US20070066780A1 - Masonry-treating agent - Google Patents
Masonry-treating agent Download PDFInfo
- Publication number
- US20070066780A1 US20070066780A1 US10/559,810 US55981004A US2007066780A1 US 20070066780 A1 US20070066780 A1 US 20070066780A1 US 55981004 A US55981004 A US 55981004A US 2007066780 A1 US2007066780 A1 US 2007066780A1
- Authority
- US
- United States
- Prior art keywords
- group
- fluorine
- monomer
- atom
- masonry
- 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
- BVCNIQVREQLQHO-UHFFFAOYSA-M C=C(C)C(=O)O[Y][Rf] Chemical compound C=C(C)C(=O)O[Y][Rf] BVCNIQVREQLQHO-UHFFFAOYSA-M 0.000 description 3
- VIGPYQIIDVBRBA-UHFFFAOYSA-N C.CCC1CO1 Chemical compound C.CCC1CO1 VIGPYQIIDVBRBA-UHFFFAOYSA-N 0.000 description 1
- XPJKRZMXXWANNQ-UHFFFAOYSA-N C1=CC=C(C2=CC=CC=C2)C=C1.C1=CC=CC=C1.C=C(Br)C(=O)OCC[Rf].C=C(C#N)C(=O)OCC[Rf].C=C(C(=O)OCCN(C)S(=O)(=O)[Rf])C(F)(F)F.C=C(C(=O)OCC[Rf])C(F)(F)F.C=C(C(=O)OCC[Rf])C1=CC=CC=C1.C=C(CC1=CC=CC=C1)C(=O)OCC[Rf].C=C(Cl)C(=O)OCCN(C)S(=O)(=O)[Rf].C=C(Cl)C(=O)OCCN1(CCCC)[Rf]S1(=O)=O.C=C(Cl)C(=O)OCC[Rf].C=C(F)C(=O)OC.C=C(F)C(=O)OC.C=C(F)C(=O)OC1CCC([Rf])CC1.C=C(F)C(=O)OCCN(C)S(=O)(=O)[Rf].C=C(F)C(=O)OCCN1(CC)[Rf]S1(=O)=O.C=C(F)C(=O)OCC[Rf].C=C(I)C(=O)OCC[Rf].C=C([Rf])C(=O)OCC[Rf].C[Rf].C[Rf] Chemical compound C1=CC=C(C2=CC=CC=C2)C=C1.C1=CC=CC=C1.C=C(Br)C(=O)OCC[Rf].C=C(C#N)C(=O)OCC[Rf].C=C(C(=O)OCCN(C)S(=O)(=O)[Rf])C(F)(F)F.C=C(C(=O)OCC[Rf])C(F)(F)F.C=C(C(=O)OCC[Rf])C1=CC=CC=C1.C=C(CC1=CC=CC=C1)C(=O)OCC[Rf].C=C(Cl)C(=O)OCCN(C)S(=O)(=O)[Rf].C=C(Cl)C(=O)OCCN1(CCCC)[Rf]S1(=O)=O.C=C(Cl)C(=O)OCC[Rf].C=C(F)C(=O)OC.C=C(F)C(=O)OC.C=C(F)C(=O)OC1CCC([Rf])CC1.C=C(F)C(=O)OCCN(C)S(=O)(=O)[Rf].C=C(F)C(=O)OCCN1(CC)[Rf]S1(=O)=O.C=C(F)C(=O)OCC[Rf].C=C(I)C(=O)OCC[Rf].C=C([Rf])C(=O)OCC[Rf].C[Rf].C[Rf] XPJKRZMXXWANNQ-UHFFFAOYSA-N 0.000 description 1
- SONUZAIPWUJMTH-UHFFFAOYSA-N C=C(Cl)C(=O)OCC(O)C[Rf].C=C(Cl)C(=O)OCC1(OC(C)=O)C[Rf]1.C=C(F)C(=O)OCC(C[Rf])OC(C)=O.C=C(F)C(=O)OCC(O)C[Rf] Chemical compound C=C(Cl)C(=O)OCC(O)C[Rf].C=C(Cl)C(=O)OCC1(OC(C)=O)C[Rf]1.C=C(F)C(=O)OCC(C[Rf])OC(C)=O.C=C(F)C(=O)OCC(O)C[Rf] SONUZAIPWUJMTH-UHFFFAOYSA-N 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
- 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
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
-
- 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
- C04B41/4838—Halogenated polymers
- C04B41/4842—Fluorine-containing polymers
Definitions
- the present invention relates to a fluorine-containing polymer for treating a masonry and a composition for treating a masonry.
