - Google Patents

Système bicomposant notamment destiné à la formation d'un adhésif

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Publication number
EP3086892A1
EP3086892A1 EP14821176.6A EP14821176A EP3086892A1 EP 3086892 A1 EP3086892 A1 EP 3086892A1 EP 14821176 A EP14821176 A EP 14821176A EP 3086892 A1 EP3086892 A1 EP 3086892A1
Authority
EP
European Patent Office
Prior art keywords
component
adhesive
component system
total mass
alkali metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14821176.6A
Other languages
German (de)
English (en)
Inventor
Christian Fourberg
Ditmar Baier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huettenes Albertus Chemische Werke GmbH
Original Assignee
Huettenes Albertus Chemische Werke GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huettenes Albertus Chemische Werke GmbH filed Critical Huettenes Albertus Chemische Werke GmbH
Publication of EP3086892A1 publication Critical patent/EP3086892A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B28/24—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 alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4805—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the type of adhesives
    • B29C65/483—Reactive adhesives, e.g. chemically curing adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • 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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/047—Zeolites
    • 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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/06—Quartz; Sand
    • C04B14/066—Precipitated or pyrogenic silica
    • 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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/10—Clay
    • C04B14/106—Kaolin
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
    • C04B24/045—Esters, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/08—Fats; Fatty oils; Ester type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • 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
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/06—Inhibiting the setting, e.g. mortars of the deferred action type containing water in breakable containers ; Inhibiting the action of active ingredients
    • C04B40/0641—Mechanical separation of ingredients, e.g. accelerator in breakable microcapsules
    • C04B40/065—Two or more component mortars
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/04—Polyesters derived from hydroxycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
    • B32B2315/02—Ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/10—Accelerators; Activators
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/40—Surface-active agents, dispersants
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00663—Uses not provided for elsewhere in C04B2111/00 as filling material for cavities or the like
    • C04B2111/00672—Pointing or jointing materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0087—Uses not provided for elsewhere in C04B2111/00 for metallurgical applications
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00939—Uses not provided for elsewhere in C04B2111/00 for the fabrication of moulds or cores

