CA2071101A1 - Monomer compositions - Google Patents
Monomer compositionsInfo
- Publication number
- CA2071101A1 CA2071101A1 CA002071101A CA2071101A CA2071101A1 CA 2071101 A1 CA2071101 A1 CA 2071101A1 CA 002071101 A CA002071101 A CA 002071101A CA 2071101 A CA2071101 A CA 2071101A CA 2071101 A1 CA2071101 A1 CA 2071101A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- acrylic
- composition according
- formula
- radical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 239000000178 monomer Substances 0.000 title claims description 30
- 239000006229 carbon black Substances 0.000 claims abstract description 12
- -1 acrylic ester Chemical class 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 9
- 239000004567 concrete Substances 0.000 claims abstract description 9
- 238000009408 flooring Methods 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 235000019241 carbon black Nutrition 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 claims description 2
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 claims description 2
- 239000008199 coating composition Substances 0.000 claims 1
- 239000004576 sand Substances 0.000 abstract description 4
- 229920005822 acrylic binder Polymers 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000004982 aromatic amines Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 150000004680 hydrogen peroxides Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 1
- OAKAPFPXXUWHMV-UHFFFAOYSA-N 2-methoxycarbonylcyclohex-3-ene-1-carboxylic acid Chemical compound COC(=O)C1C=CCCC1C(O)=O OAKAPFPXXUWHMV-UHFFFAOYSA-N 0.000 description 1
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical group CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- MRIZMKJLUDDMHF-UHFFFAOYSA-N cumene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1 MRIZMKJLUDDMHF-UHFFFAOYSA-N 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002986 polymer concrete Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/06—Acrylates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/48—Macromolecular compounds
- C04B41/483—Polyacrylates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/62—Coating or impregnation with organic materials
- C04B41/63—Macromolecular compounds
-
- 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
- C08F290/02—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 end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/60—Flooring materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
- Polymerisation Methods In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Case 154-0222 ABSTRACT
A hardenable composition suitable for flooring and for coating concrete surfaces comprise (a) an acrylic binder comprising a (meth)acrylic ester of the formula where R1 is C2-6alkylene, n is 0-3 and R2 is a radical of an aromatic or alicyclic dicarboxylic acid ester or a dicyclopentenyl radical, the value of 0 for n only being possible when R2 is a dicyclopentenyl radical, (b) a component which is one or both (preferably both) of carbon black and a polyfunctional aliphatic or aromatic polyester- or polyether- urethane oligomer.
The composition also preferably comprises aggregate such as sand. The compositions have excellent impact resistance and flexural strength.
A hardenable composition suitable for flooring and for coating concrete surfaces comprise (a) an acrylic binder comprising a (meth)acrylic ester of the formula where R1 is C2-6alkylene, n is 0-3 and R2 is a radical of an aromatic or alicyclic dicarboxylic acid ester or a dicyclopentenyl radical, the value of 0 for n only being possible when R2 is a dicyclopentenyl radical, (b) a component which is one or both (preferably both) of carbon black and a polyfunctional aliphatic or aromatic polyester- or polyether- urethane oligomer.
The composition also preferably comprises aggregate such as sand. The compositions have excellent impact resistance and flexural strength.
Description
~7~
Case 154-022 MONOMER COMPOSITIONS
This invention relates to hardenable monomer compositions of the type used to provide flooring or to coat concrete objects.
A common type of composition for use in flooring and in the coating of concrete surfaces comprises a blend of at least one cross-linkable acrylic monomer and at least one coarse filler, usually sand. This type of composition, sometimes referred to in the art as "polymer concrete", is noted for its excellent mechanical properties.
It has now been found that it is possible to prepare compositions of this type with enhanced properties. There is therefore provided, according to the present invention, a hardenable monomer composition adapted to be used in flooring and in the coating of concrete surfaces, comprising (a) binder which comprises (meth)acrylic ester of the Formula I
CH2= 1 ~~fj~(R1)n-oR2 (1) R O
wherein R is hydrogen or methyl;
Rl is C26alkylene;
n is an integer of from 0-3; and Rz is a ra~ical of an aromatic or alicyclic dicarboxylic acid ester or a dicyclopentenyl radical, n being able to be 0 only when R2 is a dicyclopenterlylradical; and (b) at least one component selected from the group consisting of (i) carbon blacks with a BET surface area of from 20-460M2/g, this being presentto the extent of from 0.01-7, preferàbly 0.01-3, more preferably 0.1-0.5, weight% of the acrylic , . . . , . -2 Case 154-0222 ~ ~ P~
monomer; and (ii) aliphatic and aromatic polyester- and polyether- urethane oligomers of molecular weight 500-2000 and a visc:osity of 2,000100,000 mPa s at 25C, having at least two ethylenically unsa~urated double bonds.
