WO2006133978A1 - (meth)acrylat-zusammensetzung mit reduzierter sauerstoffinhibierung - Google Patents
(meth)acrylat-zusammensetzung mit reduzierter sauerstoffinhibierung Download PDFInfo
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- WO2006133978A1 WO2006133978A1 PCT/EP2006/060540 EP2006060540W WO2006133978A1 WO 2006133978 A1 WO2006133978 A1 WO 2006133978A1 EP 2006060540 W EP2006060540 W EP 2006060540W WO 2006133978 A1 WO2006133978 A1 WO 2006133978A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C08K5/04—Oxygen-containing compounds
-
- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
Definitions
- Free-radical curing (meth) acrylate compositions have long been known. They are used as adhesives, sealants and coatings. A major advantage is the fast curing of these systems. However, it is disadvantageous and known that the curing of (meth) acrylate can be inhibited by the oxygen present in the air. As a result, the polymerization of the (meth) acrylates is severely restricted where the monomers are in contact with air and thus sticky surfaces are formed. However, such stickiness is a major drawback, since on the one hand there may stick dust and thus leads to visible contamination and on the other hand lead the non or weakly crosslinked monomers to a greasy and sticky surface, which is unpleasant to touch. Furthermore, the inhibition causes an odor immission and contamination by unreacted monomers.
- Another starting point for solving the problem of oxygen is the overlaying of the surface with an inert gas or working under inert gas.
- inert gases are, for example, nitrogen, argon or CO 2 .
- this method is very complicated and expensive and is typically only suitable for small surfaces.
- This also applies to another solution, namely for working under reduced pressure.
- Another way to reduce the oxygen inhibition is the use of volatile compounds or monomers, which evaporate during the polymerization and thus displace the air from the surface. This possibility is realized, for example, in the polymerization of methyl methacrylate and methyl acrylate. These monomers have high volatility and, therefore, only low oxygen inhibition is observed in formulations based on these monomers.
- a disadvantage of this solution is that problems arise with the odor and / or with the toxicity and / or safety at work due to the high amounts of volatilizing compounds.
- Another method is working at elevated temperature or annealing after polymerization at higher temperatures. As a result, the stickiness is also reduced.
- the disadvantage here however, that the heating is on the one hand cost and labor intensive and on the other hand, only for smaller areas or workpieces is practically feasible.
- the sticky layer that forms by the oxygen inhibition can also be removed. This can be done mechanically or by wiping with a suitable solvent. On the one hand, however, the removal is an additional working step and on the other hand can damage the polymerized surface.
- the use of ⁇ -dicarbonyl compounds in air-drying systems is known.
- Such air-drying systems have higher molecular weight polymers and in particular have no peroxides or hydroperoxides, but react via oxygen by oxidative crosslinking of double bonds, and are particularly very slow compared with (meth) acrylates.
- DE-A-26 01 378 discloses the use of derivatives of ⁇ -butyrolactone and ⁇ -valerolactone in air-drying polyester resins. These air-drying polyester resins are styrene-based polycondensation products of unsaturated dicarboxylic acids and polyols.
- DE-A-30 44 695 describes an air-crosslinking coating agent in which ⁇ -dicarbonyl compound is added to a copolymer.
- composition allows for rapid cure in the presence of oxygen, wherein the oxygen inhibition is reduced wholly or at least greatly, especially compared to the analogous (meth) acrylate composition without the compound of formula (I) and without the metal salt or metal complex compound of claim 1 ,
- the composition also has excellent mechanical properties that are widely variable and with which both thin and thick coatings but also sealants and adhesives can be realized.
- formulations which are free of compounds which are known to have a strong and disturbing odor such as (meth) acrylic acid methyl ester or styrene, can also be produced hereby.