Definitions

  • the present application relates to a two-component system, in particular for the formation of an adhesive which is suitable, for example, for applications in the foundry industry and / or in the construction industry.
  • Hot melt adhesives whose adhesive effect is caused by solidification of a melt must be melted before their use. This means a relatively high expenditure in terms of equipment and time.
  • Organic adhesives are detrimental in the foundry industry because they release volatile organic compounds (VOC) at the high temperatures to which molds or cores are exposed, thereby causing defects (gas bubbles) in the finished casting.
  • VOC volatile organic compounds
  • molding materials and cores are increasingly being used with inorganic binders.
  • inorganic binders In this context, it is also strives to use adhesives which do not or only to a small extent cause emissions of volatile organic compounds.
  • the compatibility of materials between organic adhesives and molded materials bonded by an inorganic binder is often not very high, which affects the reliability of the adhesive bonds.
  • thermosetting water glass adhesives The problems caused by the use of organic adhesives can be avoided if they are replaced by inorganic adhesives such as thermosetting water glass adhesives.
  • thermosetting thermosetting of water glass based adhesives
  • the chemical hardening of water glass by means of carbon dioxide or by means of esters is known as a hardener.
  • EP 0 641 748 A1 discloses a composition for fixing dowels, threaded rods and the like in cavities, in particular boreholes, in concrete, stone and brickwork, based on waterglass with at least one fine-grained, highly active reaction partner such as Si0 2 and / or Al 2 0 3 and with fillers, such as quartz powder and / or quartz sand, wherein the water glass has a molar ratio of Si0 2 to alkali oxide of> 1, 4, preferably 1, 45 to 1, 60, but ⁇ 2, and the mass also to 100 Parts by weight of water glass based 10 to 40 parts by weight of a curing agent which neutralizes the elimination of an acid with respect to the silica acid of the alkali of the water glass.
  • the water glass (optionally together with a condenser) is presented, the highly active reactants (such as Si0 2 and / or Al 2 0 3 ) added with stirring, then, also with stirring, the fillers added and then, at a high stirring speed, the hardener is added.
  • the highly active reactants such as Si0 2 and / or Al 2 0 3
  • the object of the present invention is, in particular for foundry applications, means and methods for producing fast-curing, reliable adhesives. Provide connections.
  • the curing process should preferably take place without supply of thermal energy, and preferably not be influenced to a relevant extent by the temperature of the objects to be joined.
  • the agents and methods according to the invention should not require a high technical effort in their handling.
  • the proportion of organic substances to be used for the production of the adhesive bonds should be low.
  • (B-i) a compound selected from the group consisting of cyclic esters of carbonic acid, ⁇ -butyrolactone and carboxylic acid esters of polyhydric alcohols or a mixture of two or more than two of these compounds
  • the components (A) and (B) are arranged so that no constituent of the component (A) can react with a constituent of the component (B).
  • the reactive contact of constituents of component (A) with constituents of component (B) is precluded, for example by virtue of component (A) on the one hand and component (B) on the other hand each provided in a separate container, or by the component (A) on the one hand and the component (B) on the other hand in each case in a separate chamber of a container (eg a two-chamber cartridge) are provided.
  • a separate chamber of a container eg a two-chamber cartridge
  • component (A) and component (B) are preferably present as paste or as gel.
  • the water content of component (A) is therefore preferably selected so that the alkali metal silicates (as defined above) contained in component (A) are not completely dissolved.
  • the water content of component (A) is 60% by weight or less, typically 30% to 50% by weight of the total mass of component (A), more preferably 35% to 45% by weight. , in each case based on the total mass of component (A).
  • Component (B-i) of component B is intended to act as a hardener for the alkali metal silicates contained in component (A) as component (A-i).
  • the curing of alkali metal silicates (water glass) by esters is known from the technical field of binders for foundry molding materials (water glass ester method).
  • the function of the component (B-i) can be described regularly as that of an activator for the curing of the water glass.
  • the hardening of water glass leads to the formation of polysilicic acids which have a high strength.
  • the ester or the products formed in the ester cleavage itself are not part of the curing product, based on component (A-i) already satisfy relatively small amounts of the component (B-i) to cause the curing of the water glass.
  • the proportion of organic constituents in the two-component system according to the invention can be kept low.
  • Inventive two-component systems with a low proportion of organic compounds are also suitable for applications with high requirements in terms of fire protection.
  • the molar ratio of silica to alkali metal oxide is preferably in the range from 2 to 5, particularly preferably 2.5 to 3.8.
  • the two-component system according to the invention is particularly suitable for producing an adhesive by mixing the components (A) and (B) of the two-component system according to the invention in a static mixing device.
  • Static mixing devices are apparatus for the continuous mixing of substances comprising a tube provided with suitable immovable internals. The mix is transported by impressing a pressure difference through the pipe.
  • the internals arranged in the tube are designed such that they effect a repeated division and merging of the mixed material flow and / or the formation of turbulences, whereby concentration differences or inhomogeneities within the mixed material flow are minimized.
  • Suitable forms of the internals for static mixing devices are known in the art.
  • the internals can be designed so that the flow of mixed material must pass through a labyrinth-like area.
