CN102858709A - Mineral wool fiber mats, method for producing same, and use - Google Patents
Mineral wool fiber mats, method for producing same, and use Download PDFInfo
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- CN102858709A CN102858709A CN2011800195470A CN201180019547A CN102858709A CN 102858709 A CN102858709 A CN 102858709A CN 2011800195470 A CN2011800195470 A CN 2011800195470A CN 201180019547 A CN201180019547 A CN 201180019547A CN 102858709 A CN102858709 A CN 102858709A
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H13/00—Other non-woven fabrics
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/28—Macromolecular compounds or prepolymers obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/285—Acrylic resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C08L31/04—Homopolymers or copolymers of vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacturing & Machinery (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to mineral wool fiber mats, which are stabilized by means of a binder made of polymers functionalized with epoxy groups and/or with carboxyl groups and selected cross-linking agents. Said mats can be used as an insulating material and are characterized by low or no formaldehyde emissions.
Description
Technical field
The present invention relates to the mineral wool fibre felt with selected binder-impregnated.These felts can be used as such as insulating material, as being used for the heat-insulating insulating material in roof.
Background technology
Aqueous polymer dispersions itself as the binding agent of mineral wool fibre felt is known.Be mixed with the part that consists of a large amount of patent document themes as the mineral wool felt of the crosslinked polymkeric substance of binding agent.
US-A-2008/0175997 has described the adhesive composition that is used for glassmat, and it comprises the emulsion of carboxy-functionalized polymkeric substance and the linking agent with aziridine group.Compare with conventional system, related is formaldehydeless dispersion.It is compared with known system, has comparable or even improved intensity and snappiness.This document also mention for glassmat derived from carboxy-functionalized polymkeric substance and comprise specific linking agent or comprise the known adhesive system of epoxidized oil, described linking agent for example is the polyol compound of being combined with phosphorus accelerator, the compound that contains active hydrogen of being combined with fluoroboric acid ester promotor, such as polyvalent alcohol, polyvinyl alcohol or polyacrylic ester, perhaps promote the linking agent of COOH and the esterification of OH group in the polymkeric substance.
EP-A-1,018,523 discloses polymeric dispersions, and it contains the addition polymer of the dispersion of the co-poly carboxylic acid unit that a) comprises the 5-20 % by weight, b) comprise the addition polymer of dissolving of the co-poly carboxylic acid unit of 60-100 % by weight, and c) selected alkoxylate long-chain amine as linking agent.This dispersion can be used as being used for the binding agent of mineral wool felt.
DE-T-69921163 has described based on the insulating products on the basis of the mineral wool of certain minerals fiber, and this insulating products has the size based on thermosetting resin, makes described thermosetting resin and latex mix to improve physical strength after aging.Used latex comprises especially and has hydrophilic radical, such as carboxyl, hydroxyl or carboxylate group's polymkeric substance.Mention resol as a kind of thermosetting resin.
DE-A-197 38 771 and DE-A197 20 674 have described the binding agent that is used for mineral wool, its contain a) can with the crosslinked thermoplastic polymer of resol, such as polyacrylic ester or polyvinyl ester, b) resol and c) fire retardant.
EP-A-1 164 163 has described the binding agent that is used for mineral wool, and it obtains by mixed carboxylic acid under reaction conditions and alkanolamine.The example of the carboxylic acid that uses is polyacrylic acid, polymethyl acrylic acid or polymaleic acid.
WO-A-01/05,725 have described the binding agent that is used for mineral wool, and it is by not comprising polymkeric substance but comprise amine and the reaction of the mixture of the first and second acid anhydrides obtains.The Typical Representative thing of this reaction mixture is diethanolamine, annular aliphatic acid anhydrides, for example maleic anhydride, succinyl oxide or hexahydrophthalic anhydride, and aromatic anhydride, for example Tetra hydro Phthalic anhydride.
WO-A-2007/060,236 have described the formaldehyde-free binder that is used for mineral wool, it contains the aqueous dispersion of the poly carboxylic acid of a) polymerization, b) selected alkanolamine, for example thanomin, and c) activation silane, it is by making for example organoalkoxysilane of silane, but with the reactive ketone of the enolization that contains at least one carboxylic group, perhaps obtain described ketone such as otan or methyl ethyl diketone with the reactive ketone with at least one oh group.
DE-A-100 14 399 discloses the mixture that is formed by two kinds of paradigmatic systems, and wherein a kind of system is with enforceable carboxylic group, and the second contains the functional group of the copolymerization that can react with the carboxylic group of the first paradigmatic system to form covalent linkage.
DE-A-26 04 544 discloses the binding agent that is used for the reinforced glass fibrefelt, and wherein carboxylic polymkeric substance reacts with the linking agent of the isocyanic ester that is selected from polyepoxide or end-blocking.The polymer base that limits employed binding agent is: from the constructed polymkeric substance that obtains of the ethylenic unsaturated ester of acrylic or methacrylic acid.
JP-A-2006-089,906 have described the formaldehyde-free binder that is used for mineral wool, and it contains the ethylenic copolymer with oh group and organic acid deriveding group.
WO-A-2004/085,729 have described the formaldehyde-free binder that is used for mineral wool, it contains compound and the b that a) has at least 2 cyclic ether groups) have a multipolymer of nucleophilic group.
WO-A-2006/136,614 disclose the binding agent that is used for mineral wool, it contains a) P-F binding agent and b) oxyamine or amino alcohol.
DE-A-40 24 727 discloses the reagent that is used for making the mineral wool fibre hydrophilization, it contains a) P-F binding agent, and as the b of the component of mixture of hydrophilization reagent) water-soluble nitrogen-carbonyl compound, such as urea, c) acrylic resin and d) contain the mixture of carboxylic fatty acids condensation product and organophosphate.
Also have a lot of files to describe epoxy group(ing)-or carboxyl-functionalized binding agent.US-A-2008/0214716, US-A-2006/0258248, DE-C-199 56 420 and WO-A-03/104284 have provided the example of such binding agent.WO-A-03/104284 has described the adhesive system for the production of fiberglass products, and low molecular weight epoxy compound and functionalized polymerizable compound are crosslinked in this system.US-A-2006/0258248 discloses epoxidised oil and multiple functionalized carboxylic acid or acid anhydrides combination as suitable cross-linked binder.US-A-2008/0214716 discloses the binding agent for the production of fabric, and it is derived from polymkeric substance based on ethylenically unsaturated monomers, based on the water-soluble polymers of ethylenic unsaturated carboxylic acid and the linking agent of oxyalkylated or hydroxyalkylation.DE-C-199 56 420 has described in the presence of based on the cross-linking reagent of Resins, epoxy or acrylic resin, based on water-soluble polymers and the purposes of some amine in producing moulded products of ethylenic unsaturated carboxylic acid.
For in preparation, not containing formaldehyde, release formaldehyde not when using, and keep simultaneously the product of existing performance characteristics, increasing business demand is arranged.
Summary of the invention
The object of the present invention is to provide as insulating material bonding mineral wool fibre felt very useful, that be bonded together with formaldehyde-free binder." formaldehydeless " should be interpreted as the formaldehyde content that refers to composition is less than 10ppm in the context of the present specification.
The invention provides the mineral wool fibre felt with the binding agent bonding, described binding agent contains epoxy functional and/or carboxy-functionalized multipolymer, especially contain suitably functionalized, preferably take the emulsion copolymers of dispersion form, and as the amine of linking agent and/or the derivative of amine.
In preferred implementation of the present invention, the mineral wool fibre felt contains the biosoluble fibers material by the formaldehyde-free binder bonding, uses described binding agent in the pH scope that described fiber can not suffer erosion.Ideally, this scope is positioned at more than the neutral point.This pH scope is preferably 7.5-10.
Detailed Description Of The Invention
Mineral wool fibre felt of the present invention contains glass wool and/or asbestos, can contain in principle other aggregate known to persons of ordinary skill in the art and/or other fiber.