- the present invention relates to two-component or multi-component compositions which comprise at least the following ingredients: a) at least one (meth) acrylate; b) at least one compound of formula (I); c) at least one metal salt or metal complex compound of at least one metal selected from the group of transition metals; d) at least one peroxide or at least one perester or at least one hydroperoxide; wherein a first component K1 comprises at least the ingredient c) and a second component K2 comprises at least the ingredient d).
- metal is not understood in the sense of "metallic” throughout the present document, but instead stands for a metal cation in a salt or for a metal cation bound in a complex compound to ligands.
- transition metals throughout the present document are meant both the metals of the atomic number 21-30, 39-48, 57-80 and 89 to 109 of the periodic system, ie the term also includes the so-called lanthanides and the actinides.
- the two or more component compositions comprise at least the two components K1 and K2.
- the first component K1 comprises at least the ingredient c). That is, the component K1 consists of or comprises at least one metal salt or a metal complex compound of at least one metal selected from the group of transition metals.
- the metal of the at least one metal salt or metal complex compound is a metal selected from the group consisting of cobalt, manganese, vanadium, iron, copper, chromium and zirconium.
- the second component K2 comprises at least the ingredient d). That is, component K2 consists of or comprises at least one peroxide or at least one perester or at least one hydroperoxide.
- the two- or multi-component composition contains the ingredient a), namely at least one (meth) acrylate. It is basically all in the adhesive and sealant and
- Examples of such (meth) acrylates are hydroxymethyl (meth) acrylate,
- HPA Hydroxyethyl (meth) acrylate
- HPA hydroxypropyl (meth) acrylate
- HBA hydroxybutyl (meth) acrylate
- HPA hydroxypropyl (meth) acrylate
- HPMA hydroxybutyl (meth) acrylate
- HPA hydroxypropyl (meth) acrylate
- Methacrylates are preferred over acrylates.
- the two- or multi-component composition contains the ingredient b), namely at least one compound of the formula (I).
- n hereby stands for a value of 1 to 20.
- n represents a value of 1, 2, 3, 4, 5 or 6.
- n is 1.
- the substituent R 1 is an n-valent organic radical ,
- n-valent organic radical herein and hereinafter an organic radical is referred to, to which n bonds take place.
- the substituent R 2 is an optionally substituted, alkyl group, cycloalkyl group, aryl group, aralkyl group or R 2 together with R 3 includes a ring which optionally heteroatoms in or at the ring, or R 2 is a radical OR 4 .
- R 4 is an optionally substituted, alkyl group, cycloalkyl group, aryl group or aralkyl group, or R 4 includes together with R 3 a ring which optionally has heteroatoms in or on the ring.
- the substituent R 3 is an optionally substituted,
- Alkyl group, cycloalkyl group, aryl group, aralkyl group or together with R 2 includes a ring which optionally comprises heteroatoms in or on the ring.
- the substituents R 2 and R 3 may each independently represent an alkyl group, cycloalkyl group, aryl group or aralkyl group, which may be substituted at most. Or the substituents R 2 and R 3 together form a ring. This formed ring is typically formed by interconnected carbons. However, heteroatoms can also be present in this ring, or heteroatoms can also be bonded to the atoms which form the ring.
- radicals R 2 and R 3 are connected to one another and close a ring.
- n-valent organic radical for R 1 are on the one hand divalent
- Radicals such as alkylene, phenylene, cycloalkylene, oxyalkylene and poly (oxyalkylene) groups suitable.
- Preferred are ethylene, propylene, cyclohexylene.
- trivalent to typically hexahydric radicals are possible, which are derived, for example, from cycloaliphatic or benzene derivatives.
- n-valent radicals are heteroatoms containing n-valent organic radicals R 1 .
- Suitable n-valent radicals R 1 are, in particular, those which are derived from polyols of the formula R 1 (OH) n .
- R 1 is a radical R 1 '(O) n , ie an alcohol R 1 (OH) n with n hydroxyl groups, after removal of all protons of all hydroxyl groups.