Binders which are useful in the compositions of this invention comprise acrylic monomers which, when mixed with catalysts, harden within a few hours to form polymers. Such acrylic monomers include esters of (meth)acrylic acid, preferablymethacrylic acid, and suitable examples have been described in, for example, EP 47120, USP 4,460,625, 4,097,677, 4,299,761, 4,400,413 and GB 2,220,204 the disclosure of which are incorporated herein by reference. Binders suitable for use in this invention comprise monomers of formula I
CH2 = Cl - 1l -(ORl )n ~ OR2 (1) R O
wherein R is hydrogen or methyl, R, is an alkylene group with 2 to 6 C-atoms, n is an integer of from 0 to 3, and R2 is a radical of an aromatic or alicyclic dicarboxylic acid ester or a dicyclopentenyl radical, n being able to be 0 only when R2 is a dicyclopenteny!
radical.
Preference is given to those monomers of formula I in which R is methyl, R1 is abranched alkylene group with 3 or 4 C-atoms, n is 1 and R2 is the radical of a tetrahydro-phthalic acid, which in addition is esterified with an alkanol, preferably a C,6 alkanol, more preferably methanol or ethanol.
(Meth)acrylic esters according to formula I may constitute the entire binder, or they may be mixed with other esters of acrylic or methacrylic acid. This allows the balance of properties of the composition to be adjusted. Examples of such esters are the : .
.- -: ~ , - . .. . .
Case 154-022 MONOMER COMPOSITIONS
This invention relates to hardenable monomer compositions of the type used to provide flooring or to coat concrete objects.
A common type of composition for use in flooring and in the coating of concrete surfaces comprises a blend of at least one cross-linkable acrylic monomer and at least one coarse filler, usually sand. This type of composition, sometimes referred to in the art as "polymer concrete", is noted for its excellent mechanical properties.
It has now been found that it is possible to prepare compositions of this type with enhanced properties. There is therefore provided, according to the present invention, a hardenable monomer composition adapted to be used in flooring and in the coating of concrete surfaces, comprising (a) binder which comprises (meth)acrylic ester of the Formula I
CH2= 1 ~~fj~(R1)n-oR2 (1) R O
wherein R is hydrogen or methyl;
Rl is C26alkylene;
n is an integer of from 0-3; and Rz is a ra~ical of an aromatic or alicyclic dicarboxylic acid ester or a dicyclopentenyl radical, n being able to be 0 only when R2 is a dicyclopenterlylradical; and (b) at least one component selected from the group consisting of (i) carbon blacks with a BET surface area of from 20-460M2/g, this being presentto the extent of from 0.01-7, preferàbly 0.01-3, more preferably 0.1-0.5, weight% of the acrylic , . . . , . -2 Case 154-0222 ~ ~ P~
monomer; and (ii) aliphatic and aromatic polyester- and polyether- urethane oligomers of molecular weight 500-2000 and a visc:osity of 2,000100,000 mPa s at 25C, having at least two ethylenically unsa~urated double bonds.
Binders which are useful in the compositions of this invention comprise acrylic monomers which, when mixed with catalysts, harden within a few hours to form polymers. Such acrylic monomers include esters of (meth)acrylic acid, preferablymethacrylic acid, and suitable examples have been described in, for example, EP 47120, USP 4,460,625, 4,097,677, 4,299,761, 4,400,413 and GB 2,220,204 the disclosure of which are incorporated herein by reference. Binders suitable for use in this invention comprise monomers of formula I
CH2 = Cl - 1l -(ORl )n ~ OR2 (1) R O
wherein R is hydrogen or methyl, R, is an alkylene group with 2 to 6 C-atoms, n is an integer of from 0 to 3, and R2 is a radical of an aromatic or alicyclic dicarboxylic acid ester or a dicyclopentenyl radical, n being able to be 0 only when R2 is a dicyclopenteny!
radical.
