WO2002012359A2 - Multipolymere en dispersion aqueuse, composition aqueuse et procede d'obtention d'un multipolymere en dispersion aqueuse - Google Patents
Multipolymere en dispersion aqueuse, composition aqueuse et procede d'obtention d'un multipolymere en dispersion aqueuse Download PDFInfo
- Publication number
- WO2002012359A2 WO2002012359A2 PCT/BR2001/000098 BR0100098W WO0212359A2 WO 2002012359 A2 WO2002012359 A2 WO 2002012359A2 BR 0100098 W BR0100098 W BR 0100098W WO 0212359 A2 WO0212359 A2 WO 0212359A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- multipolymer
- aqueous dispersion
- monomers
- fact
- dispersion
- Prior art date
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 7
- 239000000178 monomer Substances 0.000 claims abstract description 46
- 239000003973 paint Substances 0.000 claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 8
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 8
- 150000001993 dienes Chemical class 0.000 claims abstract description 8
- 238000010276 construction Methods 0.000 claims abstract description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001408 amides Chemical class 0.000 claims abstract description 5
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 5
- 239000000853 adhesive Substances 0.000 claims abstract description 4
- 230000001070 adhesive effect Effects 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 239000004753 textile Substances 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 21
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 14
- 239000012986 chain transfer agent Substances 0.000 claims description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- -1 2- ethylhexyl Chemical group 0.000 claims description 4
- 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
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- XHUZSRRCICJJCN-UHFFFAOYSA-N 1-ethenyl-3-ethylbenzene Chemical compound CCC1=CC=CC(C=C)=C1 XHUZSRRCICJJCN-UHFFFAOYSA-N 0.000 claims description 2
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- CHPXLAPHLQIKCA-UHFFFAOYSA-N but-3-en-2-ylbenzene Chemical compound C=CC(C)C1=CC=CC=C1 CHPXLAPHLQIKCA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 23
- 238000005406 washing Methods 0.000 abstract description 5
- 239000000123 paper Substances 0.000 abstract description 3
- 238000005562 fading Methods 0.000 abstract 1
- 238000004383 yellowing Methods 0.000 description 5
- 239000002174 Styrene-butadiene Substances 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 4
- 239000003139 biocide Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011115 styrene butadiene Substances 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- TUZBYYLVVXPEMA-UHFFFAOYSA-N butyl prop-2-enoate;styrene Chemical compound C=CC1=CC=CC=C1.CCCCOC(=O)C=C TUZBYYLVVXPEMA-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000003254 anti-foaming effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- SVTBMSDMJJWYQN-UHFFFAOYSA-N hexylene glycol Natural products CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
Definitions
- the invention refers to a multipolymer in aqueous dispersion, which is useful for application in the fields of coating, textile, adhesive, paper, civil construction, etc., and more specifically paint.
- the invention also refers to compositions containing a multipolymer and a process to obtain a multipolymer.
- Polymers in aqueous dispersion are well-known and widely used products. Efforts to develop the application of such polymers are known, e. g. since the water base is less polluting than the organic solvent base.
- the invention aims at a multipolymer in aqueous dispersion which improves mechanical properties of paint formulated therewith, as well as a process to obtain such polymer.
- the invention therefore relates, in a first embodiment, to a multipolymer in aqueous dispersion, said multipolymer being comprised of at least four monomers under the following weight percentage distribution: - from about 40% to 80% of a hard monomer,'
- multipolymers of the invention are advantageously comprised of only four monomers.
- the multipolymers of the invention as mentioned above particularly include : from about 50% to 70% of a hard monomer; from about 15% to 30% of a soft monomer, ethylenically unsaturated carboxylic acid ester at the positions ⁇ , ⁇ ; - from about 10% to 20% of a monomer selected from the group comprising conjugated dienes and butene; from about 3% to 5% of an acid selected from the group comprising acrylic acid and methacrylic acid, or amides from those acids, particularly selected from the group comprising acrylamide and methacrylamide.