- alkyl groups such as ethyl or methyl groups
- dihydric alcohols are polyetherdiols, polyesterdiols, polycarbonatediols and hydrogenated polybutadienes. Particular preference is given to diols of the formula (II)
- Copolymers is random or block. This is indicated by the use of dashed bonds in formula (II).
- Suitable trivalent radicals R 1 are, in particular, the radicals derived from triols.
- triols are glycerol (1-, 2-, 3-propanetriol), trimethylolpropane, trimethylolethane, and their alkoxylated derivatives.
- Suitable tetravalent radicals R 1 are, in particular, the radicals derived from tetrols.
- tetrols are pentaerythritol, ⁇ , ⁇ '-diglycerol (bis (2,3-dihydroxypropyl) ether), di (trimethylolpropane) (2,2'-oxybis (methylene) bis (2-ethyl) 1, 3-propanediol)) and di- (trimethylolethane) (3- (3-hydroxy-2-hydroxymethyl-2-methyl-propoxy) -2-hydroxymethyl-2-methyl-propane-1-ol), and their alkoxylated derivatives.
- Suitable hexavalent radicals R 1 are, in particular, the radicals derived from hexols. Examples of such hexols are di (pentaerythritol) (3- (3-hydroxy-2,2-bis-hydroxymethyl-propoxy) -2,2-bis-hydroxymethyl-propan-1-ol) and their alkoxylated derivatives. Further preferred radicals R 1 are derived from sugars or sugar alcohols. Such sugars are monosaccharides or disaccharides or trisaccharides. As sugar alcohols in particular Tetrite, Pentite and Hexite apply. These sugars and sugar alcohols may be chemically modified, such as alkoxylated.
- Such an alcohol R 1 (OH) n is preferably trimethylolpropane, pentaerythritol, glycerol, a sugar or a diol of the formula (II).
- a particularly preferred methyl ester is the following methyl ester:
- Transesterifications can be carried out by known methods, as described, for example, in Jerry March, “Advanced Organic Chemistry,” 3 rd Edition, John Wiley & Sons, 1985, pp. 351-353.
- the n-valent alcohol R 1 (OH) n is an OH-terminated polyurethane prepolymer.
- OH-terminated polyurethane prepolymers are obtained in the manner known to the person skilled in the art, for example by reacting at least one polyol with at least one polyisocyanate, the polyol being used in a stoichiometric excess of the hydroxyl groups over the isocyanate groups.
- R 5 represents an optionally substituted alkyl group, cycloalkyl group, aryl group or
- the compound of the formula (I) is a compound of the formula (IV) or (V)
- v 1, 2 or 3 and X is O, S or NR 7 wherein R 7 is H or an optionally substituted alkyl group, cycloalkyl group, aryl group, aralkyl group.
- v represents the values 1 or 2.
- X is preferably an oxygen atom.
- the compound of formula (I) is a compound of formula (IV) and R 1 is an OR 5 radical with R 5 being an optionally substituted, alkyl, cycloalkyl, aryl or aralkyl group or a group Formula (IM).
- the sum of m , p and q gives a value of 1 to 65.
- the building blocks which result in the preparation of these polyols from ethylene oxide, propylene oxide and butylene oxide and are therefore designated in formula (IM) as "EO”, “PO” and “BO” , in the case of copolymers, may be random or block-like, as indicated by the use of hatched bonds in formula (M)
- the arrangement can be achieved by the methods known for this purpose.
- Formula (I) is a compound of formula (V) and R 1 is an optionally substituted alkyl group, cycloalkyl group, aryl group or aralkyl group, preferably a C 1 -C 6 alkyl group.
- the compound of formula (I) is acetylbutyrolactone or cyclopentanone-2-carboxylic acid ethyl ester or cyclopentanone-2-carboxylic acid methyl ester.
- the two- or multi-component composition contains the ingredient c), namely at least one metal salt or a metal complex compound of at least one metal selected from the group of transition metals, in particular selected from the group comprising cobalt, manganese, vanadium, iron, copper, chromium and zirconium.