Preference is given to those monomers of formula I in which R is methyl, R1 is abranched alkylene group with 3 or 4 C-atoms, n is 1 and R2 is the radical of a tetrahydro-phthalic acid, which in addition is esterified with an alkanol, preferably a C,6 alkanol, more preferably methanol or ethanol.
(Meth)acrylic esters according to formula I may constitute the entire binder, or they may be mixed with other esters of acrylic or methacrylic acid. This allows the balance of properties of the composition to be adjusted. Examples of such esters are the : .
.- -: ~ , - . .. . .
3 Case 1~4 0222 hydroxyalkyl methacrylates, particularly hydroxypropyl methacrylate. Based on the total amount of monomers, the (meth)acrylates of the formula I preferably comprise 20 to l O0 percent by weight, more preferably 50-95 percent by weight, and other (meth)acrylate esters preferably comprise up to 80 percent by weight, more preferably 5-50 percent by weight, based on total weight of a binder monomer.
The catalysts which may be used for crosslinking or hardening of the preparations according to the invention include organic peroxides or hydrogen peroxides of hydrocarbons with 3-18 carbon atoms which are soluble in the monomers, salts or complexes of transition metals and/or aromatic amines as polymerization catalysts. The peroxides or hydrogen peroxides are present in quantities of 0.1 to 5 percent by weight, the salts or complexes of transition metals in quantities of 0.0005 to 2 percent by weight and the aromatic amines in quantities of 0.1 to 5 percent by weight of the total weight of acrylic monomers. Examples of suitable peroxides include benzoyl peroxide, tert. butyl perbenzoate, dilauryl peroxide and ~,~-bis-(tert.butylperoxy)-butane. Suitable hydrogen peroxides are tert.-butyl hydrogen peroxide, cumene hydrogen peroxide and diisopropylbenzene hydrogen peroxide.
The salts or complexes of transition metals are those which catalyse the oxidative hardening of drying oils and are k~own as siccatives. They are usually calcium, copper, zinc, magnesium, manganese, lead, cobalt, iron, vanadium or zirconium salts of higher aliphatic (8-30 C) carboxylic acids and naphthenic acids. Cobalt and manganese salts are preferred, such as cobalt octoate, cobalt naphthenate, cobalt acetylacetonate and the corresponding manganese salts.
The aromatic amines which may optionally be used as polymerization accelerators are well known for this purpose. Examples are aniline, N,N-dimethyl- or N,N-diethylaniline, corresponding toluidines and p-dimethylaminobenzaldehyde, these are preferably used in quantities of 0.1 to 6, rnore preferably 0.1 to 2 percent by weight, based on the weight of the monomer components.
Such a catalyst system preferably consists of a peroxide or hydrogen peroxide, an : . ........................ . :
.. . . . .
: . : - . ' 4 Cas~ 154-0222 ~ ~ 7 .~
aromatic amine and a transition metal salt.
The compositions according to the invention pre~erably contain an essentially dry aggregate, which preferably comprises 40-95 % by weight of the total composition. Any inorganic compound which is inert towards acids, bases and salts may be considered as the aggregate. For example, sand, gravel or coarser aggregate materials of typesnormaliy employed in flooring compositions and the like may be employed. For coatings, fine aggregates such as fine sand, possibly mixed with silica fume, may be employed.
These various constituents may be added shortly before application of the monomer composition, or may be contained in various packages, which are storage-stable. For example, the aggregate, the various monomers with the optional polymerization accelerators and the polymerization catalyst with the transition metal salt may be delivered in separate packages, which may be mixed together shortly before use.
Depending on the catalyst employed, the catalyst system (without accelerator) may also be pre-mixed with the aggregate, or the monomer mixture may be pre-mixed with the aggregate.
In addition to binder (and usually aggregate), the composition of the invention also comprises a third component which is at least one of two other materials, carbon black and oligomer, whose parameters will now be described.
The carbon black has a BET surface area of from 20-400 Mt/g and is present to the extent of from 0.01-7, preferably 0.01-3.0%, more preferably 0.1-0.5%, by weight of the acr~lic binder. Materials such as gas black, lamp black and furnace blac}c may be used.