Can produce glass wool with any basic reserve known from glass industry.Normally used have quartz sand, yellow soda ash and a Wingdale; Can in these raw materials, sneak into cullet, for example up to the cullet of 70 % by weight.In a conventional manner, make melt fibrillation by rotary casting or injection.
Can use the mode similar to glass wool to produce asbestos.Normally used have basalt, diabase, feldspar, rhombspar, sand and a Wingdale; These raw materials can similarly be mixed with cullet.In a conventional manner, make melt fibrillation by rotary casting.Except the raw material of usual production asbestos, also can use as refuse result from the burning or production process in slag, such as blast-furnace slag.The asbestos of this form are called slag wool, are known to persons of ordinary skill in the art equally.
Particularly preferably choice for use has glass wool or the asbestos of high biological solubility.Biological solubility should be interpreted as the ability that fiber is dissolved and degrades by endogenous material in vivo that refers to.
Add binding agent to guarantee their dimensional stability to formed microglass fiber felt or fibrous magnesium silicate felt.Subsequently by heat treated, as in hot gas flow, fibrefelt being solidified.In the process of heat treated, also from fibrefelt, removed volatile component.Such web forming process for example is described among the US 2008/0175997A1.
Alternatively, the mineral wool fibre felt also can be by wet laid random web production., fiber at first can be added in the water paste together with binding agent for this reason, deposit on mobile seating surface such as the water-permeable travelling belt, to form fibrefelt.After anhydrating, by heat treated, as in hot gas flow, fibrefelt being solidified.Such mineral wool felt production process for example is described among DE 601 23 177T2.
The mineral wool felt can also comprise other conventional material that adds.Often add mineral oil with for example, further improve processing characteristics and give the draining character that the mineral wool felt improves.In addition, when being particularly useful as insulating material, can be with such felt and aluminium foil or fibrous nonwoven web lamination.
Mineral wool fibre felt of the present invention has the binding agent that specifically contains multipolymer epoxy functional and/or carboxy-functionalized.
Epoxy functional and/or carboxy-functionalized multipolymer is preferably derived from one or more ethylenically unsaturated compounds, so that at least a in these monomers must have one or more epoxide groups and/or one or more carboxylic group.
With regard to reactive group, these embodiments or only comprise the epoxide group of copolymerization, the carboxylic group that perhaps only comprises copolymerization, or except the epoxide group of copolymerization, the carboxylic group that also comprises copolymerization, described group for example come from the unsaturated list of the ethylenic of deriving-or the unit of dicarboxylic acid.The selection of these embodiments is depended on other additive of adding to binder preparation and/or the principal reaction condition of (in the bonding such as mineral wool in the bonding process) in application especially.
Except these multipolymers, also can use fully or mostly be derived from homopolymer or the multipolymer of carboxylic ethylenically unsaturated monomers.The example has polyacrylic acid or its salt, also has an alkali metal salt of polymethyl acrylic acid or its salt, especially these polymkeric substance.
Epoxy functional and/or carboxy-functionalized multipolymer preferably includes multipolymer and/or the α of vinyl ester, the unsaturated C of β-ethylenic
3-C
8-single-or the multipolymer of dicarboxylic ester and/or the multipolymer of alkenyl aromatic compounds, each obtains with the ethylenic insatiable hunger comonomer polymerization that contains epoxide group and/or carboxylic group or its acid anhydrides.
Except containing the epoxy group(ing) monomer and/or containing the carboxylic monomer, considered that mainly following several groups of monomers are as other basis of described polymer class:
One group is made of following monomer: the monocarboxylic vinyl ester with one to 18 carbon atom, example has vinyl formate, vinyl-acetic ester, propionate, the isopropylformic acid vinyl acetate, the valeric acid vinyl acetate, the valeric acid vinyl acetate, new vinyl acetate acid, the 2 ethyl hexanoic acid vinyl acetate, the capric acid vinyl acetate, methylvinyl acetate, the vinyl ester that has the saturated branched monocarboxylic acid of 5 to 15 carbon atoms at sour integral part, especially the vinyl ester of VersaticTM acid, the vinyl ester of the saturated or unsaturated fatty acids of relative long-chain, vinyl laurate for example, stearic acid vinyl ester, and the vinyl ester of phenylformic acid and substituted benzoyl acid derivative, such as p-p t butylbenzoic acid vinyl acetate.Yet in these, particularly preferably vinyl-acetic ester is used as principal monomer.
Another group monomer is made of following monomer: α, the unsaturated C of β-ethylenic
3-C
8-single-or dicarboxylic acid preferably with C
1-C
18-alkanol is C especially
1-C
8-alkanol or C
5-C
8The ester that-cycloalkanol forms.The ester of dicarboxylic acid can be monoesters, or is preferably diester.Suitable C
1-C
8The example of-alkanol is methyl alcohol, ethanol, n-propyl alcohol, Virahol, n-butyl alcohol, 2-butanols, isopropylcarbinol, the trimethyl carbinol, n-hexyl alcohol and 2-Ethylhexyl Alcohol.The example of suitable cycloalkanol is cyclopentanol or hexalin.Example is acrylate; methacrylic ester; crotonate; maleic acid ester; itaconic ester; citraconate or fumarate, for example (methyl) methyl acrylate; (methyl) ethyl propenoate; (methyl) isopropyl acrylate; (methyl) n-butyl acrylate; (methyl) isobutyl acrylate; the own ester of (methyl) vinylformic acid 1-; (methyl) tert-butyl acrylate; (methyl) 2-ethylhexyl acrylate; toxilic acid or dimethyl fumarate; toxilic acid or DEF; toxilic acid or fumaric acid di-n-propyl ester; toxilic acid or di n butyl fumarate; toxilic acid or fumaric acid diisobutyl ester; toxilic acid or fumaric acid two n-pentyl esters; the just own ester of toxilic acid or fumaric acid two; toxilic acid or fumaric acid two cyclohexyls; toxilic acid or di-n-heptyl fumarate; toxilic acid or fumaric acid di-n-octyl; toxilic acid or fumaric acid two-(2-ethylhexyl) ester; toxilic acid or fumaric acid two ester in the positive ninth of the ten Heavenly Stems; toxilic acid or fumaric acid two ester in the positive last of the ten Heavenly stems; toxilic acid or fumaric acid two n-undecane base esters; toxilic acid or fumaric acid dilauryl ester; toxilic acid or fumaric acid myristyl ester; toxilic acid or fumaric acid two palmitoyl esters; toxilic acid or fumaric acid distearyl ester and toxilic acid or fumaric acid diphenyl ester.
This is organized preferred principal monomer and is selected from acrylate and methacrylic ester.Particularly preferably (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, the own ester of (methyl) vinylformic acid 1-, (methyl) tert-butyl acrylate, (methyl) 2-ethylhexyl acrylate.
Another group monomer is made of alkenyl aromatic compounds.The alkenyl aromatic compounds of considering is the mono-alkenyl aromatic substance.The example is vinylbenzene, Vinyl toluene, vinyl-dimethyl benzene, alpha-methyl styrene or ortho-, meta-or p-chloro-styrene.Need to should be mentioned that especially vinylbenzene is the preferred monomers in this group.
Mentioned monomer generally forms principal monomer, and it is with respect to the total amount of the monomer for the treatment of polymerization, usually accounts for to be higher than 50 % by weight, preferably to be higher than the ratio of 75 % by weight.
Another group main and vinyl ester and/or α, the unsaturated C of β-ethylenic
3-C
8-single-or dicarboxylic ester and/or the common monomer that uses of alkenyl aromatic compounds consisted of by following monomer: aliphatic, the monoene formula is undersaturated or the diene formula is undersaturated, the optional hydrocarbon that is replaced by halogen, for example C of ethene, propylene, 1-butylene, 2-butylene, iso-butylene, conjugation
4-C
8-diene (such as 1,3-butadiene, isoprene, chloroprene), vinylchlorid, vinylidene chloride, vinyl fluoride or vinylidene fluoride.
Preferably monomer is selected so that be formed on addition polymer or the multipolymer that good compatibility is arranged in the common formaldehyde-free binder preparation, it also has excellent cementing property in the production of mineral wool felt.