- Metal salts or metal complex compounds of the metals cobalt, manganese and vanadium have proved to be particularly suitable.
- mixtures of at least two metal complex compounds of at least two metals are present.
- at least one manganese complex and a cobalt complex and / or a vanadium complex is present.
- at least one cobalt complex and a manganese complex and / or a vanadium complex are present.
- metal salts or metal complex compounds in particular based on carboxylic acids, in particular naphthenates, octoates or ethylhexanoates, preferably octoates. There may be other additives such as accelerators and complexing agents.
- metal salts or metal complex compounds as described for example by Borchers, Langenfeld, Germany under the Product series be sold with the trade name Borchers® Octa-Soligen® or Borchers® Dry.
- the two- or multi-component composition contains the ingredient d), namely at least one peroxide or at least one perester or at least one hydroperoxide.
- the two- or multi-component composition may comprise further constituents, in particular these are fillers, thixotropic agents, impact modifiers, catalysts, activators, chelating ligands, solvents, plasticizers, pigments, dyes, additives such as adhesion promoters, leveling agents, emulsifiers, inhibitors and UV and Heat stabilizers etc.
- an activator can be used. Suitable activators are known to the person skilled in the art. Nonlimiting examples include: tertiary amines such as N 1 N-
- Particularly preferred activators are toluidine derivatives, especially N, N- Dialkyltoluidine.
- Suitable teriary amines, in particular p-toluidines may also be alkoxylated.
- suitable fillers are chalks, preferably coated chalks, and quartz flour, barium sulfate, fumed silica, filled or hollow glass or ceramic spheres.
- plasticizers are phthalates and adipates, in particular diisononyl phthalate, diisodecyl phthalate (DIDP) or dioctyl adipate (DOA).
- DIDP diisodecyl phthalate
- DOA dioctyl adipate
- Carboxylic acid derivatives Particularly suitable are potassium, calcium or barium octoates.
- liquid rubbers are in particular those sold under the trade name Hycar® by Noveon.
- these may be acrylate-modified butadiene-acrylonitrile copolymers, such as those from the product line Hycar® VTBNX.
- Preferred core-shell polymers are, in particular, those core-shell polymers which are commercially available under the trade name Paraloid® from Rohm and Haas. It has proven particularly advantageous when a mixture of
- Liquid rubber and core-shell polymer can be used as impact modifiers.
- the two-component or multicomponent composition preferably additionally comprises activators, fillers and possibly plasticizers.
- the two-component or multi-component composition is as free as possible of odorous compounds.
- those compounds which have a strong and unpleasant odor such as styrene or methyl (meth) acrylate, are undesirable.
- styrene-containing systems in addition to the odor, are also disadvantageous in that they prolong the drying time.
- the two or more component composition is preferably free of styrene. Likewise, they are both free of styrene and free of unsaturated polyester resins.
- the component K1 comprises at least the ingredient c) and the component K2 comprises at least the ingredient d).
- the bi- or multicomponent composition is a three-component composition.
- a preferred three-component composition is one with a third component K3, which comprises at least the ingredient a); and wherein at least the ingredient b) is part of the component K1 or K2 or K3. It is preferred here that the ingredient b) is part of the component K1.
- the two or more component composition is a two component composition.
- ingredient a) is part of
- Component K2 The ingredient b) is then part of the component K1 or K2, but preferably part of the component K1.
- This embodiment is especially preferred when the (meth) acrylate has an ether group, in particular tetrahydrofurfuryl (meth) acrylate.
- ingredient a) is part of component K1.
- the ingredient b) is then part of the component K1 or K2, but preferably part of the component K1.
- the proportion of the compound of the formula (I) is preferably 0.1 to 20 wt .-%, in particular 0.1 to 10 wt .-%, preferably 1 to 5 wt .-%, based on the weight of the two- or multi-component composition.
