WO1995018183A1 - Epoxy resins compatible with polyamine curing agents - Google Patents
Epoxy resins compatible with polyamine curing agents Download PDFInfo
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- WO1995018183A1 WO1995018183A1 PCT/US1994/014550 US9414550W WO9518183A1 WO 1995018183 A1 WO1995018183 A1 WO 1995018183A1 US 9414550 W US9414550 W US 9414550W WO 9518183 A1 WO9518183 A1 WO 9518183A1
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- WO
- WIPO (PCT)
- Prior art keywords
- component
- epoxy resin
- epoxy
- weight
- meth
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 44
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 44
- 229920000768 polyamine Polymers 0.000 title claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 13
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 title description 11
- -1 acrylate ester Chemical class 0.000 claims abstract description 15
- 150000002148 esters Chemical class 0.000 claims abstract description 13
- 239000004814 polyurethane Substances 0.000 claims abstract description 13
- 229920002635 polyurethane Polymers 0.000 claims abstract description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000193 polymethacrylate Polymers 0.000 claims abstract description 6
- 229920005862 polyol Polymers 0.000 claims abstract description 5
- 150000003077 polyols Chemical class 0.000 claims abstract description 5
- 239000004593 Epoxy Substances 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 239000004848 polyfunctional curative Substances 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- 229920003986 novolac Polymers 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims 1
- 150000003141 primary amines Chemical class 0.000 claims 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 20
- 238000000576 coating method Methods 0.000 abstract description 12
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000010348 incorporation Methods 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 7
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Chemical group 0.000 description 5
- 239000001257 hydrogen Chemical group 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- IMYZQPCYWPFTAG-UHFFFAOYSA-N Mecamylamine Chemical compound C1CC2C(C)(C)C(NC)(C)C1C2 IMYZQPCYWPFTAG-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/147—Polyurethanes; Polyureas
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Definitions
- This invention relates to epoxy resins and their uses. More particularly, the invention relates to epoxy resin compositions compatible with polyamine curing agents.
- U.S. 4,051,195 relates to blends of an epoxide resin and a poiy(meth)acrylate ester, which cure rapidly with aliphatic polyamine curing agents even at low temperatures.
- Such compositions can be employed as coatings, adhesives, castings, moldings and the like at high solids contents, including 100% solids content (so-called sêtless compositions).
- compositions comprise an important advance in the art, since the cured compositions can be formulated to range from flexible to very hard, the latter type tend to be brittle and to have low impact resistance, which are serious disadvantages for their use as coatings, moldings, castings, and the like.
- U.S.4,547,562 discloses sreteless polymeric compositions suitable for coatings and moldings formed by the addition reaction product of a first component comprising mono, di or poly amines, amine-terminated structures or an adduct of mono, di or polyamines with mono, di or polyfunctional acrylates or epoxides; and the second component comprising mono, di or poly acrylates, mixtures of mono, di or poly acrylates, or a mixture of mono, di or poly acrylates and mono, di or polyfunctional epoxides and/or glycidyl esters of acrylic acid or methacrylic acid.
- compositions when cured can be used as adhesives, varnishes, lacquers, paints, or sealants.
- the coatings tend to be brittle, with low impact resistance.
- the two component epoxy resin system of the invention comprises A) a liquid epoxy resin component containing
- the epoxy resin (component A) a) above) includes those epoxy resins having two or more 1,2-epoxy groups per molecule.
- the epoxy resins include those set forth in U.S.4,051,195, which patent is expressly incorporated herein by reference. Such epoxy resins are liquid, saturated or unsaturated, aliphatic, cycloaliphatic or heterocyclic and can be either monomeric or polymeric.
- Preferred epoxy resins for use herein are the epoxy novolac resins of formula I
- R H or CH 3
- n 0 to 4.