Except the monomer that contains epoxy group(ing) and/or carboxylic monomer, the preferred binder polymer that uses is derived from following principal monomer or its combination:
Multipolymer based on one or more vinyl ester, especially vinyl-acetic ester; Based on α, the unsaturated C of β-ethylenic
3-C
8-monocarboxylic acid and C
1-C
8Ester, the especially multipolymer of (methyl) acrylate that-alkanol forms; Based on vinyl ester and α, the unsaturated C of β-ethylenic
3-C
8-single-or dicarboxylic acid and C
1-C
8Ester, especially (methyl) acrylate that-alkanol forms and maleic acid ester/or the multipolymer of fumarate; Based on vinyl ester, especially vinyl-acetic ester, with the multipolymer of ethene; Based on α, the unsaturated C of β-ethylenic
3-C
8-single-or dicarboxylic acid and C
1-C
8Ester, especially (methyl) acrylate that-alkanol forms and maleic acid ester/or fumarate, with the multipolymer of ethene; Based on vinyl ester, ethene and α, the unsaturated C of β-ethylenic
3-C
8-single-or dicarboxylic acid and C
1-C
8Ester, especially (methyl) acrylate that-alkanol forms and maleic acid ester/or the multipolymer of fumarate; Perhaps styrene-based, and α, the unsaturated C of β-ethylenic
3-C
8-single-or dicarboxylic acid and C
1-C
8Ester, especially (methyl) acrylate that-alkanol forms, and the multipolymer of ethene and/or divinyl randomly.
The example that preferably contains the alkoxyl group monomer of using with the principal monomer copolymerization is: glycidyl allyl ether; methacryl glycidyl ether; the divinyl monoepoxide; 1; 2-epoxy group(ing)-5-hexene; 1; 2-epoxy group(ing)-7-octene; 1; 2-epoxy group(ing)-9-decene; 8-hydroxyl-6; 7-epoxy group(ing)-1-octene; 8-acetoxyl group-6; 7-epoxy group(ing)-1-octene; N-(2; the 3-epoxy group(ing))-the propyl group acrylamide; N-(2; the 3-epoxy group(ing))-the propyl methyl acid amides; 4-acrylamido phenyl glycidyl ether; 3-acrylamido phenyl glycidyl ether; 4-methacryloyl amido phenyl glycidyl ether; 3-methacryloyl amido phenyl glycidyl ether; N-glycidoxy Methacrylamide; N-glycidoxy propyl methyl acid amides; N-glycidoxy ethyl acrylamide; N-glycidoxy ethyl-methyl acrylamide; N-glycidoxy propyl group acrylamide; N-glycidoxy propyl methyl acid amides; N-glycidoxy butyl acrylamide; N-glycidoxy butyl methyl acrylamide; 4-acrylamide group methyl-2; 5-3,5-dimethylphenyl glycidyl ether; 4-methacryloyl aminomethyl-2; 5-3,5-dimethylphenyl glycidyl ether; acrylamido propyl-dimethyl-(2; the 3-epoxy group(ing)) propyl ammonium chloride; methacryloyl amido propyl-dimethyl-(2,3-epoxy group(ing))-propyl ammonium chloride and glycidyl methacrylate.Derived from the unsaturated list of ethylenic-or the monomer that contains epoxy group(ing) of glycidyl ester, for example glycidyl acrylate and the glycidyl methacrylate of dicarboxylic acid be particularly preferred.
By the monomer that contains epoxy group(ing) provide based on the weight fraction for the treatment of the polymerization single polymerization monomer total amount for being lower than 50 % by weight, preferably between 0.1 % by weight to 20 % by weight, more preferably between 1 % by weight to 10 % by weight, most preferably between 2 % by weight to 5 % by weight.
Except above-mentioned principal monomer, binder polymer used in the present invention can also contain the structural unit derived from carboxylic monomer at least.
This group monomer mainly comprises the α with 3 to 10 carbon atoms, the β-unsaturated list of single ethylenic-and dicarboxylic acid, and their water-soluble salt, such as their sodium salt, also have their acid anhydrides.The preferred monomers of this group is the unsaturated C of ethylenic
3-C
8-carboxylic acid and C
4-C
8-dicarboxylic acid, for example toxilic acid, fumaric acid, methylene-succinic acid, β-crotonic acid, vinylacetic acid, (methyl) vinylformic acid 2-carboxylic ethyl ester, acrylamido oxyacetic acid, especially vinylformic acid, methacrylic acid, the monoesters that also has toxilic acid and fumaric acid is such as toxilic acid (list-2-ethylhexyl) and ethyl maleate.
Based on the total amount for the treatment of polymerization single polymerization monomer, usually with these carboxylic monomers with less than 50 % by weight, preferably between 0.1 % by weight to 20 % by weight, more preferably between 1 % by weight to 10 % by weight, most preferably the amount between 2 % by weight to 5 % by weight is carried out copolymerization.
The binding agent that is particularly preferred for the mineral wool fibre felt contains based on polyvinyl ester, based on polyacrylic ester or based on the multipolymer of the epoxy functional of polyalkenyl aromatic substance, it comprises derived from the unsaturated list of ethylenic-or the copolymerization units of the glycidyl ester of dicarboxylic acid, the copolymerization units of preferred derived from propylene acid glycidyl ester or glycidyl methacrylate.
The binding agent that is particularly preferred for the mineral wool fibre felt contains based on polyvinyl ester, based on polyacrylic ester or based on the carboxy-functionalized multipolymer of polyalkenyl aromatic substance, it comprises derived from the unsaturated list of ethylenic-or the copolymerization units of dicarboxylic acid, preferably derived from the copolymerization units of fumaric monoalkylester or toxilic acid monoesters or derived from propylene acid or methacrylic acid.
The binding agent that is particularly preferred for the mineral wool fibre felt contains based on polyvinyl ester, based on polyacrylic ester or based on epoxy functional and the carboxy-functionalized multipolymer of polyalkenyl aromatic substance, it comprises derived from the unsaturated list of ethylenic-or the copolymerization units of the glycidyl ester of dicarboxylic acid, the copolymerization units of preferred derived from propylene acid glycidyl ester or glycidyl methacrylate, and comprise derived from the unsaturated list of ethylenic-or the copolymerization units of dicarboxylic acid, preferably derived from fumaric monoalkylester or toxilic acid monoesters, the perhaps copolymerization units of derived from propylene acid or methacrylic acid.
The embodiment of particularly preferred binding agent is based on the multipolymer derived from alkenyl aromatic compounds of epoxy functional again, preferably derived from the multipolymer of vinylbenzene or derived from propylene acid esters and/or methacrylic ester, and this embodiment comprises derived from the unsaturated list of ethylenic-or the copolymerization units of the glycidyl ester of dicarboxylic acid, the copolymerization units of preferred derived from propylene acid glycidyl ester and/or glycidyl methacrylate.
The embodiment of particularly preferred binding agent is based on the derived from alpha of epoxy functional again, the unsaturated C of β-ethylenic
3-C
8-single-or the multipolymer of the ester of dicarboxylic acid, and this embodiment comprises the copolymerization units derived from the glycidyl ester of ethylenic unsaturated monocarboxylic, the copolymerization units of preferred derived from propylene acid glycidyl ester and/or glycidyl methacrylate.
The embodiment of another kind of preferred binding agent is based on the multipolymer derived from one or more vinyl ester, especially vinyl-acetic ester of epoxy functional, and this embodiment comprises the copolymerization units derived from the glycidyl ester of ethylenic unsaturated monocarboxylic, the copolymerization units of preferred derived from propylene acid glycidyl ester and/or glycidyl methacrylate.The multipolymer of described epoxy functional can also contain the structural unit derived from following source: α, the unsaturated C of β-ethylenic
3-C
8-single-or dicarboxylic acid and C
1-C
8The ester that-alkanol forms, α, the unsaturated C of β-ethylenic
3-C
8-single-or dicarboxylic acid such as vinylformic acid, methacrylic acid or toxilic acid or fumaric acid, alkene such as ethene or divinyl, perhaps two or more combination of these monomers.