- the radical R 1 is of higher molecular weight, typically when the radical R 1 has a molecular weight of more than 100 g / mol, in particular more than 400 g / mol
- Metal complex compound calculated as metal, is preferably 0.001 to 0.5 wt .-%, in particular 0.01 to 0.4 wt .-%, preferably 0.01 to 0.2 wt .-%, based on the weight of the two- or multi-component composition.
- the proportion of the at least one (meth) acrylate preferably has the greatest proportion of the ingredients a), b), c) and d) by weight.
- the ratio a) / [a) + b) + c) + d)] is greater than 0.7, in particular 0.8-0.999, preferably 0.9-0.99.
- the proportion of (meth) acrylate is typically more than 20
- Wt .-% in particular 30-99 wt .-%, preferably 40 - 95 wt .-%, based on the weight of the two- or multi-component composition.
- ingredient b) is used stoichiometrically or in excess with respect to ingredient c). That is, the molar ratio [Formula (1)] / (n * [M])> 1, where [M] is the amount of the metal of the metal salt or metal complex compound in moles and [Formula (I)] for the amount the compound of formula (I) in mol and n represent the index in formula (I).
- the components K1, K2 and possibly the other components are stored separately from each other. For example, this can be done in barrels, hobbocks or cartridges. However, these separate bearings also includes storage in packages having two chambers interconnected by at least one partition wall.
- these may be cylindrical chambers, which may be arranged side by side (parallel) or co-centric.
- the walls of the chambers can be rigid or flexible.
- Particularly suitable are so-called twin cartridges (parallel arrangement) or cartridge-in-cartridge double cartridges (co-centric arrangement).
- An exemplary arrangement of the chambers and their configuration can be found in WO 01/44074 or in US 6,433,091 B1.
- a component may be present in a package from which this component is metered and admixed with a stream of the other component.
- An example of such a packaging or metering can be found, for example, in WO 95/24556.
- Such packaging / dosing be advantageously screwed onto a cartridge outlet or on an outlet opening of an adhesive pump.
- the admixture of one component to the other component and mixing by means of a dynamic mixer by means of a dynamic mixer.
- the one component is injected to the other component, in particular via a plurality of distributed nozzles and then mixed.
- the interference of one component in the other component can be homogeneous or in layers. Layers are obtained in particular when a small number, typically between 3 and 10, of mixing elements are arranged in a static mixer.
- a dynamic mixer or a large number of mixing elements are used in a static mixer.
- the components K1, K2 and possibly other components present are mixed together immediately before or during the application. If there are more than two components, all components can be mixed simultaneously or shifted in time.
- the mixture can be done manually or mechanically.
- the mixture is preferably carried out with the aid of a static mixer or with the aid of a dynamic mixer.
- the two-component or multi-component composition can be used in particular as an adhesive or sealant or as a coating.
- the substrates S1 and S2 being of the same or different material - curing the mixed composition
- the substrates S1 and S2 being of the same or different material - curing the mixed composition
- the substrates S1 and S2 with which the mixed two- or multi-component composition comes into contact can be more varied
- Metal alloys such as aluminum, steel, brass, copper or sheet metal, plastics such as polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene
- ABS SMC (Sheet Molding Compound), Polycarbonate (PC),
- PA Polyamide
- PET polyester
- POM polyoxymethylene
- PE polyethylene
- PP polypropylene
- the two-component or multicomponent compositions are distinguished by a marked reduction, in particularly preferred cases even by a complete elimination, of oxygen inhibition. This has the effect that the compositions are quickly tack-free and dust-dry, without the need for time-consuming post-treatment by means of heat or removal of the sticky layer. This is particularly important in applications where large areas of the composition to be cured are in contact with the air. Therefore, the application as a coating or thick-layer bonding or sealing is an application in which the advantages of the composition according to the invention become particularly apparent.
- thin-layer coatings should be mentioned as a coating, for example as a lacquer or protective coating.
- coatings are thick coatings or coatings, such as floors.