- JP-A-57-23662 describes that an acrylate having a Rf group is coated on a concrete and a stone to form a protective film.
- JP-A-07-109317 discloses a treatment agent comprising a fluorine-containing copolymer comprising a monomer having a Rf group, and a silicone-based vinyl monomer.
- JP-A-11-507687 discloses a masonry-treatment agent comprising a water-soluble polymer having a Rf group, a carboxyl group, an oxyalkylene group and a silyl group.
- EP1225187 discloses the treatment of ceramics with a polymer having a silyl group which comprises a Rf group-containing monomer, a fluorine-free monomer and a silyl group-containing monomer. Further, JP-A- 11-077677 proposes that a stone is treated with a phosphate ester having a Rf group.
- a water- and oil-repellent agent and a soil resist agent comprising a polymer containing a fluorine-containing acrylate substituted at its ⁇ -position by a fluorine atom, chlorine atom or the like are disclosed in, for example, JP-A-63-90588, JP-A-63-99285 and JP-A-1-315471. However, these have not been practically used as a masonry-treatment agent.
- PFOA perfluorooctanoic acid
- telomers have a possibility to produce PFOA when decomposed or metabolized (herein, the telomer means a long chain fuluoroalkyl group), and also that telomers have been widely used in foam fire extinguishers, care products, washing materials, carpets, textiles, paper, leather, etc., in order to impart water and oil repellency and soil resistance to them.
- One of objects of the present invention is to provide a treatment agent which imparts both of excellent water- and oil-repellency and excellent soil resistance to a masonry.
- the present invention provides a fluorine-containing polymer for masonry treatment, comprising:
- the present invention provides a fluorine-containing polymer for masonry treatment, comprising:
- the present invention provides also a composition for treating a masonry, which comprises the fluorine-containing polymer comprising (A) the fluorine-containing monomer of the formula (I) and (B) the monomer having a functional group reactive with active hydrogen, and a solvent.
- the present invention further provides a method of producing a treated masonry, which comprises applying said composition to a surface of a masonry, and then eliminating the organic solvent.
- the repeating units (A) are derived from the fluorine-containing monomer of the formula (I).
- the Rf group in the formula (I) is a fluoroalkyl group or a fluoroalkenyl group
- the Rf group is preferably a perfluoroalkyl group or a perfluoroalkenyl group.
- the fluoroalkyl group or the fluoroalkenyl group has 1 to 21 carbon atoms, particularly 1 to 6 carbon atoms, for example, 1 to 4 carbon atoms.
- fluoroalkyl group examples include —CF 3 , —CF 2 CF 3 , —CF 2 CF 2 CF 3 , —CF(CF 3 ) 2 , —CF 2 CF 2 CF 2 CF 3 , —CF 2 CF(CF 3 ) 2 , —C(CF 3 ) 3 , —(CF 2 ) 4 CF 3 , —(CF 2 ) 2 CF(CF 3 ) 2 , —CF 2 C(CF 3 ) 3 , —CF(CF 3 )CF 2 CF 2 CF 3 , —(CF 2 ) 5 CF 3 , —(CF 2 ) 3 CF(CF 3 ) 2 , —(CF 2 ) 4 CF(CF 3 ) 2 , —(CF 2 ) 7 CF 3 , —(CF 2 ) 5 CF(CF 3 ) 2 , —(CF 2 ) 6 CF(CF 3 ) 2 , and —(CF 2
- Y is an aliphatic group having 1 to 10 carbon atoms, an aromatic group or a cycloaliphatic group, each having 6 to 10 carbon atoms, a group —CH 2 CH 2 N(R 1 )SO 2 — group (in which R 1 is an alkyl group having 1 to 4 carbon atoms) or a —CH 2 CH(OY 1 )CH 2 — group (in which Y 1 is a hydrogen atom or an acetyl group).