Selected multipolymer epoxy functional and/or carboxy-functionalized is:
Multipolymer, it is derived from the vinyl ester of saturated carboxylic acid with derived from the glycidyl ester of ethylenic unsaturated carboxylic acid or derived from the unsaturated list of ethylenic-or dicarboxylic acid; Multipolymer, it is derived from the vinyl ester of saturated carboxylic acid, derived from C
1-C
8The ester that-alkanol and vinylformic acid and/or methacrylic acid and/or fumaric acid and/or toxilic acid form and derived from the glycidyl ester of ethylenic unsaturated carboxylic acid or derived from the unsaturated list of ethylenic-or dicarboxylic acid; Multipolymer, it is derived from the vinyl ester of saturated carboxylic acid, and derived from ethylene is derived from the ethylenic unsaturated carboxylic acid and derived from the glycidyl ester of ethylenic unsaturated carboxylic acid or derived from the unsaturated list of ethylenic-or dicarboxylic acid; Multipolymer, its derived from ethylene base ester, ethene, C
1-C
8The ester that-alkanol and vinylformic acid and/or methacrylic acid and/or fumaric acid and/or toxilic acid form, derived from the unsaturated list of ethylenic-or dicarboxylic acid, and derived from the glycidyl ester of ethylenic unsaturated carboxylic acid; Multipolymer, its derived from propylene acid esters and/or methacrylic ester, the unsaturated list of ethylenic-or the ester of dicarboxylic acid, derived from the glycidyl ester of ethylenic unsaturated carboxylic acid; Multipolymer, it is derived from vinylbenzene and optional divinyl, and/or derived from C
1-C
8The ester that-alkanol and vinylformic acid and/or methacrylic acid form, derived from the unsaturated list of ethylenic-or dicarboxylic acid, and derived from the glycidyl ester of ethylenic unsaturated carboxylic acid.
Should be appreciated that described polymerization can also utilize the comonomer of modifying character with ad hoc fashion jointly.General only with such auxiliary monomer as modified monomer, carry out copolymerization based on the monomer total amount for the treatment of polymerization with the amount less than 10 % by weight.
These monomers have different functions, and for example, they can be used for the stabilization of polymer dispersion, perhaps can be by crosslinked film force of cohesion or other character improved between polymerization or film stage, and/or via suitable functionality and linking agent reaction.
Can be used for monomer and/or its salt that further stable monomer normally has acid function.Above-mentioned carboxylic monomer helps to strengthen the cross-linking density in the bonding process of mineral wool fibre felt equally, except them, also can use the other monomer with other acid function, for example ethylenic unsaturated sulfonic acid, the unsaturated phosphonic acids of ethylenic or dihydrogen phosphoric acid ester, and water-soluble salt such as its sodium salt.Preferred monomers in this group is vinyl sulfonic acid and an alkali metal salt, acrylamido propanesulfonic acid and an alkali metal salt thereof and vinyl phosphonate and an alkali metal salt thereof.
The example of crosslinking coagent monomer is: has the monomer of two or more vinyl groups, has the monomer of two or more vinylidene groups, and the monomer with two or more kiki alkenyl groups.Particularly advantageous is dibasic alcohol and α, the diester that β-single ethylenic unsaturated monocarboxylic forms, and described monocarboxylic acid is preferably vinylformic acid and methacrylic acid; The diester that di-carboxylic acid and ethylenic unsaturated alcohol form; Other has the hydrocarbon of two ethylenic unsaturated groups; Perhaps diamine and α, the diamide that β-single ethylenic unsaturated monocarboxylic forms.
Example with such monomer of two non-conjugated ethylenic unsaturated double-bonds is: aklylene glycol diacrylate and dimethacrylate, such as glycol diacrylate, 1, the 2-propylene glycol diacrylate, 1, the ammediol diacrylate, 1, the 3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate or methacrylic ester and glycol diacrylate or methacrylic ester, 1,2-propylene glycol dimethacrylate, 1, the ammediol dimethacrylate, 1, the 3-butylene glycol dimethacrylate, the BDO dimethacrylate, hexanediyl ester, pentaerythritol diacrylate, and Vinylstyrene, the methacrylic vinyl acetate, vinyl acrylate, Vinyl crotonate, allyl methacrylate(AMA), allyl acrylate, diallyl maleate, diallyl fumarate, Phthalic acid, diallyl ester, methylene-bisacrylamide, vinylformic acid cyclopentadiene ester, vinyl hexanediacetate or methylene-bisacrylamide.
Yet, also can use the monomer that has more than two two keys, for example tetraene propoxy-ethane, Viscoat 295 or triallyl cyanurate.
Another group auxiliary monomer by can self-crosslinking or can form via the crosslinked auxiliary monomer of carbonyl.Example is diacetone-acryloamide(DAA), acetoacetic acid allyl ester, etheric acid vinyl acetate and acetoacetyl ethyl propenoate or AAEM.
Another group auxiliary monomer can carry out crosslinking reaction by self-crosslinking or with suitable monomer reactant and/or with the linking agent that exists under selected condition:
This group comprises the monomer with N-functional group; especially (methyl) acrylamide; allyl carbamate; vinyl cyanide; methacrylonitrile; N-methylol-(methyl) acrylamide; N-methylol allyl amino manthanoate; and N-methylol ester; the mannich base of the mannich base of-alkyl oxide or N-methylol (methyl) acrylamide or N-methylol allyl amino manthanoate; the acrylamido oxyacetic acid; Methacrylamide ylmethoxy acetic ester; N-(2; 2-dimethoxy-1-hydroxyethyl) acrylamide; N-dimethylaminopropyl (methyl) acrylamide; N-methyl (methyl) acrylamide; N-butyl (methyl) acrylamide; N-cyclohexyl (methyl) acrylamide; N-dodecyl (methyl) acrylamide; N-benzyl (methyl) acrylamide; p-hydroxy phenyl-(methyl) acrylamide; N-(3-hydroxyl-2; the 2-dimethyl propyl) Methacrylamide; ethyl-imidazolone (methyl) acrylate; N-(methyl) acryloxy ethyl imidazol(e) quinoline-1-ketone; N-(2-methacryloyl amido-ethyl) tetrahydroglyoxaline-2-ketone; N-[3-allyloxy-2-hydroxypropyl] amino-ethyl] tetrahydroglyoxaline-2-ketone; the N-vinyl formamide; NVP; perhaps, N-vinyl ethylidene-urea.
Another group auxiliary monomer is formed by hydroxy functional monomers, for example methacrylic acid and acrylic acid C
1-C
9-hydroxyalkyl acrylate, such as n-hydroxy ethyl methacrylate, n-hydroxyethyl meth acrylate, n-hydroxypropyl acrylate, n-HPMA, n-hydroxyl butylacrylic acid ester, n-hydroxyl butyl methyl acrylate, and with the affixture of oxyethane or propylene oxide.
Another group auxiliary monomer is made of the monomer that comprises silane group, such as vinyl trialkyl oxysilane, such as vinyltrimethoxy silane, vinyltriethoxysilane, alkyl vinyl dialkoxy silicane or (methyl) acryloxyalkyl trialkoxy silane are such as (methyl) acryloxy ethyl trimethoxy silane or (methyl) acryloxy propyl trimethoxy silicane.
Preferably preferably do not use within the scope of the invention any functional monomer who comprises formaldehyde free or combination.If this part as specific product optimization is necessary, rule is the compound that also will use as formaldehyde scavenger so.Its related example has N-or S-nucleophilic reagent, for example urea or sodium bisulfite and other compound of describing in the literature.Binding agent used according to the invention can obtain by any free radical polymerisation process.The example is polymerization in body, polymerization in solution, polymerization in suspension, perhaps especially letex polymerization.
The preferred binding agent that uses contains aqueous polymer dispersions, and it comprises the multipolymer that contains epoxy group(ing) and/or carboxyl described above.With these dispersions solvent-free or almost be applied to the mineral wool fibre felt under the solvent-free condition.
Except the polymkeric substance that contains epoxy group(ing) and/or carboxyl, dispersion preferably used according to the invention contains protective colloid and/or emulsifying agent.