- epoxy novolac resins of formula I are usually mixtures of ortho, meta and para isomers. Also preferred are epoxy resins of formula II
- R H or CH 3
- the multifunctional (meth)acrylate esters (component A)b) above) useful in the practice of the invention include those esters set forth in U.S. 4,051,195, which is expressly incorporated herein by reference. These multifunctional (meth) acrylate esters should have a viscosity not greater than 5000 cps, and preferably not greater than 500 cps.
- Preferred esters are diols or triols, optionally ethoxylated and/or propoxylated with from 1 to 8 EO and/or PO groups, wherein all hydroxyl groups are in the form of acrylate esters, e.g. trimetha ⁇ ol triacrylate. Most preferred are esters of the following formulae:
- x is an integer of from 2-6
- y is an integer of from 1 -6 and R 1 is H or CH 3 .
- Examples of compounds within the above formulae include 1,3-propanediol diacrylate, 1,6-hexanediol diacrylate, and tripropyleneglycol diacrylate.
- multifunctional (meth) acrylate esters having a viscosity above 500 cps are present, they are preferably present in relatively small quantities, e.g. from 0.1 to 25%, based on the total weight of (meth)acrylate ester.
- Such higher viscosity esters are e.g. sugar polyacrylates, and in fact their presence may be useful in increasing the crosslink density of the cured epoxy.
- multifunctional methacrylate esters are within the scope of the invention, these esters are usually somewhat less desirable for use herein than the corresponding multifunctional acrylate esters due to their somewhat slower rates of reaction and more limited miscibility with the epoxy resins.
- the multifunctional (meth)acryiate esters are in the form of esters of (meth)acrylic acid, e.g. in the case of a triol or higher polyol having one or more free hydroxyl groups
- the nonesterified hydroxyl groups can be present as such or in the form of C 1 -C 3 alkoxy groups, preferably methoxy. It is however usually preferred to esterify all hydroxyl groups with (meth)acrylic acid.
- R is H or CH 3
- R 1 is H or CH 3 , n is an integer of from 0-6,
- n is an integer of from 0-6, and
- n + m 1-6, preferably 2-6,
- component A)b) above when used as component A)b) above, greatly improves the impact resistance and flexibility of the cured compositions, even without the presence of any polyurethane di(meth)acrylate (component A)c) above).
- the polyurethane poly(meth) acrylates (component A)c) above) contain from 2 to 6 (meth) acrylate groups, are aliphatic or aromatic polyurethane derivatives, are highly viscous or solid, having a weight average molecular weight in the range of from 1200 to 5000, preferably 1200 to 1800. They are employed in amounts ranging from 0.1 to 25%, preferably 1 to 15%,and more preferably 1 to 10% by weight, based on the combined weight of components A)a) and A)b).
- polyurethane diacrylates are usually prepared by reacting a diisocyanate with hydroxyethyl acrylate in a 1 :1 molar ratio, so that the resulting adduct contains a free isocyanate group, and then reacting two moles of this adduct with one mole of a dihydroxy polyether or polyester.
- the hardener component (component B)) of the present two component epoxy resin systems are aliphatic polyamines such as polyalkyiene polyamines, e.g. ethylenediamine (H 2 NCH 2 CH 2 NH 2 ) dimethylethylene diamine (CH 3 NHCH 2 CH 2 NHCH 3 ), diethylenetriamine (H 2 NCH 2 CH 2 NHCH 2 CH 2 NH 2 ), tetramethylene diamine (H 2 NCH 2 CH 2 CH 2 CH 2 NH 2 ), triethylenetetramine (H 2 NCH 2 CH 2 NHCH 2 CH 2 NHCH 2 CH 2 NH 2 ), hexamethylene diamine (H 2 N(CH 2 ) 6 NH 2 ), etc.