- the aliphatic group is preferably an alkylene group, particularly having 1 to 4 carbon atoms, for example, 1 or 2 carbon atoms.
- the aromatic group and the cycloaliphatic group may be substituted or unsubstituted.
- the fluoroether group has at least one repeating unit (an oxyperfluoroalkylene group) selected from the group consisting of the repeating units: —C 3 F 6 O—, —C 2 F 4 O— and —CF 2 O—.
- the —C 3 F 6 O— group is —CF 2 CF 2 CF 2 O— or —CF 2 C(CF 3 )FO—.
- the —C 2 F 4 O— group is generally —CF 2 CF 2 O—.
- the total number of the oxyperfluoroalkylene repeating units is 1 to 200, for example, 1 to 100, and particularly 5 to 50.
- the fluoroether group has a terminal group which is directly bonded to the oxyperfluoroalkylene repeating unit.
- the terminal group examples include a hydrogen atom, a halogen atom (e.g., a fluorine atom), an alcohol group (e.g., HOCH 2 —), an epoxy group (for example, an amine group (e.g., H 2 N—), a carboxylic acid group (e.g., HOOC—), an acid halide group (e.g., F(O ⁇ )C—) and a chloromethyl group (ClH 2 C—).
- the fluoroether group may have a fluoroalkylene group having 1 to 10 carbon atoms, particularly a perfluoroalkylene group, in addition to the oxyperfluoroalkylene repeating unit and the terminal group. Examples of the fluoroalkylene group having 1 to 10 carbon atoms are —CF 2 — and —CF 2 CF 2 —.
- fluoroether group particularly, a perfluoroether group which is an example of the Rf group
- Rf group examples include the followings:
- fluorine-containing monomer examples include the followings: wherein Rf is a linear or branched fluoroalkyl or fluoroalkenyl group having 1 to 21 carbon atoms, or a fluoroether group having totally 1 to 200 repeating units selected from the group consisting of the repeating units: —C 3 F 6 O—, —C 2 F 4 O— and —CF 2 O—.
- examples of the functional group reactive with hydrogen atom includes a silane group, a phosphate group (or a phosphoric acid group), a carboxylate group (a carboxylic acid group), a sulfonate group (or a sulfonic acid group) and a glycidyl group.
- the monomer (B) is preferably a compound having a carbon-carbon double bond and a functional group reactive with active hydrogen.
- a monomer having the silane group is preferably a compound having a silane group (particularly a terminal silane group) and a carbon-carbon double bond.
- the monomer having the silane group may be a terminal silane coupling agent.
- silane group-containing monomer examples include:
- a monomer having the phosphate group examples include 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, acid phosphoxypropyl methacrylate, 3-chloro-2-acid phosphoxypropyl methacrylate, and 2-methacryloyloxyethyl acid phosphate monoethanolamine half salt.
- a monomer having the carboxylate group examples include methacrylic acid, acrylic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl phthalate, 2-acryloyloxyethyl phthalate, 2-methacryloyloxyethyl hexahydrophthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, 2-acryloyloxypropyl hexahydrophthalate, 2-acryloyloxypropyl tetrahydrophthalate, maleic anhydride and citraconic anhydride.
- a monomer having the sulfonate group examples include acrylamide-tert-butyl sulfonic acid, and 2-acrylamide-2-methylpropane sulfonic acid.
- a monomer having the glycidyl group examples include glycidyl methacrylate and glycidyl acrylate.
- the amount of the monomer having a functional group reactive with hydrogen atom (B) may be from 0.01 parts to 50 parts by weight, from 0.1 parts to 20 parts by weight, based on 100 parts by weight of the fluorine-containing polymer.
- the fluorine-containing polymer may contain (C) an other monomer, in addition to the fluorine-containing monomer (A) and the monomer having a functional group (B).
- the other monomer (C) may be a fluorine-free monomer.
- the fluorine-free monomer may be an alkyl group-containing monomer.
- the fluorine-free monomer may be a fluorine-free alkyl (meth)acrylate.