Protective colloid is the polymerizable compound that is used for stabilising dispersions that exists in emulsion polymerization process.
The example of suitable protective colloid is polyvinyl alcohol; polyalkylene glycol; derivatived cellulose; starch derivative and gelatine derivative are perhaps from the acrylamide of the amino methacrylic ester of acrylate, the band of NVP, N-caprolactam, N-vinylcarbazole, 1-vinyl imidazole, 2-vinyl imidazole, 2-vinyl pyridine, 4-vinylpridine, acrylamide, Methacrylamide, band amino, band amino and/or the polymkeric substance of being with amino Methacrylamide to be derived.To comprehensive description of other suitable protective colloid referring to Houben-Weyl; vitochemical method (Methoden der organischen Chemie); the XIV/1 volume; macromolecular substance (Macromolecular substances); Georg-Thieme-Verlag; Stuttgart, 1961, the 411 to 420 pages.
Emulsifying agent is the lower molecular weight surface active cpd, and it is present in and is used for stabilising dispersions in the letex polymerization.Dispersion used according to the invention can neutralize ions and/or non-ionic and/or amphoteric emulsifier, the most preferably combination of nonionic emulsifying agent or nonionic emulsifying agent and anionic emulsifier.The tabulation of suitable emulsifying agent is referring to Houben-Weyl, vitochemical method (Methoden der organischen Chemie), the XIV/1 volume, macromolecular substance (Macromolecular substances), Georg-Thieme-Verlag, Stuttgart, 1961, the 192-208 pages or leaves.
Protective colloid can reach 20 % by weight based on the ratio of dispersion, preferably in the scope of 1 % by weight to 10 % by weight, especially in the scope of 2 % by weight to 8 % by weight.
Emulsifier based can reach 10 % by weight equally in the ratio of dispersion, preferably in the scope of 1 % by weight to 6 % by weight.
Binding agent used according to the invention contains at least a following linking agent that is selected from: amine, the derivative of amine (preferably including the amine of hydrophobically modified), and acid amides (especially amidated amine).The amine that uses as linking agent or the derivative of amine should alkoxylated or hydroxyalkylations.
Linking agent used according to the invention comprises such as single-or polyamines, especially diamines, preferred aliphat is single-or diamines or aromatic series list-or diamines.The amino group of linking agent used according to the invention can be primary amino, secondary amine and/or tertiary amine groups group.Preferably, described linking agent contains one or more primary aminos or secondary amine group.
What be preferably used as linking agent is the some of them amine groups by being converted into the derivative of the amine of amide group group with the hydrophobicity acid-respons.The derivative of described amine can have one or more amide group groups.
Particularly preferably be the use polyaminoamide.Polyaminoamide generally is the condensation product of unsaturated fatty acids and polyamines.The product of this compounds can be called
Commerce is buied.The example of such compound is referring to EP-A-1, and 533,331.
Preferred linking agent is from the derivative group of amine with amide structure: oligopolymer or polymerizable compound, its derived from carboxylic acid, especially derived from single-or dicarboxylic acid, perhaps derived from the mixture of the such carboxylic acid that comprises the ethylenic unsaturated carboxylic acid, and derived from diamines, oligomeric amine or polyamines.The ethylenic unsaturated carboxylic acid can form polymer, is preferably the polymer of 2 to 10 carboxylic acid.
Particularly preferred crosslinking polymer is derived from unsaturated carboxylic acid and diamines, perhaps derived from dimer and diamines or the oligomeric amine of ethylenic unsaturated carboxylic acid.
The ASTM D 2073 amine values of further preferred linking agent are between the every gram linking agent of 100 to 2000mg KOH, preferably between the every gram linking agent of 250 to 1000mg KOH from polyaminoamide.
Particularly preferably use
Series (Cognis GmbH, Germany(Germany Kening Co.,Ltd)) linking agent, as
Or
Linking agent used according to the invention exists with the amount of 0.1 % by weight to 10 % by weight usually based on binding agent.
The concentration of preferred linking agent is between the 1-10 % by weight, especially between the 2-7 % by weight.
When existence in the multipolymer of binding agent contains the auxiliary monomer of carbonyl, also can also occur crosslinked via these groups.The linking agent that can be used for this purpose comprises and is selected from following compound: two-or poly-
Azoles quinoline, two-or poly-imino-
Azoles quinoline, carbodiimide, two-or polyepoxide or blocked isocyanate (for example at EP-A-206, described in 059).
Can be used for the compound with metal ion of the divalence of being at least further crosslinked in addition.The compound of discussing can form complex compound or coordinate bond with the carboxylic group of binder polymer.This group compound generally includes Al
3+, Zn
2+, Sn
2+, Sn
4+, Ti
4+, TiO
2+, Hf
4+, HfO
2+, Zr
4+, ZrO
2+And the salt of other polyvalent ion.In the ideal case, these ions other component of binding agent can be incorporated into crosslinked in, thereby improve cross-linking density.Poly-(vinyl alcohol) through being commonly used for protective colloid is exactly an example.
Binding agent used according to the invention can also contain common additive.These comprise, for example, reduce film coalescence aid, softening agent, damping fluid, pH control reagent, dispersion agent, defoamer, filler, dyestuff, pigment, silane coupling agent, thickening material, viscosity modifier, solvent and/or the sanitas of film forming minimum temperature (" MFT ").
Binding agent used according to the invention should be used in the preparation that is adjusted to the pH value in the optimum range, and this scope provides the suitable reactivity of polymeric binder functional group and cross-linker groups.Described pH scope is preferably more than neutral point.Preferably, this pH scope is 7.5-10.
After the letex polymerization for the preparation of polymeric dispersions, perhaps after adding linking agent such as amidation amine, can obtain suitable pH value, perhaps can subsequently by adding pH control reagent, suitable pH value be set in preparation.
By, consecutive steps common at free-radical emulsion polymerization or in batches under the step, prepare the polymeric dispersions that particularly preferably uses.
The enforcement of the aqueous emulsion polymerization of the ethylenically unsaturated monomers that free radical causes is extensively described, therefore be well known to those of ordinary skill in the art [referring to, for example, polymer science and engineering encyclopedia (Encyclopedia of Polymer Science and Engineering) the 8th volume, the the 659th to 677 page, John Wiley﹠amp; Sons, Inc., 1987; D.C.Blackley, letex polymerization (Emulsion Polymerisation), the 155th to 465 page, Applied Science Publishers, Ltd., Essex, 1975; D.C.Blackley, polymer latex (Polymer Latices), the 2nd edition, I volume, the 33rd to 415 page, Chapman﹠amp; Hall, 1997; H.Warson, the application of synthetic resin emulsion (The Applications of Synthetic Resin Emulsions), the 49th to 244 page, Ernest Bonn.Ltd.London, 1972; D.Diederich, the 1990,24, the 135th to 142 pages of the chemistry in our epoch (Chemie in unserer Zeit), Verlag Chemie, Weinheim; J.Piirma,, letex polymerization (Emulsion Polymerisation), the 1st to 287 page, Academic Press, 1982;
The dispersion of synthesising macromolecule copolymer (Dispersionen synthetischer Hochpolymerer), the 1st to 160 page, Springer-Verlag, Berlin, 1969 and patent document DE-A 40 03 422].Typically, often by dispersant aid ethylenically unsaturated monomers is dispersed in the aqueous medium, uses at least a radical polymerization initiator to make its polymerization.
Use water miscible and/or oil-soluble initiator system, such as peroxydisulfate, azo-compound, hydrogen peroxide, organic hydroperoxide or dibenzoyl peroxide.They can be used alone, perhaps use with the reductibility compound combination, as the redox catalysis system, described reductibility compound for example is: iron (II) salt, Sodium Pyrosulfite, sodium bisulfite, S-WAT, V-Brite B, sodium sulfoxylate formaldehyde, 2-hydroxy phenyl hydroxymethyl-sulfonic acid or its sodium salt, 4-p-methoxy-phenyl hydroxymethyl-sulfinic acid or its sodium salt, 2-hydroxyl-2-sulfino (sulfinato) acetic acid or its disodium salt or zinc salt, and 2-hydroxyl-2-sulfino propionic acid or its disodium salt, perhaps xitix or its salt or saccharosonic acid or its salt.