- polyalkyiene polyamines e.g. ethylenediamine (H 2 NCH 2 CH 2 NH 2 ) dimethylethylene diamine (CH 3 NHCH 2 CH 2 NHCH 3 ), diethylenetriamine (H 2 NCH 2 CH 2 NHCH 2 CH 2
- polyamide curing agents i.e. amidoamines obtained by reacting a polyamine such as the above with straight or branched chain saturated aliphatic polycarboxylic acids, e.g. having from 2-50 carbon atoms in the alkylene groups, in which each carboxylic acid group has been reacted with a molecule of a polyamine.
- the resulting polyamides must contain at least two amine groups that are primary and/or secondary in nature.
- Preferred polyamide curing agents are the reaction products of one mol of a C 36 fatty diacid from the dimerization of a C 18 unsaturated fatty acid with two mols of diethylenetriamine or triethylenetetramine.
- polyamines containing epoxy groups can be employed herein.
- the hardener component can optionally contain quantities of other ingredients, e.g. from 0.001 to 65% by weight, based on the weight of polyamine curing agent, of ingredients such as accelerators, fillers, reinforcing agents, dyes, pigments and other additives.
- the percentage ratio by weight of component A)a) to component A)b) is from 85:15 to 20:80.
- the particular ratio selected within the above range is not critical and will depend on the particular components chosen and the properties desired for the cured epoxy product.
- Components A and B are used in an equivalent ratio of epoxy groups plus acrylate groups in the epoxy resin component to amine hydrogen atoms in the hardener component of from 0.85:1 to 1:1.15, preferably from 0.95:1 to 1:1.05, and more preferably 1:1.
- the two component epoxy resin systems of the invention are applied by mixing together the epoxy resin component and the hardener component in the absence of solvents and applying the mixture at a temperature of from 0° to 150°F, preferably from 40° to 110oF, and more preferably from 40° to 95oF.
- solvents thereto such as hydrocarbons, ethers, alcohols, esters, ketones, etc.
- solvents are highly undesirable, acting to reduce the solids contents, presenting environmental and safety problems, and causing a reduction in physical properties, e.g. in thick coatings of 20-1000 mils, solvents will be trapped in the coatings, resulting in cheesey films.
- the two component epoxy resin system can be used as an adhesive system to bond two like or different substrates together as with other epoxy adhesives; as tough resilient nonbrittle coatings having high impact resistance for hard surfaces, including coatings for floors; as casting, molding and potting compositions; and as encapsulating compositions.
- the epoxy system can be used immediately after mixing due to its low viscosity, even at a relatively high solids content, and its increased reactivity even at relatively low cure temperatures. Short cure times are also achieved.
- the cured mixtures exhibit excellent flexibility, impact resistance, and good chemical resistance.
- thick coatings containing 100% solids content e.g. from 0.5 to 1 inch thick, can be readily applied to a substrate.
- the epoxy systems of the invention can also be used as paint compositions, when mixed with paint pigments.
- the paint coatings resulting from their use are unusually tough, adhesive and chemically resistant.
- a two component epoxy resin system is prepared from the following ingredients:
- DER 331 is the diglycidyl ether of bisphenol A.
- PHOTOMER® 6022 is an aromatic polyurethane containing six acrylate groups, a viscosity of from 500-800 poises, and a weight average molecular weight of 800.
- PHOTOMER® 4127 is a neopentylglycol- 2PO- diacrylate.
- a two component epoxy resin system is prepared from the following ingredients:
- VERSAMINE ® A-50 is an epoxy derivative of diethylenetriamine.
- a two component epoxy resin system is prepared from the following ingredients:
- PHOTOMER® 4025 is bisphenol A-8EO- diacrylate.
- a two component epoxy resin system is prepared from the following ingredients:
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
The incorporation of polyurethane poly(meth)acrylate(s) into a composition comprising epoxy resin(s), multifunctional (meth)acrylate ester(s) of a polyol which forms an ester with (meth)acrylic acid, and a polyamine curing agent results in cured epoxy resin(s) that are hard and nonbrittle with high impact resistance and finds use as an adhesive or coating.