- the fluorine-free alkyl (meth)acrylate is generally a monomer of the formula: X 1 —CX 2 ⁇ CH 2 (i) wherein X 1 is an alkyl carboxylate group (the number of carbon atoms in the alkyl group: 1 to 18), and X 2 is a hydrogen atom or a methyl group.
- the fluorine-containing polymer may not contain the fluorine-free alkyl (meth)acrylate.
- the fluorine-containing polymer may contain the other monomer other than the fluorine-free alkyl (meth)acrylate.
- the other monomer are Rf group-free monomers such as ethylene, vinyl halide (for example, vinyl chloride), vinylidene halide (for example, vinylidene chloride), styrene, vinyl alkyl ketone, isoprene, chloroprene, butadiene, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, polypropyleneglycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylamino (meth)acrylate, trimethyl-(2-hydroxy-3-methacryloyloxypropyl) ammonium chloride and 3-chloro-2-hydroxyprop
- the amount of the other monomer may be from 0 to 100 parts by weight, for example, from 0 to 90 parts by weight; particularly from 1 to 70 parts by weight, based on 100 parts by weight of the fluorine-containing monomer (A).
- the fluorine-containing polymer can be prepared by any of conventional polymerization methods.
- the conditions of polymerization reaction can be arbitrarily selected.
- the polymerization procedure includes a bulk polymerization, a solution polymerization and an emulsion polymerization.
- the solution polymerization is generally preferable.
- the molecular weight of the fluorine-containing polymer may be generally from 5,000 to 1,000,000 (for example, measured in GPC and in terms of polystyrene).
- the treatment agent is in the form of a solution wherein the fluorine-containing polymer is dissolved in an organic solvent.
- the organic solvent may be an alcohol, an ester, a ketone, a halogenated hydrocarbon, or a petroleum organic solvent.
- the concentration of the fluorine-containing polymer may be, for example, from 0.1 to 50% by weight.
- the treatment agent may contain an antifreezing agent, a viscosity-adjusting agent, an ultraviolet absorbing agent, an antioxidant, a pH adjuster, a defoaming agent, an antiseptic agent, a flame retardant, etc. according to necessity.
- the treatment agent is applied to a substrate (masonry) to impart the water- and oil-repellency and the soil resistance to the substrate.
- the substrate is masonry such as stone.
- the masonry include stone, brick, concrete and tile.
- stone include natural stone (for example, marble and granite), and artificial stone.
- a method of treating the substrate is as follows.
- the treatment agent is applied to the substrate.
- the application can be can be performed by coating, dipping, brushing, etc.
- the organic solvent is removed.
- the removal of the organic solvent can be performed by, for example, the drying.
- the drying can be performed at a temperature of, for example, 0° C. to 200° C.
- the application amount of the fluorine-containing polymer may be 0.05 to 50 g, for example, 0.1 to 20 g, especially 1 to 10 g, per 1 m 2 of the surface area of the masonry.
- the treatment agent can give the water-repellent oil-repellent performance to the masonry surface, since the treatment agent contains the fluorine-containing polymer.
- the adhesion of a soil to masonry can be prevented, even if the soil is an aqueous soil or is an oily soil.
- a soil was put on a treated substrate, and droplets were left for 24 hours and wiped off with a paper towel.
- the evaluation was conducted according to the following criteria.
- the polymerization reaction was conducted to give a polymer solution in the same procedure as in Example 1 except that CF 3 CF 2 CF 2 CF 2 CH 2 CH 2 OCOCCl ⁇ CH 2 was changed to CF 3 CF 2 CF 2 CF 2 CH 2 CH 2 OCOCH ⁇ CH 2 .
- the polymer solution was diluted with butyl acetate to adjust the solid concentration to 3%, the treatment was conducted and the soil resistance test was conducted. The results are shown in Table 1 and Table 2.
- a gas chromatography revealed that a polymerization reaction conversion was at least 97%.
- the polymer solution was diluted with butyl acetate to adjust the solid concentration to 3%, the treatment was conducted and the soil resistance test was conducted. The results are shown in Table 1 and Table 2.
- Example 1 The polymerization reaction was conducted to give a polymer solution in the same procedure as in Example 1 except that CF 3 CF 2 CF 2 CF 2 CH 2 CH 2 OCOCCl ⁇ CH 2 was changed to CF 3 CF 2 CF 2 CF 2 CH 2 CH 2 OCOCF ⁇ CH 2 .