- the two- or multi-component compositions are particularly suitable for
- the two- or multi-component composition is characterized by a very rapid curing. This is very important, in particular, when the articles produced have to be loaded or processed quickly, be it, for example, coating or passing over a coating or moving or transporting an adhesive or sealing compound.
- compositions are particularly suitable as assembly adhesives.
- mounting adhesives are suitable for use for bonding to a production line in the industrial production of articles, in particular of everyday objects such as white goods, such as washing machines, or of vehicles, in particular of automobiles.
- the hardening time of the base coat was the time, measured after admixing the last ingredient, in which the
- Metal spatula could not touch the glass surface.
- the sand-filled pipette guided over the coating surface left a trail of sand on the surface.
- the sand was lightly wiped off with a brush.
- the dry point was determined as the "dry point” at which sand no longer adhered to the surface, and the drying time was calculated from the distance traveled from the starting point to the "dry point” and the hardening time of the base layer.
- the first component K1 was prepared as follows. The (meth) acrylate was first the liquid rubber in a
- the second component K2 was prepared as follows. The chalk and plasticizer and optionally acetylbutyrolactone and optionally activator were mixed well in a speed mixer. Subsequently, the metal catalyst solutions were added and also stirred well in the Speedmixer. It was not degassed.
- compositions of Table 8 are prepared analogously, except that here acetylbutyrolactone was formulated as a component of the component K1.
- the open time of the static mixer was stated as "working life" in Table 7 and 8.
- the drying time was determined by sanding (manually)
- the drying time U in Table 7 and 8 was the time at which the sand returned from the static mixer Shake off adhesive bead.
- Table 9 shows the mechanical values of bonds.
- the tensile strength and elongation at break of the cured two-component compositions Ref. 16 and 36 were measured on a Zwick / Roell Z005 tractor to ISO 527 at 200 mm / min.
- the tensile shear strengths of substrates bonded by means of Ref. 16 and 36 were measured on a tractor Zwick / Roell Z005 according to ISO 4587 / DIN EN 1465, at 10 mm / min.
- Table 10 shows that the replacement of (meth) acrylate with styrene greatly increases the cure time of the base coat than the
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/922,130 US20100297457A1 (en) | 2005-06-17 | 2006-03-08 | (Meth) acrylate composition featuring reduced oxygen inhibition |
JP2008516254A JP2008546856A (ja) | 2005-06-17 | 2006-03-08 | 酸素による阻害が低減されたことを特徴とする(メタ)アクリレート組成物 |
CA 2612275 CA2612275A1 (en) | 2005-06-17 | 2006-03-08 | (meth)acrylate composition featuring reduced oxygen inhibition |
EP06724967.2A EP1893701B1 (de) | 2005-06-17 | 2006-03-08 | (meth)acrylat-zusammensetzung mit reduzierter sauerstoffinhibierung |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20050105396 EP1734087A1 (de) | 2005-06-17 | 2005-06-17 | (Meth)Acrylat-Zusammensetzung mit reduzierter Sauerstoffinhibierung |
EP05105396.5 | 2005-06-17 |
Publications (1)
Publication Number | Publication Date |
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WO2006133978A1 true WO2006133978A1 (de) | 2006-12-21 |
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Application Number | Title | Priority Date | Filing Date |
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PCT/EP2006/060540 WO2006133978A1 (de) | 2005-06-17 | 2006-03-08 | (meth)acrylat-zusammensetzung mit reduzierter sauerstoffinhibierung |
Country Status (6)
Country | Link |
---|---|
US (1) | US20100297457A1 (de) |
EP (2) | EP1734087A1 (de) |
JP (1) | JP2008546856A (de) |
CN (1) | CN101198660A (de) |
CA (1) | CA2612275A1 (de) |
WO (1) | WO2006133978A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2492329A1 (de) | 2011-02-22 | 2012-08-29 | Sika Technology AG | (Meth)acrylat-Zusammensetzung mit verringerter Oberflächenklebrigkeit |
Families Citing this family (5)
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KR20130142882A (ko) | 2010-06-01 | 2013-12-30 | 리켄 테크노스 가부시키가이샤 | 도료 및 접착제 조성물, 접착 방법 및 적층체 |
DE102011078785B4 (de) | 2011-07-07 | 2013-03-07 | Hilti Aktiengesellschaft | Härterzusammensetzung, diese enthaltendes Mehrkomponenten-Mörtelsystem, dessen Verwendung sowie Patrone, Kartusche oder Folienbeutel enthaltend ein Mehrkomponenten - Mörtelsystem |
JP6615129B2 (ja) * | 2014-06-24 | 2019-12-04 | スリーエム イノベイティブ プロパティズ カンパニー | 接着剤前駆体組成物、2剤型接着剤キット、及び接着剤組成物の製造方法 |
FR3030547B1 (fr) * | 2014-12-22 | 2018-08-17 | Arkema France | Sirop (meth)acrylique liquide, procede d'impregnation d'un substrat fibreux par ledit sirop, et materiau composite obtenu apres polymerisation dudit sirop d'impregnation |
GB2613613A (en) | 2021-12-09 | 2023-06-14 | Henkel IP & Holding GmbH | Curable (meth) acrylate compositions |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2601378A1 (de) * | 1976-01-15 | 1977-07-21 | Bayer Ag | Zusatzbeschleuniger enthaltende lufttrocknende polyesterharze |
US4343921A (en) * | 1978-11-06 | 1982-08-10 | Usm Corporation | Adhesive composition |
US4442138A (en) * | 1982-02-22 | 1984-04-10 | Westinghouse Electric Corp. | Substrate pretreatment with a metal-beta keto ester complex in the method of curing an anaerobic resin |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006342266A (ja) * | 2005-06-09 | 2006-12-21 | Japan Composite Co Ltd | ラジカル硬化性樹脂組成物及びその硬化方法 |
-
2005
- 2005-06-17 EP EP20050105396 patent/EP1734087A1/de not_active Withdrawn
-
2006
- 2006-03-08 CN CNA2006800217591A patent/CN101198660A/zh active Pending
- 2006-03-08 CA CA 2612275 patent/CA2612275A1/en not_active Abandoned
- 2006-03-08 EP EP06724967.2A patent/EP1893701B1/de not_active Not-in-force
- 2006-03-08 US US11/922,130 patent/US20100297457A1/en not_active Abandoned
- 2006-03-08 JP JP2008516254A patent/JP2008546856A/ja active Pending
- 2006-03-08 WO PCT/EP2006/060540 patent/WO2006133978A1/de active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2601378A1 (de) * | 1976-01-15 | 1977-07-21 | Bayer Ag | Zusatzbeschleuniger enthaltende lufttrocknende polyesterharze |
US4343921A (en) * | 1978-11-06 | 1982-08-10 | Usm Corporation | Adhesive composition |
US4442138A (en) * | 1982-02-22 | 1984-04-10 | Westinghouse Electric Corp. | Substrate pretreatment with a metal-beta keto ester complex in the method of curing an anaerobic resin |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2492329A1 (de) | 2011-02-22 | 2012-08-29 | Sika Technology AG | (Meth)acrylat-Zusammensetzung mit verringerter Oberflächenklebrigkeit |
EP2878643A1 (de) | 2011-02-22 | 2015-06-03 | Sika Technology AG | (Meth)acrylat-Zusammensetzung mit verringerter Oberflächenklebrigkeit |
Also Published As
Publication number | Publication date |
---|---|
EP1734087A1 (de) | 2006-12-20 |
CA2612275A1 (en) | 2006-12-21 |
CN101198660A (zh) | 2008-06-11 |
EP1893701A1 (de) | 2008-03-05 |
US20100297457A1 (en) | 2010-11-25 |
EP1893701B1 (de) | 2017-06-28 |
JP2008546856A (ja) | 2008-12-25 |
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