Can be before polymerization or middle polymkeric substance protective colloid and/or the emulsifying agent of adding.Can add again again polymer stabilizer and/or emulsifying agent equally subsequently.Then choose wantonly this dispersion is further mixed with the additive that imagination is used for required application.
Can be at equipment preparation binding agent of the present invention, for example steel basin and/or the suitable mixing tank for this purpose known to persons of ordinary skill in the art.
After preparing binding agent, general direct it is applied to mineral wool fibre with the slag wool production fibrefelt.This can finish with related application method known to persons of ordinary skill in the art, for example uses the dispersion spray fiber.After using and after the heat treated moistening fiber non-woven web raw material, reactive adhesive cures, solidify and stablize thus the mineral wool fibre felt.Preferably induce curing reaction by improving temperature.Will know that such as those of ordinary skills solidification rate can be by other measure impact by prescription.Typical solidification value is preferably 70 ℃-250 ℃, especially 130 ℃-180 ℃.
The present invention also provides the method for producing the above mineral wool fibre felt that limits, and said method comprising the steps of:
I) use crosslinkable composition to the mineral wool fibre felt that does not bond, described composition contains multipolymer epoxy group(ing) and/or carboxylic, and the linking agent that is selected from the derivative of amine or amine; And
J) pass through the crosslinked of binding agent, make mineral wool fibre strike up partnership to form the mineral wool fibre felt of bonding.
Mineral wool fibre felt of the present invention has made up comparable physical strength and application performance, and its formaldehyde discharges very low and preferably do not have formaldehyde to discharge.
Mineral wool fibre felt of the present invention is particularly useful as insulating material, in particular for heat insulation, and the thermal isolation of the structure of more especially be used for building and the structure object of any classification.
Following examples are used for illustrating the present invention.Except as otherwise noted, the umber among the embodiment and per-cent are by weight.
Embodiment
Embodiment
Dispersion A
In the glass steel basin that is equipped with whipping appts (anchor stirrer), feeding unit and electronic temp control, dissolving is 2.97 parts in 60 parts of deionized waters
EPN 287 nonionic emulsifier (from Clariant), 0.5 part
LS anionic emulsifier (from Clariant), 0.25 part of sodium-acetate, 0.51 part of sodium vinyl sulfonate, 0.04 part of Sodium Pyrosulfite and 0.00023 part of ferric sulfate (II) ammonium (be 1% solution) are to form initial charging.
Under stirring, 5 parts of vinyl-acetic ester emulsifications in initial charging, then, will initially be feeded and will be heated to 65 ℃, in the time of 40 ℃, add 0.22 part of solution that Sodium Persulfate forms in 1.77 parts of deionized waters, to start polyreaction.
In case internal temperature arrives 65 ℃, begins to be metered into 95 parts of vinyl-acetic esters and 3 parts of glycidyl methacrylate, and continue 240 minutes.In reaction, keep internal temperature at 65 ℃.Add in the metering of monomer and to finish front 30 minutes, in 30 minutes process, temperature is brought up to 85 ℃ from 65 ℃, and simultaneously, in 30 minutes process, add 0.11 part of solution that Sodium Persulfate forms in 1.77 parts of deionized waters.
After the metering interpolation of monomer is finished, this batch kept 60 minutes, then cooling at 85 ℃.
Solids content: 60.7%
Viscosity RVT(23 ℃ of Bu Shi (Brookfield)), axle 2,20rpm:780mPas
pH：4.2
Dispersion B
In the glass steel basin that is equipped with whipping appts (anchor stirrer), feeding unit and electronic temp control, in 31.5 parts of deionized waters, dissolve 0.25 part during beginning
A3065 nonionic emulsifier (from Cognis) is to prepare initial charging.
Simultaneously, in the container that separates, dissolving is 2.72 parts in 55.6 parts of deionized waters
A 3065 and 2 parts
FES 77 anionic emulsifier (from Cognis).Under strong agitation, with following monomer mixture emulsification in this solution with the preparation monomer emulsion: 30 parts of methyl methacrylates, 10 parts of butyl acrylates, 60 parts of vinylbenzene, 1.5 parts of glycidyl methacrylate, 2 parts of methacrylic acids and 1 part of vinylformic acid.
Then, prepare the solution (=oxidizing agent solution) of 0.195 part of Sodium Persulfate in 2.92 parts of deionized waters, and the solution (=reductant solution) of 0.1 part of Sodium Pyrosulfite in 0.91 part of deionized water.
To initially feed and be heated to 80 ℃.Subsequently, in initial charging, dropwise add 2.85%(by weight) monomer emulsion and 22.8%(by weight) reductant solution.After 5 minutes, add 33.3% oxidizing agent solution in this mixture with initiated polymerization.After having spent again 15 minutes, begin to be metered into monomer emulsion and initiator system (Oxidizing and Reducing Agents solution), this process of monomer emulsion has been continued 240 minutes, add this process in the time of to two kinds of solution of initiator system and continued 225 minutes.In the middle of causing and measure, reaction keeps the internal temperature of reactor at 80 ℃.
After the metering interpolation of monomer is finished, in 5 minutes process, add 0.023 part
The solution that Foamex 805 defoamers (from Evonik) form in 0.13 part of deionized water.Horse back dropwise adds 1 part of methyl methacrylate to polymkeric substance in 10 minutes process subsequently.Added fast the solution that 0.065 part of Sodium Persulfate forms in 0.21 part of deionized water after, temperature rises to 85 ℃ and kept 90 minutes at 85 ℃.Then, internal temperature is down to 65 ℃, adds 0.11 part
AW 70(is from 70% the aqueous solution of the tertbutyl peroxide of Akzo) solution that in 0.42 part of deionized water, forms.After 15 minutes, adding 0.11 part of solution that Sodium Pyrosulfite forms in 0.42 part of deionized water, is 15 minutes time of lag subsequently.At once repeat this operation thereafter.Add the solution that 0.033 part of ammoniacal liquor (be 25% solution) forms in 0.13 part of deionized water after, internal temperature is down to below 40 ℃, use the ammonia soln pH of dilution to be set to 4.5.
Solids content: 53.1%
Brookfield viscosity RVT(23 ℃), axle 1,20rpm:120mPas
pH：4.5
The cross-linking density of the dispersion of mensuration glycidyl-functionalised and the mixture of amidation amine (linking agent)
Mainly utilize the resol of the three-dimensional netted thing that can solidify to form tight engagement to produce mineral wool fibre according to prior art.High cross-linking density causes having the very formation of the plastics of thermoset nature.The combination of the polymeric dispersions of glycidyl-functionalised and suitable linking agent, the amidation amine of described linking agent as describing in the present invention can solidify to form the highly cross-linked polymer system with thermoset nature equally.Therefore, use hereinafter cross-linking density as the tolerance of the validity of bonding system.
Measure cross-linking density by measuring insoluble composition after the thermal treatment, from the film that the mixture of dispersion and linking agent forms.Method therefor is similar to the method for describing among the US-A-2008/0175997.Under all situations, the film thickness that is applied to the substrate of plane polishing (planar-ground) sheet glass is 250 microns, uses dinethylformamide (DMF) as solvent.Use Mathis Labdryer LTE-S baking box that film is carried out thermal conditioning.The thermal conditioning time of the embodiment that below lists is 10 minutes.In the meantime, the temperature that is exposed to of the dried film of conversion.Corresponding temperature clearly, has shown the embodiments of the invention of studying in the table in following table.
Before taking off film, prepare in the following manner sample: with dispersion with suitable be that (solids content by dispersion is calculated) 3 % by weight and that be 6 % by weight linking agent mixes.That use in the embodiment that this paper lists is Cognis
150 products.Use amidation amine by the pattern that provides, under slowly stirring, in 5 minutes, it is incorporated in the dispersion.Subsequently, measure the pH value of mixture, find to depend on used dispersion and the amount of linking agent, this pH value is between 8 and 9.5.