- Hard monomer is understood as the one that originates a polymer with Tg greater than about 40 °C.
- Soft monomer designates monomers that originate a polymer with a Tg lower than about 25 °C.
- Hard monomers are preferably selected from the group comprising styrene, ⁇ -methyl styrene, p-tert-butyl styrene, 3 _ ethyl styrene and methyl vinyl toluene. Styrene is particularly preferred.
- An ethylenically unsaturated carboxylic acid ester at the positions ⁇ , ⁇ is advantageously selected from the group comprising alkyl esters, preferably methyl, ethyl, butyl and 2-ethylhexyl, of acrylic or methacrylic acids. Butyl acrylate and methyl acrylate are preferred.
- a conjugated diene monomer is advantageously selected from butadiene and isoprene.
- Butadiene is the preferred conjugated diene.
- the ethylenically unsaturated carboxylic acid amide is preferably acrylamide.
- Tg glass transition temperature
- Polymers of the invention are used as aqueous dispersions, obtained by means of a process which is also an object of the invention, and which is different from the state of the art for not making use of the addition of polymeric dispersing agents with molecular weight of more than 1000 for the esteric stabilization of the polymer dispersed particles, for instance as disclosed in the patent US 4,322,328, or the addition of emulsifiers such as a salt of acyl ester of a hidroximethanephosphonic acid to optimize the adherence of the paint to the substrates, for instance as disclosed in the patent US 4,169,086.
- - surfactants may be anionic or non-ionic ' - chain transfer agent is not added initially, but subsequently with the monomers or the remainder of the monomers;
- Process ingredients such as surfactants, chain transfer agent, initiator, coalescent, antifoaming and biocide agents, are products well-known by one skilled the art and do not, in their generality, limit the scope of the invention.
- process variables directly or indirectly affect final product characteristics.
- Variables such as temperature, chain transfer agent concentration and monomer composition can affect properties such as Tg, minimum film formation temperature, gel content (insolubles), etc.
- Surfactant composition, initial quantity of monomers at the start of the reaction and the initial quantity of initiator can directly affect particle size distribution.
- the monomer mix composition added during the process can affect the polymer particle structure.
- compositions of matter including the multipolymer as described are compositions presenting better mechanical resistance as such, better resistance to the loss of such mechanical and color properties.
- paint compositions it is observed that in comparison to similar paints containing other state of the art polymers, in the washing capacity test as described by the U. S. standard ASTM 2486-96, there is an unforeseen increase in wear resistance.
- ultraviolet light exposure tests for whitening and yellowing as per the U. S. standard ASTM G-53-96 show that the white color is better maintained and there is stronger resistance to the appearance of yellow color.
- composition comprising a multipolymer according to the aforementioned characteristics. It is particularly a latex paint composition for civil constructions, containing about 3% to about 10% of the multipolymer of the invention, providing for a high cost-benefit relation in comparison to other paints as obtained with prior art polymers.
- paint 3 mixing of two polymers, namely styrene-butadiene and styrene- butyl acrylate, so as to present about the same weight of styrene, butadiene and butyl acrylate as in paint 1.
- Paints 1, 2 and 3 were evaluated for their washing resistance and UV resistance regarding whiteness and yellowing (paint 4 was also evaluated in this criteria), as per the attached figures.
- Figure 1 presents washing resistance results just for paints 1, 2 and 3, according to method ASTM 2486-96, after curing in oven at 60 °C for 16 hours.
- the X axis shows paint reference while the Y axis show cycle numbers up to which a film made with the paint resists.
- Figures 2 and 3 respectively present whiteness and yellowing results for up to a 35 day-exposure of ultraviolet light according to the test ASTM G-53-96, measured by a Elrepho Datacolor 2000 device.
- the whiteness of paint 1 reaches a very close value, despite a bit lower than paint 4, which is considered as excellent, i. e. with styrene/butyl acrylate polymer.
- the whiteness of paint 1 after longer periods is better than paints 2 and 3.
- 35-day yellowing of paint 1 containing the multipolymer of the invention is significantly lower than paints 2 and 3, based on styrene -butadiene or styrene-butadiene plus styrene-butyl acrylate, being closer to the performance of paint 4, based on styrene-butyl acrylate.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
L'invention porte sur un multipolymère en dispersion aqueuse utilisable dans les domaines des revêtements, des textiles, des adhésifs, du papier, du bâtiment et des peintures plus spécifiques, sur des compositions contenant ledit multipolymère, et sur son procédé de préparation. Ledit multipolymère en dispersion aqueuse comporte au moins quatre monomères dont: un monomère sur; un ester d'acide carboxylique non saturé en éthylène aux positions α, β; un monomère choisi parmi des diènes conjugées ou un butène congugé; et un ester d'acide carboxylique non saturé en éthylène aux positions α, β ou ses amides. Les peintures économiques pour bâtiments contenant le multipolymère de l'invention présentent une meilleure résistance au lavage et une moindre décoloration que celles contenant les polymères utilisés habituellement.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2001277424A AU2001277424A1 (en) | 2000-08-08 | 2001-08-08 | Multipolymer in aqueous dispersion, water-based composition and process to obtain a multipolymer in aqueous dispersion |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BR0003660-9A BR0003660A (pt) | 2000-08-08 | 2000-08-08 | Multipolìmero em dispersão aquosa, composição de base aquosa, e processo de obtenção de multipolìmero em dispersão aquosa |
| BRPI0003660-9 | 2000-08-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2002012359A2 true WO2002012359A2 (fr) | 2002-02-14 |
| WO2002012359A3 WO2002012359A3 (fr) | 2002-04-25 |
Family
ID=3944983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/BR2001/000098 WO2002012359A2 (fr) | 2000-08-08 | 2001-08-08 | Multipolymere en dispersion aqueuse, composition aqueuse et procede d'obtention d'un multipolymere en dispersion aqueuse |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU2001277424A1 (fr) |
| BR (1) | BR0003660A (fr) |
| WO (1) | WO2002012359A2 (fr) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7141596B2 (en) | 2003-10-08 | 2006-11-28 | Incyte Corporation | Inhibitors of proteins that bind phosphorylated molecules |
| WO2008068066A3 (fr) * | 2006-12-08 | 2008-11-20 | Henkel Ag & Co Kgaa | Agent fixatif pour fibres de kératine |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2939657A1 (de) * | 1979-09-29 | 1981-04-16 | Basf Ag, 6700 Ludwigshafen | Bindemittel fuer papierstreichmassen |
| DE3708992A1 (de) * | 1987-03-19 | 1988-09-29 | Dow Chemical Co | Waesserige polymerdispersion aus einem cyanoalkylester ungesaettigter carbonsaeuren enthaltenden polymer und ihre verwendung zum beschichten von papier |
| DE69226173T2 (de) * | 1992-01-10 | 1999-02-18 | Sumitomo Dow Ltd., Osaka | Verfahren zur herstellung eines copolymer-latices und dessen verwendung |
-
2000
- 2000-08-08 BR BR0003660-9A patent/BR0003660A/pt not_active Application Discontinuation
-
2001
- 2001-08-08 AU AU2001277424A patent/AU2001277424A1/en not_active Abandoned
- 2001-08-08 WO PCT/BR2001/000098 patent/WO2002012359A2/fr active Search and Examination
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7141596B2 (en) | 2003-10-08 | 2006-11-28 | Incyte Corporation | Inhibitors of proteins that bind phosphorylated molecules |
| WO2008068066A3 (fr) * | 2006-12-08 | 2008-11-20 | Henkel Ag & Co Kgaa | Agent fixatif pour fibres de kératine |
Also Published As
| Publication number | Publication date |
|---|---|
| BR0003660A (pt) | 2002-03-26 |
| AU2001277424A1 (en) | 2002-02-18 |
| WO2002012359A3 (fr) | 2002-04-25 |
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