Description
EPOXY RESINS COMPATIBLE WITH POLYAMINE CURING AGENTS BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to epoxy resins and their uses. More particularly, the invention relates to epoxy resin compositions compatible with polyamine curing agents.
2. Statement of Related Art
U.S. 4,051,195 relates to blends of an epoxide resin and a poiy(meth)acrylate ester, which cure rapidly with aliphatic polyamine curing agents even at low temperatures. Such compositions can be employed as coatings, adhesives, castings, moldings and the like at high solids contents, including 100% solids content (so-called soiventless compositions).
While these compositions comprise an important advance in the art, since the cured compositions can be formulated to range from flexible to very hard, the latter type tend to be brittle and to have low impact resistance, which are serious disadvantages for their use as coatings, moldings, castings, and the like.
U.S.4,547,562 discloses soiventless polymeric compositions suitable for coatings and moldings formed by the addition reaction product of a first component comprising mono, di or poly amines, amine-terminated structures or an adduct of mono, di or polyamines with mono, di or polyfunctional acrylates or epoxides; and the second component comprising mono, di or poly acrylates, mixtures of mono, di or poly acrylates, or a mixture of mono, di or poly acrylates
and mono, di or polyfunctional epoxides and/or glycidyl esters of acrylic acid or methacrylic acid.
Such compositions when cured can be used as adhesives, varnishes, lacquers, paints, or sealants. However, here again when used as coatings the coatings tend to be brittle, with low impact resistance.
This patent also contains the teaching that isocyanate and hydroxyl-terminated polyurethanes have high viscosities and "cannot be used as components of a liquid, soiventless system" (column 3, lines 1-8).
DESCRIPTION OF THE INVENTION
Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term "about".
It has now been discovered that the presence of small quantities of polyurethane poly(meth)acrylates in certain two component liquid soiventless epoxy resin systems results in cured epoxy resins that are hard, nonbrittle, and possess high impact resistance. This result is surprising, especially in view of the teachings of U.S.4,547,562 that hydroxyl-terminated polyurethanes cannot be used in such systems.
The two component epoxy resin system of the invention comprises A) a liquid epoxy resin component containing
a) at least one epoxy resin having at least two 1,2-epoxy groups; b) at least one multifunctional (meth)acrylate ester which is a polyol having at least two hydroxyl groups, in the form of an ester with acrylic acid or methacrylic acid; and
c) at least one polyurethane poly(meth)acrylate;
and
B) a liquid hardener component containing a polyamine curing agent.
The epoxy resin (component A) a) above) includes those epoxy resins having two or more 1,2-epoxy groups per molecule. The epoxy resins include those set forth in U.S.4,051,195, which patent is expressly incorporated herein by reference. Such epoxy resins are liquid, saturated or unsaturated, aliphatic, cycloaliphatic or heterocyclic and can be either monomeric or polymeric.
Preferred epoxy resins for use herein are the epoxy novolac resins of formula I
where R = H or CH3 and
n = 0 to 4.
The above epoxy novolac resins of formula I are usually mixtures of ortho, meta and para isomers.
Also preferred are epoxy resins of formula II
wherein R= H or CH3 and
m = 0 to 4.
Even more preferred are epoxy resins of formula II which are the diglycidyl ethers from epichlorohydrin and bisphenol A or bisphenol F, i.e. compounds of Formula II where R is methyl or hydrogen and m = 0.
The multifunctional (meth)acrylate esters (component A)b) above) useful in the practice of the invention include those esters set forth in U.S. 4,051,195, which is expressly incorporated herein by reference. These multifunctional
(meth) acrylate esters should have a viscosity not greater than 5000 cps, and preferably not greater than 500 cps. Preferred esters are diols or triols, optionally ethoxylated and/or propoxylated with from 1 to 8 EO and/or PO groups, wherein all hydroxyl groups are in the form of acrylate esters, e.g. trimethaπol triacrylate. Most preferred are esters of the following formulae:
CH2 = CH - COO(CH2)xOOC - CH = CH2 (III)
wherein x is an integer of from 2-6, and
wherein y is an integer of from 1 -6 and R1 is H or CH3.