- the polymer solution was diluted with butyl acetate to adjust the solid concentration to 3%, the treatment was conducted and the soil resistance test was conducted. The results are shown in Table 1 and Table 2. TABLE 1 Soil resistance test (granite) Olive Oil Waste oil Red wine Coffee Example 1 5 5 4 5 Comparative Example 1 2 2 2 2 2 Comparative Example 2 3 3 2 3 Untreated 1 1 1 1 Example 2 5 5 5 5 Example 3 5 4 4 5
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Paints Or Removers (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/973,106 US9382363B2 (en) | 2003-06-09 | 2010-12-20 | Masonry-treating agent |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003-163462 | 2003-06-09 | ||
JP2003163462 | 2003-06-09 | ||
PCT/JP2004/008243 WO2004108779A1 (ja) | 2003-06-09 | 2004-06-07 | メーソンリー処理剤 |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2004/008243 A-371-Of-International WO2004108779A1 (ja) | 2003-06-09 | 2004-06-07 | メーソンリー処理剤 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/973,106 Division US9382363B2 (en) | 2003-06-09 | 2010-12-20 | Masonry-treating agent |
Publications (1)
Publication Number | Publication Date |
---|---|
US20070066780A1 true US20070066780A1 (en) | 2007-03-22 |
Family
ID=33508754
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/559,810 Abandoned US20070066780A1 (en) | 2003-06-09 | 2004-06-07 | Masonry-treating agent |
US12/973,106 Expired - Fee Related US9382363B2 (en) | 2003-06-09 | 2010-12-20 | Masonry-treating agent |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/973,106 Expired - Fee Related US9382363B2 (en) | 2003-06-09 | 2010-12-20 | Masonry-treating agent |
Country Status (5)
Country | Link |
---|---|
US (2) | US20070066780A1 (de) |
EP (1) | EP1640387B1 (de) |
JP (1) | JP4305448B2 (de) |
CN (1) | CN100374474C (de) |
WO (1) | WO2004108779A1 (de) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100227173A1 (en) * | 2007-05-15 | 2010-09-09 | Daikin Industries, Ltd. | Water-repellent oil-repellent antifouling agent having good solubility in solvent |
US8674031B2 (en) | 2008-11-11 | 2014-03-18 | Daikin Industries, Ltd. | Method of preparing water- and oil-repellent soil-resistant composition |
US8975348B2 (en) | 2010-02-12 | 2015-03-10 | E I Du Pont De Nemours And Company | Non-aqueous composition comprising partially fluorinated methacrylic polymers |
US9382504B2 (en) | 2008-12-19 | 2016-07-05 | 3M Innovative Properties Company | Composition and method to provide stain release and stain repellency properties to substrates |
US9410054B2 (en) | 2008-12-19 | 2016-08-09 | 3M Innovative Properties Company | Composition and method for providing stain release or stain repellency to substrates |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4329760B2 (ja) | 2003-06-09 | 2009-09-09 | ダイキン工業株式会社 | ケイ素を含有する含フッ素表面処理剤 |
WO2007127267A2 (en) * | 2006-04-27 | 2007-11-08 | Dow Corning Corporation | Composition for treating masonry |
WO2010044479A1 (en) * | 2008-10-13 | 2010-04-22 | Daikin Industries, Ltd. | Fluorine- and silicon-containing treatment agent for concretes |
WO2011122442A1 (ja) * | 2010-03-30 | 2011-10-06 | ダイキン工業株式会社 | α-クロロアクリレートを使用した撥水撥油剤 |
US20200199276A1 (en) * | 2017-07-25 | 2020-06-25 | Daikin Industries, Ltd. | Fluorine-containing polymer, mold release agent composition and mold release method |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4366300A (en) * | 1980-06-03 | 1982-12-28 | Pcuk - Produits Chimiques Ugine Kuhlmann | Composition and process for the protection of materials against spots or stains |