In experiment, dispersion A and B have been measured the dependency of degree of crosslinking to temperature.In the situation of dispersion A, also measured the dependency of degree of crosslinking to the amount of linking agent.Higher temperature, the thermal conditioning time of growing and the crosslinker concentration of optimization have active influence to degree of crosslinking.The amount that does not add the insoluble composition in the film of the dispersion A of linking agent and B is used as comparative example.
Table
As apparent from the table, compare (each example does not all add linking agent) use of suitable linking agent in example with comparative example V1 with V2 and improved the mark of insoluble composition, improved thus cross-linking density, cross-linking density is the amount of the linking agent that adds and the function of temperature.Can also find out obviously that the effect that increases cross-linking density is played in the existence of carboxylic group among the dispersion B, be reflected in the increase of per-cent of insoluble composition, this test 5 and test 8 relatively clear especially.
Claims (18)
1. the mineral wool fibre felt that forms with the binding agent bonding, described binding agent contains epoxy functional and/or carboxy-functionalized emulsion copolymers, and as the amine of linking agent and/or the derivative of amine.
2. mineral wool fibre felt according to claim 1, wherein said epoxy functional and/or carboxy-functionalized emulsion copolymers is polyvinyl ester, polyacrylic ester or polyalkenyl aromatic substance, described emulsion copolymers comprises derived from the unsaturated list of ethylenic-or the copolymerization units of the glycidyl ester of dicarboxylic acid, and/or comprises derived from the unsaturated list of ethylenic-or the salt of dicarboxylic acid or described carboxylic acid or copolymerization units of acid anhydrides.
3. mineral wool fibre felt according to claim 2, wherein said epoxy functional and/or carboxy-functionalized emulsion copolymers is derived from alkenyl aromatic compounds, preferably derived from vinylbenzene, and/or derived from propylene acid esters and/or methacrylic ester, described emulsion copolymers comprises derived from ethylenic unsaturated monocarboxylic glycidyl ester, the copolymerization units of preferred derived from propylene acid glycidyl ester and/or glycidyl methacrylate, and/or comprise derived from the unsaturated list of ethylenic-or dicarboxylic acid, the perhaps copolymerization units of the salt of described carboxylic acid or acid anhydrides.
4. mineral wool fibre felt according to claim 2, wherein said epoxy functional and/or carboxy-functionalized emulsion copolymers derived from alpha, the unsaturated C of β-ethylenic
3-C
8-single-or the ester of dicarboxylic acid, described emulsion copolymers comprises the copolymerization units derived from ethylenic unsaturated monocarboxylic glycidyl ester, preferred derived from propylene acid glycidyl ester and/or glycidyl methacrylate, and/or comprises derived from the unsaturated list of ethylenic-or the salt of dicarboxylic acid or described carboxylic acid or copolymerization units of acid anhydrides.
5. mineral wool fibre felt according to claim 2, wherein said epoxy functional and/or carboxy-functionalized emulsion copolymers is derived from one or more vinyl ester, described emulsion copolymers comprises derived from ethylenic unsaturated monocarboxylic glycidyl ester, the copolymerization units of preferred derived from propylene acid glycidyl ester and/or glycidyl methacrylate, and/or comprise derived from the unsaturated list of ethylenic-or dicarboxylic acid, the perhaps copolymerization units of the salt of described carboxylic acid or acid anhydrides, and/or comprise derived from the unsaturated list of ethylenic-or dicarboxylic acid, the perhaps copolymerization units of the salt of described carboxylic acid or acid anhydrides.
6. mineral wool fibre felt according to claim 5, the emulsion copolymers of wherein said epoxy functional also contains the structural unit derived from following structure: C except containing the structural unit derived from one or more vinyl ester
1-C
8-alkanol and α, the unsaturated C of β-ethylenic
3-C
8-single-or the dicarboxylic acid ester, the α that form, the unsaturated C of β-ethylenic
3-C
8-single-or two or more combination of dicarboxylic acid, alkene or these monomers.
7. mineral wool fibre felt according to claim 2, the emulsion copolymers of wherein said epoxy functional is selected from following multipolymer: multipolymer, it is derived from the vinyl ester of saturated carboxylic acid with derived from the glycidyl ester of ethylenic unsaturated carboxylic acid; Multipolymer, it is derived from the vinyl ester of saturated carboxylic acid, derived from C
1-C
8The ester that-alkanol and vinylformic acid and/or methacrylic acid and/or fumaric acid and/or toxilic acid form, and derived from the glycidyl ester of ethylenic unsaturated carboxylic acid; Multipolymer, it is derived from the vinyl ester of saturated carboxylic acid, and derived from ethylene is derived from the ethylenic unsaturated carboxylic acid and derived from the glycidyl ester of ethylenic unsaturated carboxylic acid; Multipolymer, its derived from ethylene base ester, ethene, C
1-C
8The ester that-alkanol and vinylformic acid and/or methacrylic acid and/or fumaric acid and/or toxilic acid form is derived from the ethylenic unsaturated carboxylic acid and derived from the glycidyl ester of ethylenic unsaturated carboxylic acid; Multipolymer, the ester of its derived from propylene acid esters and/or methacrylic ester, ethylenic unsaturated carboxylic acid is derived from the glycidyl ester of ethylenic unsaturated carboxylic acid; Multipolymer, it is derived from vinylbenzene and divinyl, and/or derived from C
1-C
8The ester that-alkanol and vinylformic acid and/or methacrylic acid form is derived from the ethylenic unsaturated carboxylic acid and derived from the glycidyl ester of ethylenic unsaturated carboxylic acid.
8. mineral wool fibre felt according to claim 7, wherein said polymkeric substance are the polyvinyl esters of epoxy functional that contains the vinyl acetate monomer unit of at least 50 % by weight.
9. at least one described mineral wool fibre felt in 8 according to claim 1 wherein introduced described binding agent with the form of the aqueous dispersion of polymkeric substance.
10. at least one described mineral wool fibre felt in 9 according to claim 1, the content of wherein said binding agent is in the scope of 0.1 % by weight to 10 % by weight, preferably in the scope of 0.5 % by weight to 5 % by weight.
11. at least one described mineral wool fibre felt in 10 according to claim 1, that wherein said linking agent is selected from is single-or polyamines, preferred aliphat is single-or diamines or aromatic series list-or diamines.
12. at least one described mineral wool fibre felt in 10 according to claim 1, wherein said linking agent is selected from the acid amides with one or more amide groups, and especially polyaminoamide very particularly preferably is the condensation product of unsaturated fatty acids and polyamines.
13. the mineral wool fibre felt of claim 12, wherein said linking agent is selected from polyaminoamide, and the ASTM D 2073 amine values of described polyaminoamide are between the every gram linking agent of 100 to 2000mg KOH, preferably between the every gram linking agent of 250 to 1000mg KOH.
14. the mineral wool fibre felt of claim 12, use therein linking agent neither oxyalkylated neither hydroxyalkylation.
15. at least one described mineral wool fibre felt in 14 according to claim 1, the amount of use therein linking agent take binding agent as the basis in the scope of 0.1 % by weight to 10 % by weight, preferably in the scope of 1 % by weight to 10 % by weight, especially in the scope of 2 % by weight to 7 % by weight.
16. produce the method for mineral wool fibre felt according to claim 1, said method comprising the steps of:
I) use crosslinkable composition to mineral wool fibre, described composition contains epoxy functional and/or carboxy-functionalized emulsion copolymers, and the linking agent that is selected from the derivative of amine or amine; And
J) pass through the crosslinked of binding agent, make mineral wool fibre strike up partnership to form the mineral wool fibre felt of bonding.
17. method according to claim 16 is wherein used described crosslinkable composition with the form of aqueous dispersion.
18. each the described mineral wool fibre felt in 15 is as the purposes of insulating material according to claim 1, in particular for heat insulation, more especially is used for the thermal isolation of the structure object of the structure of building and any classification, is preferred for the heat insulation of roof.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102010015575.6 | 2010-04-19 | ||
| DE201010015575 DE102010015575A1 (en) | 2010-04-19 | 2010-04-19 | Mineral wool fiber mats, process for their preparation and use |
| PCT/EP2011/001434 WO2011131279A1 (en) | 2010-04-19 | 2011-03-23 | Mineral wool fiber mats, method for producing same, and use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102858709A true CN102858709A (en) | 2013-01-02 |
Family
ID=44121542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800195470A Pending CN102858709A (en) | 2010-04-19 | 2011-03-23 | Mineral wool fiber mats, method for producing same, and use |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20130095719A1 (en) |
| EP (1) | EP2560928A1 (en) |
| CN (1) | CN102858709A (en) |
| AR (1) | AR081826A1 (en) |
| BR (1) | BR112012026455A2 (en) |
| DE (1) | DE102010015575A1 (en) |
| WO (1) | WO2011131279A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262920A (en) * | 2014-09-03 | 2015-01-07 | 安徽梦谷纤维材料科技有限公司 | Fiber-reinforced resin solar bracket and preparation method thereof |
| CN104354406A (en) * | 2014-10-22 | 2015-02-18 | 安徽梦谷纤维材料科技有限公司 | Charging pile board and preparation method thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102012100025A1 (en) | 2012-01-03 | 2013-07-04 | Groz-Beckert Kg | Apparatus and method for producing a mineral wool fiber part |
| DE102013222770A1 (en) * | 2013-11-08 | 2015-05-13 | Wacker Chemie Ag | Use of binder compositions for the production of textile fabrics |
| RU2681856C2 (en) | 2014-04-11 | 2019-03-13 | Басф Се | Method of obtaining aqueous polymer dispersion |
| FR3074798B1 (en) | 2017-12-11 | 2019-11-15 | Saint-Gobain Isover | INSULATING PRODUCT COMPRISING MINERAL FIBERS AND A BINDER |
| US20240109993A1 (en) * | 2020-12-02 | 2024-04-04 | Tsinghua University | Crosslinked copolymer having repeating unit carrying amide group and carboxyl and/or its ammonium salt and repeating unit of a-monoolefin |
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|---|---|---|---|---|
| DE2604544A1 (en) | 1976-02-06 | 1977-08-11 | Basf Ag | BINDING AGENT FOR STRENGTHENING GLASS FIBER MATS |
| US4297453A (en) * | 1980-05-12 | 1981-10-27 | Monsanto Company | Compositions of epichlorohydrin rubber and nylon |
| DE3521618A1 (en) | 1985-06-15 | 1986-12-18 | Bayer Ag, 5090 Leverkusen | POLYISOCYANATE PREPARATION IN WATER AND THEIR USE AS ADDITIVES FOR AQUEOUS ADHESIVES |
| DE4003422A1 (en) | 1990-02-06 | 1991-08-08 | Basf Ag | WAITER POLYURETHANE PREPARATIONS |
| DE4024727A1 (en) | 1990-08-03 | 1992-02-06 | Gruenzweig & Hartmann | Mineral wool prods. with hydrophilic properties - by treating mineral wool with mixt. of PF resin binder, nitrogen-carbonyl cpd., aq. acrylic] resin micro-sol and specified surfactant |
| DE19720674C1 (en) | 1997-02-03 | 1998-09-03 | Gruenzweig & Hartmann | Binder for fire resistant mineral wool products |
| DE19735959A1 (en) * | 1997-08-19 | 1999-02-25 | Basf Ag | Thermally curable, aqueous binding agent composition |
| US8105690B2 (en) * | 1998-03-03 | 2012-01-31 | Ppg Industries Ohio, Inc | Fiber product coated with particles to adjust the friction of the coating and the interfilament bonding |
| FR2782711B1 (en) | 1998-09-01 | 2001-05-25 | Saint Gobain Isover | PROCESS FOR IMPROVING THE MECHANICAL STRENGTH OF A MINERAL WOOL INSULATING PRODUCT, INSULATING PRODUCT AND SIZING COMPOSITION |
| DE19900459A1 (en) * | 1999-01-08 | 2000-07-13 | Basf Ag | Polymer dispersion |
| EP1086932A1 (en) | 1999-07-16 | 2001-03-28 | Rockwool International A/S | Resin for a mineral wool binder comprising the reaction product of an amine with a first and second anhydride |
| DE19956420C1 (en) | 1999-11-24 | 2001-03-15 | Alberdingk Boley Gmbh | Binder composition, for molding, particularly for molding wood fibers, comprises carboxylated polymer, amine and crosslinker, can be cured at low temperature |
| DE10014399A1 (en) | 2000-03-23 | 2001-10-04 | Wacker Polymer Systems Gmbh | Crosslinkable polymer composition useful as a textile binder, comprises a carboxy-functional copolymer and a copolymer having carboxy-reactive groups |
| EP1164163A1 (en) | 2000-06-16 | 2001-12-19 | Rockwool International A/S | Binder for mineral wool products |
| US6548155B1 (en) | 2000-07-19 | 2003-04-15 | Johns Manville International, Inc. | Fiber glass mat |
| AU2003245285A1 (en) | 2002-06-06 | 2003-12-22 | Georgia-Pacific Resins, Inc. | Epoxide-type formaldehyde free insulation binder |
| JP4772502B2 (en) | 2003-03-25 | 2011-09-14 | 三洋化成工業株式会社 | Binder composition for mineral fiber and mineral fiber mat |
| US7160979B2 (en) | 2003-11-24 | 2007-01-09 | Henkel Corporation | Polyamides |
| JP2006089906A (en) | 2004-08-25 | 2006-04-06 | Sanyo Chem Ind Ltd | Binder for mineral fiber |
| DE102004061144A1 (en) * | 2004-12-16 | 2006-06-22 | Basf Ag | Use of formaldehyde-free aqueous binders for substrates |
| US20060258248A1 (en) | 2005-05-11 | 2006-11-16 | Shooshtari Kiarash A | Fiberglass binder comprising epoxidized oil and multifunctional carboxylic acids or anhydrides |
| DE102005029479A1 (en) | 2005-06-24 | 2007-01-04 | Saint-Gobain Isover G+H Ag | Process for producing bonded mineral wool and binder therefor |
| DE102005037113A1 (en) * | 2005-08-03 | 2007-02-08 | Basf Ag | Use of a thermally curable aqueous composition as a binder for substrates |
| DE102005056791B4 (en) | 2005-11-28 | 2014-04-30 | Saint-Gobain Isover G+H Ag | Composition, mineral wool binder containing this composition and use of this composition |
| US20080175997A1 (en) | 2007-01-19 | 2008-07-24 | Goldstein Joel E | Emulsion polymer binder with azirdine crosslinking agent for glass fiber webs |
-
2010
- 2010-04-19 DE DE201010015575 patent/DE102010015575A1/en not_active Withdrawn
-
2011
- 2011-03-23 CN CN2011800195470A patent/CN102858709A/en active Pending
- 2011-03-23 US US13/639,060 patent/US20130095719A1/en not_active Abandoned
- 2011-03-23 WO PCT/EP2011/001434 patent/WO2011131279A1/en active Application Filing
- 2011-03-23 EP EP11711459A patent/EP2560928A1/en not_active Withdrawn
- 2011-03-23 BR BR112012026455A patent/BR112012026455A2/en not_active IP Right Cessation
- 2011-04-18 AR ARP110101329 patent/AR081826A1/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262920A (en) * | 2014-09-03 | 2015-01-07 | 安徽梦谷纤维材料科技有限公司 | Fiber-reinforced resin solar bracket and preparation method thereof |
| CN104354406A (en) * | 2014-10-22 | 2015-02-18 | 安徽梦谷纤维材料科技有限公司 | Charging pile board and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102010015575A1 (en) | 2011-10-20 |
| WO2011131279A1 (en) | 2011-10-27 |
| US20130095719A1 (en) | 2013-04-18 |
| BR112012026455A2 (en) | 2016-08-09 |
| EP2560928A1 (en) | 2013-02-27 |
| AR081826A1 (en) | 2012-10-24 |
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