Examples of compounds within the above formulae include 1,3-propanediol diacrylate, 1,6-hexanediol diacrylate, and tripropyleneglycol diacrylate. Where multifunctional (meth) acrylate esters having a viscosity above 500 cps are present, they are preferably present in relatively small quantities, e.g. from 0.1 to 25%, based on the total weight of (meth)acrylate ester. Such higher viscosity esters are e.g. sugar polyacrylates, and in fact their presence may be useful in increasing the crosslink density of the cured epoxy.
While multifunctional methacrylate esters are within the scope of the invention, these esters are usually somewhat less desirable for use herein than the corresponding multifunctional acrylate esters due to their somewhat slower rates of reaction and more limited miscibility with the epoxy resins.
Where less than all hydroxy groups in the multifunctional (meth)acryiate esters are in the form of esters of (meth)acrylic acid, e.g. in the case of a triol or higher polyol having one or more free hydroxyl groups, the nonesterified
hydroxyl groups can be present as such or in the form of C1-C3 alkoxy groups, preferably methoxy. It is however usually preferred to esterify all hydroxyl groups with (meth)acrylic acid.
It has also been discovered, and is a feature of this invention, that di(meth)acrylate esters of the formula
wherein R is H or CH3,
R1 is H or CH3,
n is an integer of from 0-6,
m is an integer of from 0-6, and
n + m = 1-6, preferably 2-6,
when used as component A)b) above, greatly improves the impact resistance and flexibility of the cured compositions, even without the presence of any polyurethane di(meth)acrylate (component A)c) above).
The polyurethane poly(meth) acrylates (component A)c) above) contain from 2 to 6 (meth) acrylate groups, are aliphatic or aromatic polyurethane derivatives, are highly viscous or solid, having a weight average molecular weight in the range of from 1200 to 5000, preferably 1200 to 1800. They are employed in amounts ranging from 0.1 to 25%, preferably 1 to 15%,and more preferably 1 to 10% by weight, based on the combined weight of components A)a) and A)b). Preferred are polyurethane di-acrylates having a weight average molecular weight in the range of from 1200 to 1800. These polyurethane diacrylates are usually prepared by reacting a diisocyanate with hydroxyethyl acrylate in a 1 :1 molar ratio, so that the resulting adduct contains a free isocyanate group, and then reacting two moles of this adduct with one mole of a dihydroxy polyether or polyester.
The hardener component (component B)) of the present two component epoxy resin systems are aliphatic polyamines such as polyalkyiene polyamines, e.g. ethylenediamine (H2NCH2CH2NH2) dimethylethylene diamine (CH3NHCH2CH2NHCH3), diethylenetriamine (H2NCH2CH2NHCH2CH2NH2), tetramethylene diamine (H2NCH2CH2CH2CH2NH2), triethylenetetramine (H2NCH2CH2NHCH2CH2NHCH2CH2NH2), hexamethylene diamine
(H2N(CH2)6NH2), etc. Preferred for use herein are polyamide curing agents, i.e. amidoamines obtained by reacting a polyamine such as the above with straight or branched chain saturated aliphatic polycarboxylic acids, e.g. having from 2-50 carbon atoms in the alkylene groups, in which each carboxylic acid group has been reacted with a molecule of a polyamine. The resulting polyamides must contain at least two amine groups that are primary and/or secondary in nature. Preferred polyamide curing agents are the reaction products of one mol of a C36 fatty diacid from the dimerization of a C18 unsaturated fatty acid with two mols of diethylenetriamine or triethylenetetramine. Also, polyamines containing epoxy groups can be employed herein.