  • Static mixing devices typically have lower investment, operating and maintenance costs compared to dynamic mixing devices because they have a smaller number of moving equipment components.
  • the component (A) preferably has a dynamic viscosity in the range from 1 Pa.s to 70 Pa.s, determined according to DIN 53019-01 with a rotational viscometer VT 550 from Haake with a rotary spindle 100 at a temperature of 20 ° C.
  • the components - Te (B) at a temperature of 20 ° C preferably has a dynamic viscosity in the range of 0, 1 Pa * s to 20 Pa * s, preferably 1 Pa * s to 20 Pa * s, determined DIN 53019-01 with a Haake's VT 550 rotary viscometer with SV1 spindle and Haake SV measuring cup.
  • the sample is heated to 20 ° C during sample preparation. Subsequently, the immersion of the measuring spindle takes place up to the dipping mark. In the low-voltage state of the measuring arrangement, the torque load cell is set to zero. Subsequently, the measurement is carried out until the constancy of the measured value at a given speed. In this case, a thixotropic material behavior is to be considered.
  • the upper limits of the dynamic viscosities of component (A) and component (B) are determined, in particular, by the fact that highly viscous substances are difficult to handle and are difficult to mix with one another.
  • the lower limits of the dynamic viscosities of component (A) and component (B) are in particular determined by the fact that the adhesive when applying to a splice should not flow uncontrolled beyond the boundaries of the splice.
  • component (A) nor for the component (B) of the two-component system according to the invention is the presence of further constituents in addition to the above-defined constituents (A-i), (A-ii) or (B-i) excluded.
  • the component (A) may be formed by, for example, a conventional thermosetting waterglass adhesive.
  • component (B) of the two-component system according to the invention comprises as further constituents
  • amorphous silica is preferably selected from the group consisting of fumed silicas, precipitated silicas, silica fume condensate and mixtures thereof
  • the component (B) of the two-component system according to the invention particularly preferably comprises as further constituents
  • (B-ii) amorphous silica wherein the amorphous silica is preferably selected from the group consisting of fumed silicas, precipitated silicas, silica fume condensate and mixtures thereof, wherein the mass fraction of component (B-ii) is preferably 20% by weight or less is, based on the total mass of component (B),
  • component (B) contains component (B-ii)
  • the proportion by mass of component (B-ii) as defined above is preferably 20% by weight or less, based on the total mass of component (B).
  • the mass fraction of constituent (B-ii) is preferably 2% by weight to 20% by weight, particularly preferably 5% by weight to 15% by weight, based in each case on the total mass of component (B),
  • component (B) contains component (B-iii)
  • the proportion by mass of component (B-iii) as defined above is preferably 40% by weight or less based on the total weight of component (B).
  • the mass fraction of constituent (B-iii) is preferably from 10% by weight to 25% by weight, particularly preferably from 10% by weight to 15% by weight, based in each case on the total mass of component (B).
  • Component (B) contains component (B-ii) and component (B-iii). thus, the content by mass of the component (B-ii) as defined above is preferably 20% by weight or less, and the content by mass of the component (B-iii) as defined above is preferably 40% by weight or less, based on the total mass of the component Component (B).
  • the mass fraction of components (B-ii) and (B-iii) taken together is thus preferably at most 60 wt .-%, based on the total mass of component (B).
  • Silicic acid is a collective term for compounds of general formula (Si0 2) m ⁇ nH 2 0 according to DIN 55943: 2001-10 is a silica produced by wet chemical, thermal or pyrogenic processes silica, which is characterized by x-ray or electron diffraction as amorphous.
  • Precipitated silicas are a finely divided amorphous form of silica prepared by precipitation from aqueous alkali metal silicate solution (waterglass) with mineral acids, eg, sulfuric acid, or with carbon dioxide.
  • Pyrogenic silicas also called fumed silica, CAS No. 1 12945-52-5) are a finely divided amorphous form of silica prepared by flame hydrolysis of silicon tetrachloride.
  • silica fume condensate obtainable by reduction of quartz with carbon in the arc furnace.
  • Such a product which is produced as a by-product in the production of silicon and ferrosilicon by reduction of quartz with a carbonaceous material, is also designated by the trade name "microsilica” or “silica fume” (CAS No. 69012-64-2 ).
  • Amorphous silica for use as component (B-ii) preferably consists of particles having a primary particle size in the range of 5 nm to 1 ⁇ m.
  • the function of the optional ingredient (B-ii) amorphous silica is i.a. in that the viscosity and / or thixotropy of component (B) to influence and the material compatibility of the organic component (Bi) containing component (B) with the predominantly or exclusively composed of inorganic substances component (A) to improve and thus the mutual wetting and mixing the components (A) and (B).
  • component (B-ii) in the mixture formed by mixing the components (A) and (B) increases the molar ratio of silica to alkali metal oxide (see above) compared to the molar ratio of silica to alkali metal oxide in component (Ai), and thus accelerates the hardening.
  • the amorphous silica of component (B-ii) participates in the curing of the water glass and is incorporated into the resulting polysilicic acids.
  • the mechanical properties of the cured material, its shrinkage and adhesion to surfaces are significantly improved by the addition of the amorphous silica.
  • the amorphous silica (B-ii) is separated from the components of component (A).
  • amorphous silicon dioxide as component (B-ii) of the component (B) of the two-component system, and not as a separate component.
  • the amorphous silica is incorporated into the component (B), which thus preferably obtains an gel-like paste-like consistency.
  • Zeolites Component (B-iii) are crystalline aluminosilicates of the general formula
  • Zeolites are characterized by a framework and pore structure, which among other things allows the absorption of water.