The carbon black has the effect of reducing the deleterious effect of oxygen, especially at the surface, and pot life and tack-free time are substantially improved without any impairment of the properties of the final polymer. The reactivity of the monomercomposition is also improved.
The oligomers used in compositions according to the invention are aliphatic and aromatic polyester- and polyether-urethanes having at least two unsaturated double bonds, . .
. ' ' . ~ ~ ' , ' 5 Case 154~ L
preferably at least three such bonds, so that they are capable of crosslinking with acrylic binders. Preferred oligomers have molecular weights in the range of 500-2000, preferably1000-2000,morepreferably1000-1400andviscositiesof 200G-100,000, more preferably 12,000-100,000, and most preferably 60,000-75,000 mPa s (at 25C). Such oligomers may be made, for example, by the reaction of carboxyl groups of acrylic acid or methacrylic acid monomer with a polyester- or polyether- urethane. This can be done during or after the preparation of the polyester- or polyether- urethane. Examples of suitable oligomers which are useful in the working of this invention are:
NAME SOURCE NATURE MW VISCOSITY
GENOMER Rahn AG aliphatic, 1000-1200 70,000 T1200 Zurich triacylate GENOMER " " ~1600 52,000 GENOMER " aliphatic D1500 B diacrylate EBECRYL UCB aromatic 2,000 30,000 205 Belgium triacrylate EBECRYL " aromatic 1,500 4,000 210 diacrylate EBECRYL " aliphatic 2,000 14,000 1259 triacrylate EBECRYL " aliphatic 1,000 2,000 1290 hexaacrylate When an oligomer is used as component (b), compounds of formula I comprise 20-93%, preferably 50-80%, other (meth)acrylates comprise up to 73%, preferably 7-37% and oligomer comprises 7-60%, preferably 13-40% by total weight of acrylic binder and oligomer.
In an especially preferred embodiment, the compositions according to the invention comprise both carbon black and oligomer.
The catalysts which may be used for crosslinking or hardening of the preparations according to the invention include organic peroxides or hydrogen peroxides of hydrocarbons with 3-18 carbon atoms which are soluble in the monomers, salts or complexes of transition metals and/or aromatic amines as polymerization catalysts. The peroxides or hydrogen peroxides are present in quantities of 0.1 to 5 percent by weight, the salts or complexes of transition metals in quantities of 0.0005 to 2 percent by weight and the aromatic amines in quantities of 0.1 to 5 percent by weight of the total weight of acrylic monomers. Examples of suitable peroxides include benzoyl peroxide, tert. butyl perbenzoate, dilauryl peroxide and ~,~-bis-(tert.butylperoxy)-butane. Suitable hydrogen peroxides are tert.-butyl hydrogen peroxide, cumene hydrogen peroxide and diisopropylbenzene hydrogen peroxide.
The salts or complexes of transition metals are those which catalyse the oxidative hardening of drying oils and are k~own as siccatives. They are usually calcium, copper, zinc, magnesium, manganese, lead, cobalt, iron, vanadium or zirconium salts of higher aliphatic (8-30 C) carboxylic acids and naphthenic acids. Cobalt and manganese salts are preferred, such as cobalt octoate, cobalt naphthenate, cobalt acetylacetonate and the corresponding manganese salts.
The aromatic amines which may optionally be used as polymerization accelerators are well known for this purpose. Examples are aniline, N,N-dimethyl- or N,N-diethylaniline, corresponding toluidines and p-dimethylaminobenzaldehyde, these are preferably used in quantities of 0.1 to 6, rnore preferably 0.1 to 2 percent by weight, based on the weight of the monomer components.
Such a catalyst system preferably consists of a peroxide or hydrogen peroxide, an : . ........................ . :
.. . . . .
: . : - . ' 4 Cas~ 154-0222 ~ ~ 7 .~
aromatic amine and a transition metal salt.
The compositions according to the invention pre~erably contain an essentially dry aggregate, which preferably comprises 40-95 % by weight of the total composition. Any inorganic compound which is inert towards acids, bases and salts may be considered as the aggregate. For example, sand, gravel or coarser aggregate materials of typesnormaliy employed in flooring compositions and the like may be employed. For coatings, fine aggregates such as fine sand, possibly mixed with silica fume, may be employed.