In addition to the polyamine curing agent, the hardener component can optionally contain quantities of other ingredients, e.g. from 0.001 to 65% by weight, based on the weight of polyamine curing agent, of ingredients such as accelerators, fillers, reinforcing agents, dyes, pigments and other additives.
In the compositions of the invention, the percentage ratio by weight of component A)a) to component A)b) is from 85:15 to 20:80. The particular ratio selected within the above range is not critical and will depend on the particular components chosen and the properties desired for the cured epoxy product.
Components A and B are used in an equivalent ratio of epoxy groups plus acrylate groups in the epoxy resin component to amine hydrogen atoms in the hardener component of from 0.85:1 to 1:1.15, preferably from 0.95:1 to 1:1.05, and more preferably 1:1.
The two component epoxy resin systems of the invention are applied by mixing together the epoxy resin component and the hardener component in the
absence of solvents and applying the mixture at a temperature of from 0° to 150°F, preferably from 40° to 110ºF, and more preferably from 40° to 95ºF.
It is of course also possible to add solvents thereto, such as hydrocarbons, ethers, alcohols, esters, ketones, etc., but due to the liquid nature of the present compositions, such solvents are unnecessary. Moreover, for many applications solvents are highly undesirable, acting to reduce the solids contents, presenting environmental and safety problems, and causing a reduction in physical properties, e.g. in thick coatings of 20-1000 mils, solvents will be trapped in the coatings, resulting in cheesey films.
The two component epoxy resin system can be used as an adhesive system to bond two like or different substrates together as with other epoxy adhesives; as tough resilient nonbrittle coatings having high impact resistance for hard surfaces, including coatings for floors; as casting, molding and potting compositions; and as encapsulating compositions.
The epoxy system can be used immediately after mixing due to its low viscosity, even at a relatively high solids content, and its increased reactivity even at relatively low cure temperatures. Short cure times are also achieved. The cured mixtures exhibit excellent flexibility, impact resistance, and good chemical resistance.
Since the present epoxy system does not require any organic solvent, thick coatings containing 100% solids content, e.g. from 0.5 to 1 inch thick, can be readily applied to a substrate.
The epoxy systems of the invention can also be used as paint compositions, when mixed with paint pigments. The paint coatings resulting from
their use are unusually tough, adhesive and chemically resistant.
The invention will be illustrated but not limited by the following examples.
EXAMPLES
Example 1
A two component epoxy resin system is prepared from the following ingredients:
COMPONENT A:
acrylate
parts per equiv. wt. epoxy
Ingredient hundred equivalents
DER 331(1) 60 190 0.316
PHOTOMER® 6022rø 20 130 0.154
PHOTOMER® 4127(3) 20 180 0.111
100 0.581
COMPONENT B:
parts per
hundred parts amine amine of Component equiv. wt. hydrogen
Ingredient A equivalents
DETA(4) 12 20.6 0.581
(1)DER 331 is the diglycidyl ether of bisphenol A.
(2)PHOTOMER® 6022 is an aromatic polyurethane containing six acrylate groups, a viscosity of from 500-800 poises, and a weight average molecular weight of 800.
(3)PHOTOMER® 4127 is a neopentylglycol- 2PO- diacrylate.
(4)DETA is diethylenetriamine.
Example 2
A two component epoxy resin system is prepared from the following
ingredients:
COMPONENT A:
acrylate
parts per equiv. wt. epoxy ingredient hundred equivalents
DER 331 60 190 0.316
PHOTOMER® 6022 20 130 0.154
PHOTOMER® 4127 20 180 0.111
100 0.581
COMPONENT B:
parts per
hundred parts amine amine of Component equiv. wt hydrogen
Ingredient A equivalents
VERSAMINE® A-50(5) 25 43 0.581
(5)VERSAMINE ® A-50 is an epoxy derivative of diethylenetriamine.
Example 3
A two component epoxy resin system is prepared from the following ingredients:
COMPONENT A:
acrylate
parts per equiv. wt epoxy
Ingredient hundred equivalents
DER 331 75 190 0.395
PHOTOMER® 4025(6) 25 270 0.093
100 0.488
COMPONENT B:
parts per
hundred parts amine amine of Component equiv. wt hydrogen
Ingredient A equivalents
DETA 10 20.6 0.488
(6)PHOTOMER® 4025 is bisphenol A-8EO- diacrylate.
Example 4
A two component epoxy resin system is prepared from the following ingredients:
COMPONENT A:
acrylate
parts per equiv. wt epoxy ingredient hundred equivalents
DER 331 75 190 0.395
PHOTOMER® 4025(6) 25 270 0.093
100 0.488
COMPONENT B:
parts per
hundred parts amine amine of Component equiv. wt hydrogen
Ingredient A equivalents
VERSAMINE ® A-50 21 43 0.488
Claims
1. A two component epoxy resin system comprising
A) a liquid epoxy resin component containing
a) at least one epoxy resin having at least 21,2-epoxy groups; b) at least one multifunctional (meth)acrylate ester which is a polyol having at least two hydroxyl groups in the form of an ester with acrylic acid or methacrylic acid; and
c) from about 0.1 to about 25% parts by weight, based on the weight of a) plus b), of at least one polyurethane poly(meth)- acrylate; and
B) a liquid hardener component containing a polyamine curing agent.
2. The epoxy resin system of claim 1 wherein from about 1 to about 15% by weight of component A)c) is present in the epoxy resin component.
3. The epoxy resin system of claim 1 wherein component A)c) has a weight average molecular weight in the range of from about 1200 to about 5000.
4. The epoxy resin system of claim 3 wherein the molecular weight of component A)c) is in the range of from about 1200 to about 1800.
5. The epoxy resin system of claim 1 wherein the percentage ratio by weight of component A)a) to component A)b) is from about 85: 15 to about 20:80.
6. The epoxy resin system of claim 1 wherein component A)a) is an epoxy novolac resin of formula II 
wherein R = H or CH3, and n = 0 to 4.
7. The epoxy resin system of claim 6 wherein n in formula I is from 0-2.
8. The epoxy resin system of claim 6 wherein n in formula I is equal to zero or 1
9. The epoxy system of claim 1 wherein component A)b) has a viscosity not greater than about 5000 cps.
10. The epoxy system of claim 9 wherein said viscosity is not greater than about 500 cps.
11. The epoxy system of claim 1 wherein component A)b) is at least one of the following:
(i) a diol or triol having all hydroxy groups in the form of an acrylate ester and wherein the diol or triol is optionally ethoxylated and/or propoxylated with from 1 to 8 EO and/or PO groups; (ii) an acrylate ester of the formula CH2 = CH - COO(CH2)xOOC - CH =CH2 (III)
wherein x is an integer of from 2-6; and
(iii) an acrylate ester of the formula
R1
I CH2 = CH-COO(CH2CHO)γOC-CH = CH2 (IV)
wherein y is an integer of from 1-6 and R is H or CH3.
12. The epoxy resin system of claim 1 wherein the polyamine curing agent of component B) is a straight or branched chain saturated aliphatic polycarboxylic acid in which each carboxylic acid group is in the form of an amide with a polyamine, wherein the amide contains at least two primary and/or secondary amine groups.
13. The epoxy system of claim 1 wherein component A)b) is at least one di(meth)acryiate ester of the formula
this is revised
v 
wherein R is H or CH3,
R1 is H or CH3, n is an integer of from 0-6,
m is an integer of from 0-6,
and n + m = 1-6.
14. The epoxy system of claim 13 wherein in formula IV n + m = 2-6.
15. A curable liquid epoxy resin component comprising
a) at least one epoxy resin containing at least two 1 ,2-epoxy groups; b) at least one multifunctional (meth)acrylate ester which is a polyol having at least two hydroxyl groups in the form of an ester with acrylic acid or methacrylic acid; and
c) from about 0.1 to about 25% parts by weight, based on the weight of a) plus b), of at least one polyurethane poly(meth)acrylate.
16. The epoxy resin component of claim 15 wherein the percentage ratio by weight of component A)a) to component A)b) is from about 85:15 to about 20:80, and from about 1 to about 15% by weight of component A)c) is present therein.
17. A two component epoxy resin system comprising
A) a liquid epoxy resin component containing
a) at least one epoxy resin having at least two 1,2-epoxy groups, and
b) at least one di(meth)acrylate ester of the formula 
wherein R is H or CH3,
R1 is H or CH3,
n is an integer of from 0-6,
m is an integer of from 0-6,
and n + m = 1-6;
and
B) a liquid hardener component containing a polyamine curing agent.
18. The epoxy resin system of claim 17 wherein in component A)b) n + m = 2-6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17496593A | 1993-12-29 | 1993-12-29 | |
| US08/174,965 | 1993-12-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1995018183A1 true WO1995018183A1 (en) | 1995-07-06 |
Family
ID=22638259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1994/014550 WO1995018183A1 (en) | 1993-12-29 | 1994-12-23 | Epoxy resins compatible with polyamine curing agents |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO1995018183A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0675144A3 (en) * | 1994-03-16 | 1996-04-03 | Air Prod & Chem | Flexibilized polyepoxide resins incorporating poly-n-methylated secondary amines. |
| US6911109B2 (en) * | 2000-12-11 | 2005-06-28 | Henkel Corporation | Two-part, room temperature curable epoxy resin/ (meth)acrylate compositions and process for using same to bond substrates |
| US7071263B2 (en) | 2003-05-19 | 2006-07-04 | 3M Innovative Properties Company | Epoxy adhesives and bonded substrates |
| US9207373B2 (en) | 2007-04-10 | 2015-12-08 | Stoncor Group, Inc. | Methods for fabrication and highway marking usage of agglomerated retroreflective beads |
| WO2018226710A1 (en) * | 2017-06-09 | 2018-12-13 | Hexion Inc. | Epoxy resin systems for composites |
| EP4520774A1 (en) * | 2023-09-11 | 2025-03-12 | Sika Technology AG | Use of acrylates in epoxy systems |
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| JPS63118388A (en) * | 1986-11-06 | 1988-05-23 | Aica Kogyo Co Ltd | Adhesive for flexible vinyl chloride polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0675144A3 (en) * | 1994-03-16 | 1996-04-03 | Air Prod & Chem | Flexibilized polyepoxide resins incorporating poly-n-methylated secondary amines. |
| US6911109B2 (en) * | 2000-12-11 | 2005-06-28 | Henkel Corporation | Two-part, room temperature curable epoxy resin/ (meth)acrylate compositions and process for using same to bond substrates |
| US7071263B2 (en) | 2003-05-19 | 2006-07-04 | 3M Innovative Properties Company | Epoxy adhesives and bonded substrates |
| US9207373B2 (en) | 2007-04-10 | 2015-12-08 | Stoncor Group, Inc. | Methods for fabrication and highway marking usage of agglomerated retroreflective beads |
| WO2018226710A1 (en) * | 2017-06-09 | 2018-12-13 | Hexion Inc. | Epoxy resin systems for composites |
| US11292871B2 (en) | 2017-06-09 | 2022-04-05 | Hexion Inc. | Epoxy resin systems for composites |
| EP4520774A1 (en) * | 2023-09-11 | 2025-03-12 | Sika Technology AG | Use of acrylates in epoxy systems |
| WO2025056521A1 (en) | 2023-09-11 | 2025-03-20 | Sika Technology Ag | Use of acrylates in epoxy systems |
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