  • the crystal lattices of the zeolites are composed of Si0 4 and Al0 4 tetrahedra, which are each linked to one another via oxygen bridges and form rings or prisms. These in turn combine with other secondary building blocks, each containing up to 16 Si or Al atoms.
  • zeolites (B-iii) improves the long-term stability of adhesive bonds produced according to the invention. It is currently believed that this is due to absorption of component (A) water (A-ii) by the zeolite (B-iii).
  • the release of water after preparation of the adhesive bond is a process that extends over several days and limits the life of the adhesive bond, unless appropriate countermeasures are taken.
  • the use of one or more zeolites as component (B-iii) prolongs the life of the adhesive bond (in particularly preferred embodiments, up to four weeks or longer) because the absorbent action of the zeolites (B-iii) slows the release of water. For applications in which no long life of the adhesive bond is required, but also inventive two-component systems without component (B-iii) are suitable.
  • component (B) contains a two-component system according to the invention
  • fly ash preferably fly ash of hard coal combustion, prefers fly ash from hard coal-fired power plants
  • the proportion of the component (Ai) of the component (A) to the component (B-ii) of the component (B) of the preferred two-component system of the present invention determines the ratio of silica to alkali metal oxide in the component (A) and (B ) and thus has a significant influence on the curing rate of the mixture and the proportion of binding polysilicic acids in the cured adhesive. Preference is given to a two-component system according to the invention, wherein the ratio
  • component (B-ii) of component B in the range from 10: 1 to 70: 1, preferably in the range from 20: 1 to 50: 1, particularly preferably in the range from 30: 1 to 40: 1.
  • the ratio is preferably in the component (B) of the two-component system according to the invention
  • the compounds of component (Bi) of component (B) of the two-component system according to the invention are esters which are capable of curing on mixing the component (A) with component (B) according to the method of the binders for Foundry molding materials to effect known water glass ester method.
  • component (B-i) of component (B) of the two-component system according to the invention are cyclic esters of carbonic acid of the formula (I)
  • R- 1 and R 2 are each independently selected from the group consisting of hydrogen, unbranched alkyl groups having 1 to 6 carbon atoms and branched alkyl groups having 4 to 6 carbon atoms. Particularly preferred are the cyclic carbonic acid esters from the group consisting of ethylene carbonate, propylene carbonate and butylene carbonate.
  • Another group of compounds which are preferably used as or in component (Bi) of component (B) of the two-component system according to the invention are carboxylic acid esters of polyhydric alcohols.
  • Polyhydric alcohols are alcohols having two or more hydroxy groups per molecule.
  • esters to be used according to the invention one, several or all hydroxyl groups of the polyhydric alcohol are esterified by carboxylic acids.
  • carboxylic acid esters of polyhydric alcohols from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol and glycerol.
  • carboxylic acid esters of polyhydric alcohols from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, mono- and di-acetic acid esters are preferred according to the invention.
  • Preferred carboxylic acid esters of glycerol according to the invention are compounds of the formula (II)
  • R 3 , R 4 and R 5 are each independently selected from the group consisting of hydrogen and acyl groups -C (O) R 6 , wherein R 6 in the acyl groups is independently selected from the group consisting of straight chain alkyl groups of 1 to 6 carbon atoms and branched chain alkyl groups of 4 to 6 carbon atoms, provided that at least one of R 3 , R 4 and R 5 is an acyl group as defined herein.
  • Particularly preferred are mono-, di- and tri-acetic acid esters of glycerol.
  • the diacetic acid ester of glycerol is also referred to as diacetin.
  • the tri-acetic acid ester of glycerol is also referred to as triacetin.
  • component (Bi) of component (B) of the two-component system according to the invention is particularly preferably formed from a mixture consisting of one or more compounds of the formula (I), for example propylene carbonate, and one or more compounds of the formula (II), for example the acetic triester of Glycerols (triacetin).
  • component (A) of the two-component system according to the invention one, several or all of the alkali metal silicates (Ai) present are preferably selected from the group consisting of sodium silicate, potassium silicate and mixtures thereof.
  • component (A) of the two-component system according to the invention comprises as further constituent
  • Ingredient (A-iii) does not contain alkali metal silicates having a molar ratio of silica to alkali metal oxide in the range of 2 to 5 (these are included in component (A-i)) and no amorphous forms of silica (component B-ii).
  • the fillers of ingredient (A-iii) are preferably used in the form of naturally occurring minerals.
  • quartz especially in the form of quartz sand or quartz powder
  • the aluminosilicates especially clay minerals and clays, in particular kaolins and bentonites (containing as the main constituent the mineral montmorillonite), are preferred.
  • the filler or at least one of the fillers is preferably selected so as to be identical or at least similar to the molding material contained in the parts to be joined of a foundry mold.
  • Ingredient (A-iii) contains no zeolites.
  • Corresponding fillers are also used in conventional thermosetting water-glass adhesives and are thus known to the person skilled in the art. Fillers are materials which undergo little or no volume shrinkage when a mixture formed from the two-component system according to the invention is cured. The function of the filler is to adjust the desired dynamic viscosity of component (A), and to achieve a desired degree of filling in the adhesive formed from the two-component system according to the invention.
  • fillers (A-iii) which are capable of binding or storing water by swelling or in some other way. This applies, for example, to the above-mentioned clays and clay minerals. It has been shown that the addition of water-binding fillers (A-iii) to component (A) of the two-component system according to the invention improves the long-term stability of adhesive bonds produced according to the invention. It will presently believed to be due to binding of component (A) water (A-ii) by the water-binding filler (A-iii). The release of water after preparation of the adhesive bond is a process that extends over several days and limits the life of the adhesive bond, unless appropriate countermeasures are taken.
  • water-binding fillers (A-iii) prolongs the service life of the adhesive bond, as the water-binding action of the fillers (A-iii) slows down the release of water.
  • two-component systems without water-binding fillers (A-iii) are suitable.
  • the ratio is preferably in the component (A) of the two-component system according to the invention
  • the total content of the components (A) and (B) of the two-component organic carbon system of the present invention is 6% by weight or less , preferably 5.5 wt .-% or less, more preferably 4 wt .-% or less, based on the total mass of the components (A) and (B).
  • the carbon content is determined by means of an elemental analysis (combustion analysis), preferably by means of the Vario Max CNS system from Elementar.
  • the component (A) of a two-component system according to the invention contains as further constituents
  • the sum of the mass fractions of constituents (A-iv) as defined above and (Av) as defined above is preferably 2% by weight or less, based on the total mass of component (A).
  • surfactants also commonly referred to as “wetting agents” or “wetting agents”
  • Suitable anionic see surfactants especially those with a sulfate, sulfonate or a phosphate group.
  • the anion of the anionic surfactant is preferably selected from the group consisting of oleylsulfate, stearylsulfate, palmitylsulfate, myristylsulfate, laurylsulfate, decylsulfate, octylsulfate, 2-ethylhexylsulfate, 2-ethyloctylsulfate, 2-ethyldecylsulfate, palmitoleylsulfate, linolylsulfate, laurylsulfonate, 2-ethyldecylsulfonate, palmitylsulfonate , Stearyl sulfonate, 2-ethyl stearyl sulfonate, linolyl sulfonate, hexyl phosphate, 2-ethylhexyl phosphate, capryl phosphate, lauryl phosphate,
  • surfactants are sodium ethylhexyl sulfate and sodium octyl sulfate.
  • the surfactants (A-iv) are used as pure substances or in the form of aqueous solutions having a surfactant content of 10% by weight or more, based on the weight of the aqueous solution. However, only the masses of the surfactants themselves count for the calculation of the mass fraction of the surfactants (A-iv) on component (A). If surfactants (A-iv) are used in the form of aqueous solutions, their water content is that of constituent (A-ii ).
  • mineral oil is a collective term for liquid distillation products derived from mineral resources (petroleum, lignite, coal, wood, peat) .
  • the main constituent of mineral oils are mixtures of saturated chain hydrocarbons (paraffins), aromatic hydrocarbons and alicyclic hydrocarbons (naphthenic hydrocarbons)
  • the addition of mineral oil (Av) enhances the wettability of component (A) and extends the time until component (A) forms a skin by reaction of the alkali metal silicates (Ai) with CO 2 contained in the ambient air is troublesome and undesirable in the production of adhesive bonds, as it hinders the adhesion of the adhesive to the surfaces of the articles to be joined
  • the phenomenon of skin formation is known from water-glass adhesives It is currently believed that the addition of mineral oil is a passivation of the alkali metal silicates (Ai) with respect to the reaction with C0 2 causes.
  • a two-component system according to the invention is preferred whose components (A) and (B) are coordinated with respect to their composition and their mass ratio so that the mixture formed by mixing the components (A) and (B) has a pot life in the range of one minute to 1 hour, preferably 2 minutes to 1 hour, more preferably in the range of 3 minutes to 30 minutes.
  • Pot life also referred to as processing time, is the period during which a multi-component adhesive can be used after its ingredients have been mixed.
  • the pot life is determined by method 4.3 of DIN EN 014022.
  • the pot life is determined by the curing rate, which depends on the composition of components (A) and (B) as described above, in particular with regard to the components (Ai) and (if present) (B-ii).
  • the pot life can be varied, and depending on the desired application, two-component systems according to the invention can be provided with the appropriate pot life. While pot lives of less than 30 minutes are particularly suitable for foundry applications, longer pot lives are acceptable for applications in the construction industry.
  • the mixture formed by mixing the components (A) and (B) of the two-component system according to the invention is an adhesive.
  • the mixing of components (A) and (B) of the two-component system according to the invention is preferably carried out in a static mixing device (as described above).
  • Another aspect of the present invention relates to a kit for producing an adhesive comprising
  • the static mixing device is preferably part of a device for applying an adhesive to a splice, for example an adhesive device of the type typically used for the application of organic two-component adhesives such as polyurethane or epoxy two-component adhesives.
  • an adhesive device of the type typically used for the application of organic two-component adhesives such as polyurethane or epoxy two-component adhesives.
  • Corresponding devices are known in the art and typically include a two-chamber cartridge and a static mixing device in the form of a mixing tube.
  • Another aspect of the present invention relates to the use of a two-component system according to the invention or a kit according to the invention for producing an adhesive bond between objects to be joined.
  • the adhesive produced according to the invention is applied to one or more splices.
  • an adhesive point is understood to be a coherent area to be acted upon by the adhesive on a surface of one of the objects to be joined.
  • the adhesive is spot-shaped on a splice, for example, e.g. in the form of a dot with a diameter of 2 mm or smaller, preferably 1, 5 mm or smaller, applied, or in the form of a bead, typically in the form of a bead having a diameter of 3 mm or less, preferably 2 mm or less.
  • the viscosity of the adhesive should be chosen so that it can - if desired - be applied to splices of low expansion, without going beyond the limit of the splice.
  • the use of a two-component system according to the invention is not limited to splices with the dimensions exemplified here.
  • kits according to the invention for producing an adhesive bond wherein the objects to be joined by the adhesive bond at the splices contain one or more inorganic materials selected from the group of ceramic materials, in particular from the group consisting of oxides and silicates.
  • the objects to be joined by the adhesive bond are particularly preferably parts of a foundry mold, wherein the parts to be joined of a foundry mold preferably each contain mold primers bound by a binder formed by curing (preferably thermal curing) one or more alkali metal silicates.
  • a foundry mold By dividing a foundry mold here are understood forms (which define the outer contours of the casting to be produced), cores (which define the inner contours of the casting to be produced) and feeders, as well as parts of such shapes, cores and feeders.
  • a core is formed, by connecting parts of a mold according to the invention to a mold and by connecting parts of a feeder according to the invention to a feeder.
  • foundry molds using water glass as a binder is known in the art.
  • mold bases for the production of molds commonly used materials are used such as quartz or zircon sand, chamotte, mullite, olivine, chrome ore, vermiculite or other refractory mold base materials.
  • quartz or zircon sand, chamotte, mullite, olivine, chrome ore, vermiculite or other refractory mold base materials According to the standard DIN 51060 "Refractory ceramic raw materials and refractory products" materials are referred to as refractory with resistance to temperatures of> 1500 ° C and as highly refractory with resistance to temperatures of> 1800 ° C.
  • a particularly preferred field of application of two-component systems according to the invention is the production of adhesive bonds between parts of a feeder, and in particular between a feeder insert and a breaker core (preferably a croning breaker core).
  • Another particularly preferred field of application of two-component systems according to the invention is the production of adhesive bonds between parts of G mananrough- and / or running structures.
  • Such structures are typically composed of two or more parts, usually in the form of tubular sections, preferably made of highly refractory ceramic material, wherein the individual parts are joined together by adhesive bonding.
  • Another particularly preferred field of application of two-component systems according to the invention is the production of adhesive bonds between cores or parts of cores.
  • a further aspect of the present invention relates to the use of a static mixing device for producing an adhesive, wherein the adhesive is prepared by mixing the components (A) and (B) of a two-component Systems (preferably in one of the preferred embodiments described above) is made in the static mixer.
  • Another aspect of the present invention relates to a method of making an adhesive comprising the step
  • the mixing of components (A) and (B) of a two-component system according to the invention is preferably carried out in a static mixing device.
  • a further aspect of the present invention relates to a method for producing an adhesive bond between articles to be joined, comprising the steps:
  • the two-component system according to the invention, the kit according to the invention and the method according to the invention are suitable, for example, for applications in the foundry industry and in the construction industry.
  • the curing process of an adhesive formed according to the invention by mixing the components (A) and (B) of a two-component system according to the invention is not significantly influenced by the temperature of the articles to be joined. This is an advantage for use in joining parts of a foundry mold since foundry molded parts bonded with a thermoset binder (e.g., waterglass) often still have some residual temperature after curing (typically in the range of 40 to 80 ° C).
  • a thermoset binder e.g., waterglass
  • Adhesive compounds prepared by the process of the invention are characterized by high tensile strength and low sensitivity to changes in the humidity of the surrounding air.
  • Adhesive bonds prepared by the process according to the invention in particular using the particularly preferred embodiments of the two-component system according to the invention described above, are also less susceptible to contact with water, e.g. when treating according to the invention by an adhesive bond connected parts of a foundry mold with an aqueous size.
  • adhesive bonds produced by the process according to the invention have a high stability to thermal loads.
  • the respective components (A) and (B) of the two-component systems 1 to 13 were mixed in a static mixer.
  • a two-chamber cartridge with the A: B volume ratio of 10: 1 with mounted static mixing tube was used for systems 1 to 7.
  • 66 g of component A were filled into the first chamber bubble-free.
  • In the second chamber 5 g of component B were also filled bubble-free.
  • the cartridge was tempered at 20 ° C. Subsequently, 30 g of sample material were pressed out with a corresponding punch from the mixing tube of the cartridge after discarding a minimum flow.
  • a two-chamber cartridge with the A: B volume ratio of 10: 1 with mounted static mixing tube was used. 72 g of component A were filled into the first chamber without bubbles. In the second chamber 5 g of component B were also filled bubble-free. The cartridge was tempered at 20 ° C.
  • a mixture consisting of kaolin and quartz powder is used as constituent (A-iii), in which the weight ratio of kaolin to quartz powder is 2: 1.
  • two-component systems according to the invention having different pot lives can be produced. While two-component systems according to the invention having pot lives of less than 30 minutes are particularly suitable for use in joining parts of a foundry mold, the two-component systems according to the invention with longer pot lives are particularly suitable for applications in the construction industry.
  • Component (A) Component (B)
  • Component (A) Component (B)

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Civil Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Dispersion Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Mold Materials And Core Materials (AREA)

Abstract

L'invention concerne un système bicomposant notamment destiné à la formation d'un adhésif, et convenant par exemple à des applications dans l'industrie de la fonderie et dans l'industrie de la construction.
EP14821176.6A 2013-12-23 2014-12-19 Système bicomposant notamment destiné à la formation d'un adhésif Withdrawn EP3086892A1 (fr)

Applications Claiming Priority (2)

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DE102013227151 2013-12-23
PCT/EP2014/078898 WO2015097108A1 (fr) 2013-12-23 2014-12-19 Système bicomposant notamment destiné à la formation d'un adhésif

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JP (1) JP6474819B2 (fr)
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DE102017107657A1 (de) * 2017-01-04 2018-07-05 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Schlichtezusammensetzung, umfassend organische Esterverbindungen und partikuläres, amorphes Siliziumdioxid, zur Verwendung in der Gießereiindustrie
CN108393430B (zh) * 2017-02-04 2020-05-08 济南圣泉集团股份有限公司 一种铸造水玻璃用固化剂
US10759697B1 (en) 2019-06-11 2020-09-01 MSB Global, Inc. Curable formulations for structural and non-structural applications
JP2021074725A (ja) * 2019-11-06 2021-05-20 トヨタ自動車株式会社 鋳型用接着剤の製造方法、鋳型の製造方法、及び鋳型

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WO2003066253A1 (fr) * 2002-02-07 2003-08-14 Iko Minerals Gmbh Procede de production de sable de fonderie, en particulier recycle, a des fins de fonderie

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WO2015097108A1 (fr) 2015-07-02
US20160311724A1 (en) 2016-10-27
MX2016008350A (es) 2016-10-28
US10106462B2 (en) 2018-10-23
KR20160102000A (ko) 2016-08-26
JP2017508824A (ja) 2017-03-30
JP6474819B2 (ja) 2019-02-27

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