These various constituents may be added shortly before application of the monomer composition, or may be contained in various packages, which are storage-stable. For example, the aggregate, the various monomers with the optional polymerization accelerators and the polymerization catalyst with the transition metal salt may be delivered in separate packages, which may be mixed together shortly before use.
Depending on the catalyst employed, the catalyst system (without accelerator) may also be pre-mixed with the aggregate, or the monomer mixture may be pre-mixed with the aggregate.
In addition to binder (and usually aggregate), the composition of the invention also comprises a third component which is at least one of two other materials, carbon black and oligomer, whose parameters will now be described.
The carbon black has a BET surface area of from 20-400 Mt/g and is present to the extent of from 0.01-7, preferably 0.01-3.0%, more preferably 0.1-0.5%, by weight of the acr~lic binder. Materials such as gas black, lamp black and furnace blac}c may be used.
The carbon black has the effect of reducing the deleterious effect of oxygen, especially at the surface, and pot life and tack-free time are substantially improved without any impairment of the properties of the final polymer. The reactivity of the monomercomposition is also improved.
The oligomers used in compositions according to the invention are aliphatic and aromatic polyester- and polyether-urethanes having at least two unsaturated double bonds, . .
. ' ' . ~ ~ ' , ' 5 Case 154~ L
preferably at least three such bonds, so that they are capable of crosslinking with acrylic binders. Preferred oligomers have molecular weights in the range of 500-2000, preferably1000-2000,morepreferably1000-1400andviscositiesof 200G-100,000, more preferably 12,000-100,000, and most preferably 60,000-75,000 mPa s (at 25C). Such oligomers may be made, for example, by the reaction of carboxyl groups of acrylic acid or methacrylic acid monomer with a polyester- or polyether- urethane. This can be done during or after the preparation of the polyester- or polyether- urethane. Examples of suitable oligomers which are useful in the working of this invention are:
NAME SOURCE NATURE MW VISCOSITY
GENOMER Rahn AG aliphatic, 1000-1200 70,000 T1200 Zurich triacylate GENOMER " " ~1600 52,000 GENOMER " aliphatic D1500 B diacrylate EBECRYL UCB aromatic 2,000 30,000 205 Belgium triacrylate EBECRYL " aromatic 1,500 4,000 210 diacrylate EBECRYL " aliphatic 2,000 14,000 1259 triacrylate EBECRYL " aliphatic 1,000 2,000 1290 hexaacrylate When an oligomer is used as component (b), compounds of formula I comprise 20-93%, preferably 50-80%, other (meth)acrylates comprise up to 73%, preferably 7-37% and oligomer comprises 7-60%, preferably 13-40% by total weight of acrylic binder and oligomer.
In an especially preferred embodiment, the compositions according to the invention comprise both carbon black and oligomer.
6 Case 154~2,~
These preparations may be used to repair concrete objects or surfaces. In this work, a preparation according to the invention is applied to the surface requiring repair and is allowed to harden at the ambient temperature. However, they may also be used for the impregnation or coating of porous materials, especially concrete, or for filling cracks.
These preparations are particularly useful as flooring compositions.
Apart from good water resistance and heat resistance, the polymeric compositionsobtained from the hardening of the monomeric compositions acccrding to the invention are especially notable fortheir increased resistance to impact, their compression strength and flexural strength, and their outstanding àdhesive strength.
The invention is further described with reference to the following examples in which the parts and percentages are by weight.
Component I is an ester of tetrahydrophthalic acid monomethyl ester and hydroxypropyl methacrylate. Component ll is a hydroxypropyl methacrylate. The oligomer is the product GENOMER T 1200 from Rahn AG, Zurich.
The carbon black used is a furnace black with a BET surface area of 80 m2/g ("Printex"
300 from the company Degussa AG).
The pot life and absence of tackiness of the polymeric concrete mass obtained are determined at room temperature.
Examples 1-7 (Table 1) show the advantages of the use of carbon black in the proportions of the invention.
Examples 8-14 (Table 2) show the advantages of the addition cf oligomer according to the invention. The impact resistance (in milliJoules/sq. Cm.)and the flexuq~al and compression strengths (both in Newtons/sq. mm.) are determined by standard methods widely used in the art.
.. . : . .
.
These preparations may be used to repair concrete objects or surfaces. In this work, a preparation according to the invention is applied to the surface requiring repair and is allowed to harden at the ambient temperature. However, they may also be used for the impregnation or coating of porous materials, especially concrete, or for filling cracks.
These preparations are particularly useful as flooring compositions.
Apart from good water resistance and heat resistance, the polymeric compositionsobtained from the hardening of the monomeric compositions acccrding to the invention are especially notable fortheir increased resistance to impact, their compression strength and flexural strength, and their outstanding àdhesive strength.
The invention is further described with reference to the following examples in which the parts and percentages are by weight.
Component I is an ester of tetrahydrophthalic acid monomethyl ester and hydroxypropyl methacrylate. Component ll is a hydroxypropyl methacrylate. The oligomer is the product GENOMER T 1200 from Rahn AG, Zurich.
The carbon black used is a furnace black with a BET surface area of 80 m2/g ("Printex"
300 from the company Degussa AG).
The pot life and absence of tackiness of the polymeric concrete mass obtained are determined at room temperature.
Examples 1-7 (Table 1) show the advantages of the use of carbon black in the proportions of the invention.
Examples 8-14 (Table 2) show the advantages of the addition cf oligomer according to the invention. The impact resistance (in milliJoules/sq. Cm.)and the flexuq~al and compression strengths (both in Newtons/sq. mm.) are determined by standard methods widely used in the art.
.. . : . .
.
7 Case 154-0222 Examples 1~-24 (Table 3) show the advantages of the use of both carbon black andoligomer.
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Claims (9)
1. A hardenable monomer composition adapted to be used in flooring and in the coating of concrete surfaces, comprising (a) binder which comprises (meth)acrylic ester of the Formula I
(I) wherein R is hydrogen or methyl;
R1 is C2,6alkylene;
n is an integer of from 0-3; and R2 is a radical of an aromatic or alicyclic dicarboxylic acid ester or a dicyclopentenyl radical, n being able to be 0 only when R2 is a dicyclopentenyl radical; and b) at least one component selected from the group consisting of (i) carbon blacks with a BET surface area of from 20-460M2/g, this being present to the extent of from 0.01-7, preferably 0.01-3.0, more preferably 0.1-0.5 weight % of the acrylic monomer; and (ii) aliphatic and aromatic polyester- and polyether- urethane oligomers of molecular weight 500-2000 and a viscosity of 2000-100,000 mPa s at 25°C, having at least two ethylenically unsaturated double bonds.
(I) wherein R is hydrogen or methyl;
R1 is C2,6alkylene;
n is an integer of from 0-3; and R2 is a radical of an aromatic or alicyclic dicarboxylic acid ester or a dicyclopentenyl radical, n being able to be 0 only when R2 is a dicyclopentenyl radical; and b) at least one component selected from the group consisting of (i) carbon blacks with a BET surface area of from 20-460M2/g, this being present to the extent of from 0.01-7, preferably 0.01-3.0, more preferably 0.1-0.5 weight % of the acrylic monomer; and (ii) aliphatic and aromatic polyester- and polyether- urethane oligomers of molecular weight 500-2000 and a viscosity of 2000-100,000 mPa s at 25°C, having at least two ethylenically unsaturated double bonds.
2. A hardenable monomer compositions according to claim 1, wherein the composition comprises aggregate preferably to the extent of from 40-95% by weight of the total composition.
3. A hardenable monomer composition according to claim 1 or claim 2, wherein R is methyl, R1 is a branched C3-4alkylene, n is 1 and R2 is the radical of a 12 Case 154-0222 tetrahydrophthalic acid which has been esterified with an alkanol, preferably a C1-6 alkanol, more preferably methanol or ethanol.
4. A hardenable monomer composition according to any one of the claims 1-3, wherein component (b) is a carbon black and the binder additionally comprises (meth)acrylic esters other than those of Formula I to the extent of up to 80%, preferably 5-50% by weight of total acrylic monomer.
5. A hardenable monomer composition according to any one of claims 1-3, wherein component (b) is oligomer and there is present in the composition from 20-93%, preferably 50-80%, of esters of Formula 1, up to 73%, preferably 7-37%, of (meth)acrylic acid esters other than those of Formula I, and from 7-60%, preferably 13-40%, by weight of oligomer, all by weight of the total weight of binder and oligomer.
6. A hardenable monomer composition according to claim 4 or claim 5, wherein the(meth)acrylic esters other than those of Formula I are hydroxyalkyl methacrylates.
7. A hardenable monomer composition according to any one of claims 1-3, wherein the composition comprises both carbon black and oligomer.
8. A flooring composition comprising a hardenable monomer composition according to any one of claims 1-7.
9. A coating composition for use on concrete subtrates, comprising a hardenable monomer composition according to any one of claims 1-7.
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4119648 | 1991-06-14 | ||
DEP4119648.1 | 1991-06-14 | ||
DEP4119646.5 | 1991-06-14 | ||
DE4119646 | 1991-06-14 | ||
DEP4119647.3 | 1991-06-14 | ||
DE4119647 | 1991-06-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2071101A1 true CA2071101A1 (en) | 1992-12-15 |
Family
ID=27202591
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002071101A Abandoned CA2071101A1 (en) | 1991-06-14 | 1992-06-12 | Monomer compositions |
Country Status (11)
Country | Link |
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JP (1) | JP2696039B2 (en) |
AT (1) | AT398966B (en) |
AU (1) | AU654717B2 (en) |
BE (1) | BE1005805A3 (en) |
CA (1) | CA2071101A1 (en) |
CH (1) | CH684795A5 (en) |
DE (1) | DE4218414C2 (en) |
ES (1) | ES2059235B1 (en) |
FR (1) | FR2677656B1 (en) |
GB (1) | GB2256645B (en) |
IT (1) | IT1255669B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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DE4242356A1 (en) * | 1992-12-15 | 1994-06-16 | Sandoz Ag | Monomer preparations for the construction industry |
DE19549104A1 (en) * | 1995-12-29 | 1997-07-03 | Remmers Bauchemie Gmbh | Pigmented plastic floor and process for its manufacture |
NL1005690C2 (en) * | 1997-04-01 | 1998-10-05 | Zijlstra & Co Verf B V | Flexible building filler and sealant composition |
PL2607438T3 (en) | 2011-12-21 | 2015-03-31 | Henkel Ag & Co Kgaa | Dry bonding acrylate adhesive layers |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2029898C2 (en) * | 1970-06-18 | 1986-01-30 | Karl Ullrich GmbH & Co, 6451 Mainhausen | Coating agent for mineral building materials or asphalt |
SU424836A1 (en) * | 1971-03-30 | 1974-04-25 | POLYMERBETON MIX | |
DE2155232B2 (en) * | 1971-11-06 | 1975-11-20 | Vki-Rheinhold & Mahla Ag, 6800 Mannheim | /kTQfc.U.ll QTIQ.QS.-B RT. IQ .U .7 S Manufacture of elements for the construction industry |
DE2209149A1 (en) * | 1972-02-26 | 1973-09-06 | Roehm Gmbh | PROCESS FOR MANUFACTURING MOLDED BODIES SUBSTANTLY FROM MINERAL BUILDING MATERIALS |
US4197225A (en) * | 1976-05-19 | 1980-04-08 | Rohm And Haas Company | Polymer concrete compositions and cured products thereof |
ZA7803231B (en) * | 1976-07-07 | Rohm & Haas | Monomer compositions | |
US4299761A (en) * | 1979-03-19 | 1981-11-10 | Rohm And Haas Company | Polymer concrete compositions, methods of application thereof, and polymerized products thereof |
SU835987A1 (en) * | 1979-05-24 | 1981-06-07 | Калушский Филиал Всесоюзного Научно- Исследовательского И Проектногоинститута Галургии | Polymer-concrete mix |
US4400413A (en) * | 1980-08-29 | 1983-08-23 | Rohm And Haas Company | Acrylic polymer concrete compositions |
ZA815786B (en) * | 1980-08-29 | 1982-08-25 | Rohm & Haas | Monomer compositions,polymer concrete compositions containing them and their use |
SU996378A1 (en) * | 1981-07-03 | 1983-02-15 | Калушский Филиал Всесоюзного Научно-Исследовательского И Проектного Института Галургии | Polymeric concrete mix |
US4460625A (en) * | 1981-07-16 | 1984-07-17 | Rohm And Haas Company | Method of coating and impregnating concrete substrates, and products obtained thereby |
JPS58204008A (en) * | 1982-05-24 | 1983-11-28 | Hitachi Ltd | Photosensitive resin composition |
US4932750A (en) * | 1982-12-09 | 1990-06-12 | Desoto, Inc. | Single-coated optical fiber |
SU1209672A1 (en) * | 1983-12-28 | 1986-02-07 | Центральный научно-исследовательский и проектно-экспериментальный институт промышленных зданий и сооружений | Polymerconcrete mix |
US4556701A (en) * | 1984-03-30 | 1985-12-03 | Rohm And Haas Company | Impregnant compositions for porous substrates |
JPS6271573A (en) * | 1985-09-24 | 1987-04-02 | Dainippon Ink & Chem Inc | Actual spot painting and curing method for floor surface |
JPH0618844B2 (en) * | 1985-11-29 | 1994-03-16 | 日本合成ゴム株式会社 | Liquid radiation curable resin composition |
SU1465432A1 (en) * | 1987-03-23 | 1989-03-15 | Калушский Филиал Всесоюзного Научно-Исследовательского И Проектного Института Галургии | Polymer-concrete mix composition |
DE3822202A1 (en) * | 1988-07-01 | 1990-01-04 | Sandoz Ag | Acrylic acid esters and homopolymeric compounds thereof |
DE3920795C2 (en) * | 1988-07-01 | 1999-06-24 | Mbt Holding Ag | Asymmetric diesters, processes for their preparation and preparations containing them |
SU1701686A1 (en) * | 1989-07-07 | 1991-12-30 | Калушский Филиал Всесоюзного Научно-Исследовательского И Проектного Института Галургии | Polymer-concrete mixture |
JPH03265561A (en) * | 1990-03-13 | 1991-11-26 | Hitachi Chem Co Ltd | Production of high-density oxide superconductor |
-
1992
- 1992-06-04 DE DE4218414A patent/DE4218414C2/en not_active Expired - Lifetime
- 1992-06-09 BE BE9200531A patent/BE1005805A3/en not_active IP Right Cessation
- 1992-06-10 FR FR9207173A patent/FR2677656B1/en not_active Expired - Lifetime
- 1992-06-10 GB GB9212306A patent/GB2256645B/en not_active Expired - Lifetime
- 1992-06-11 CH CH1845/92A patent/CH684795A5/en not_active IP Right Cessation
- 1992-06-11 ES ES09201224A patent/ES2059235B1/en not_active Expired - Fee Related
- 1992-06-12 AU AU18173/92A patent/AU654717B2/en not_active Expired
- 1992-06-12 CA CA002071101A patent/CA2071101A1/en not_active Abandoned
- 1992-06-12 AT AT0121092A patent/AT398966B/en not_active IP Right Cessation
- 1992-06-12 JP JP4153278A patent/JP2696039B2/en not_active Expired - Lifetime
- 1992-06-12 IT ITRM920441A patent/IT1255669B/en active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
JP2696039B2 (en) | 1998-01-14 |
DE4218414C2 (en) | 2001-04-05 |
GB2256645A (en) | 1992-12-16 |
CH684795A5 (en) | 1994-12-30 |
AT398966B (en) | 1995-02-27 |
ATA121092A (en) | 1994-07-15 |
IT1255669B (en) | 1995-11-09 |
ES2059235B1 (en) | 1995-10-01 |
FR2677656A1 (en) | 1992-12-18 |
FR2677656B1 (en) | 1993-10-22 |
BE1005805A3 (en) | 1994-02-01 |
ITRM920441A0 (en) | 1992-06-12 |
ITRM920441A1 (en) | 1993-12-12 |
GB2256645B (en) | 1995-03-15 |
AU654717B2 (en) | 1994-11-17 |
JPH05239379A (en) | 1993-09-17 |
AU1817392A (en) | 1992-12-17 |
ES2059235A1 (en) | 1994-11-01 |
DE4218414A1 (en) | 1992-12-17 |
GB9212306D0 (en) | 1992-07-22 |
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