US4592930A (en) * | 1984-05-11 | 1986-06-03 | The Dow Chemical Company | Perfluorocarbon based polymeric coatings having low critical surface tensions |
US5021316A (en) * | 1988-10-06 | 1991-06-04 | Daikin Industries, Ltd. | Coated carriers for developing electrostatic images |
US5021501A (en) * | 1986-05-28 | 1991-06-04 | Daikin Industries, Ltd. | Fluorine-containing water-repellent oil-repellent composition |
US5069941A (en) * | 1988-03-16 | 1991-12-03 | Daikin Industries, Ltd. | Water- and oil-repellent antifouling finishing agent |
US5128389A (en) * | 1988-02-01 | 1992-07-07 | Daikin Industries, Ltd. | Hard coating agents comprising fluorine-containing acxylate copolymers |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6390588A (ja) | 1986-10-06 | 1988-04-21 | Daikin Ind Ltd | 撥水撥油剤 |
JPS6399285A (ja) | 1986-05-28 | 1988-04-30 | Daikin Ind Ltd | 撥水撥油剤 |
JP2770387B2 (ja) | 1988-03-16 | 1998-07-02 | ダイキン工業株式会社 | 防汚加工剤 |
JPH0778154B2 (ja) * | 1991-07-11 | 1995-08-23 | ヘキスト合成株式会社 | 含フッ素アクリル系共重合体水性エマルジョンの製造方法及びその組成物 |
JP3278243B2 (ja) | 1993-06-18 | 2002-04-30 | キヤノン株式会社 | 光電変換装置 |
JPH07109317A (ja) | 1993-10-14 | 1995-04-25 | Shin Etsu Chem Co Ltd | 含フッ素共重合体 |
US6037429A (en) | 1995-06-16 | 2000-03-14 | 3M Innovative Properties Company | Water-soluble fluorochemical polymers for use in water and oil repellent masonry treatments |
FR2762000B1 (fr) * | 1997-04-09 | 1999-05-14 | Atochem Elf Sa | Synthese de copolymeres fluores en milieu hydrocarbone |
JPH1177677A (ja) | 1997-09-03 | 1999-03-23 | Mitsui Chem Inc | 繊維補強熱可塑性樹脂シートの製造方法 |
JP3961644B2 (ja) * | 1997-10-22 | 2007-08-22 | 関西ペイント株式会社 | 撥水性を有する共重合体水溶液もしくは水分散液、及びその製造方法、及びこれを含む水性塗料組成物 |
JP2000264757A (ja) * | 1999-03-23 | 2000-09-26 | Daikin Ind Ltd | 石材の表面改質剤及び改質方法 |
JP4242531B2 (ja) * | 1999-11-29 | 2009-03-25 | 富士化成工業株式会社 | グラフト共重合体及び組成物 |
JP2002105433A (ja) * | 2000-10-02 | 2002-04-10 | Lion Corp | フッ素含有表面処理剤 |
FR2816622A1 (fr) * | 2000-11-15 | 2002-05-17 | Atofina | Copolymeres fluores pour le traitement hydrophobe et oleophobe des materiaux de construction |
ATE432298T1 (de) | 2001-01-19 | 2009-06-15 | 3M Innovative Properties Co | Fluorovinyloligomerkomponente mit silangruppen, flüssigzusammensetzungen daraus und beschichtungsverfahren |
JP4247657B2 (ja) * | 2001-07-30 | 2009-04-02 | Dic株式会社 | 防汚加工方法、及び該加工方法を施した基材 |
CN1167756C (zh) * | 2001-08-01 | 2004-09-22 | 温岭市力宝化工建材有限公司 | 石材保护剂及其制造方法 |
WO2004041880A1 (ja) * | 2002-11-08 | 2004-05-21 | Daikin Industries, Ltd. | メーソンリー処理剤 |
US20070197717A1 (en) * | 2004-04-09 | 2007-08-23 | Akihiko Ueda | Polymer for masonry treatment and treating agent |
-
2004
- 2004-06-07 EP EP04736265.2A patent/EP1640387B1/de not_active Not-in-force
- 2004-06-07 WO PCT/JP2004/008243 patent/WO2004108779A1/ja active Application Filing
- 2004-06-07 JP JP2005506847A patent/JP4305448B2/ja not_active Expired - Fee Related
- 2004-06-07 US US10/559,810 patent/US20070066780A1/en not_active Abandoned
- 2004-06-07 CN CNB2004800144002A patent/CN100374474C/zh not_active Expired - Fee Related
-
2010
- 2010-12-20 US US12/973,106 patent/US9382363B2/en not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4366300A (en) * | 1980-06-03 | 1982-12-28 | Pcuk - Produits Chimiques Ugine Kuhlmann | Composition and process for the protection of materials against spots or stains |
US4592930A (en) * | 1984-05-11 | 1986-06-03 | The Dow Chemical Company | Perfluorocarbon based polymeric coatings having low critical surface tensions |
US5021501A (en) * | 1986-05-28 | 1991-06-04 | Daikin Industries, Ltd. | Fluorine-containing water-repellent oil-repellent composition |
US5128389A (en) * | 1988-02-01 | 1992-07-07 | Daikin Industries, Ltd. | Hard coating agents comprising fluorine-containing acxylate copolymers |
US5069941A (en) * | 1988-03-16 | 1991-12-03 | Daikin Industries, Ltd. | Water- and oil-repellent antifouling finishing agent |
US5021316A (en) * | 1988-10-06 | 1991-06-04 | Daikin Industries, Ltd. | Coated carriers for developing electrostatic images |
US5071725A (en) * | 1988-10-06 | 1991-12-10 | Daikin Industries, Ltd. | Fluorinated copolymer coated carriers for developing electrostatic images |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100227173A1 (en) * | 2007-05-15 | 2010-09-09 | Daikin Industries, Ltd. | Water-repellent oil-repellent antifouling agent having good solubility in solvent |
KR101554114B1 (ko) | 2007-05-15 | 2015-09-17 | 다이킨 고교 가부시키가이샤 | 용제 용해성이 양호한 발수 발유 방오제 |
US8674031B2 (en) | 2008-11-11 | 2014-03-18 | Daikin Industries, Ltd. | Method of preparing water- and oil-repellent soil-resistant composition |
US9382504B2 (en) | 2008-12-19 | 2016-07-05 | 3M Innovative Properties Company | Composition and method to provide stain release and stain repellency properties to substrates |
US9410054B2 (en) | 2008-12-19 | 2016-08-09 | 3M Innovative Properties Company | Composition and method for providing stain release or stain repellency to substrates |
US8975348B2 (en) | 2010-02-12 | 2015-03-10 | E I Du Pont De Nemours And Company | Non-aqueous composition comprising partially fluorinated methacrylic polymers |
Also Published As
Publication number | Publication date |
---|---|
EP1640387A4 (de) | 2009-02-18 |
EP1640387B1 (de) | 2014-06-04 |
CN100374474C (zh) | 2008-03-12 |
JP4305448B2 (ja) | 2009-07-29 |
EP1640387A1 (de) | 2006-03-29 |
WO2004108779A1 (ja) | 2004-12-16 |
US20110086971A1 (en) | 2011-04-14 |
US9382363B2 (en) | 2016-07-05 |
CN1795216A (zh) | 2006-06-28 |
JPWO2004108779A1 (ja) | 2006-07-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9382363B2 (en) | Masonry-treating agent | |
KR101630137B1 (ko) | 용제 용해성이 양호한 발수 발유 방오제 | |
ZA200507474B (en) | Surface-treating agent comprising fluoropolymer | |
US8586184B2 (en) | Fluorine-containing polymer and aqueous treatment agent | |
US20070197717A1 (en) | Polymer for masonry treatment and treating agent | |
EP2362883B1 (de) | Verfahren zur herstellung einer wasser- und ölabweisenden schmutzabweisenden zusammensetzung | |
CA2251367A1 (en) | Waterborne fluoropolymer solutions for treating hard surfaces | |
WO2007127267A2 (en) | Composition for treating masonry | |
JP2009041031A (ja) | メーソンリー処理用組成物 | |
US6120892A (en) | Waterborne fluoropolymer solutions for treating hard surfaces |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: DAIKIN INDUSTRIES, LTD., JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:UEDA, AKIHIKO;MAEDA, MASAHIKO;FUKUDA, TERUYUKI;AND OTHERS;REEL/FRAME:017363/0029;SIGNING DATES FROM 20050107 TO 20050209 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |