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Patent US5616645 - Gelled fluoride resin fine particle dispersion, method of production thereof ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsThe present invention relates to a gelled fluoride resin fine particle dispersion for use as a coating, to a method of production thereof, and to a method using this gelled fluoride resin fine dispersion to protect an alkaline inorganic hardened body. The objective of the present invention is to provide...http://www.google.com/patents/US5616645?utm_source=gb-gplus-sharePatent US5616645 - Gelled fluoride resin fine particle dispersion, method of production thereof, and preservation method for an alkaline inorganic hardened body utilizing the sameAdvanced Patent SearchTry the new Google Patents, with machine-classified Google Scholar results, and Japanese and South Korean patents.Publication numberUS5616645 APublication typeGrantApplication numberUS 08/272,612Publication dateApr 1, 1997Filing dateJul 11, 1994Priority dateOct 30, 1990Fee statusLapsedAlso published asDE4192711T0, DE4192711T1, WO1992007886A1Publication number08272612, 272612, US 5616645 A, US 5616645A, US-A-5616645, US5616645 A, US5616645AInventorsShin'ichi Kuwamura, Yoshinobu Deguchi, Tokio Goto, Fumio YoshinoOriginal AssigneeDainippon Ink & Chemicals, Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (24), Referenced by (23), Classifications (28), Legal Events (5) External Links: USPTO, USPTO Assignment, EspacenetGelled fluoride resin fine particle dispersion, method of production thereof, and preservation method for an alkaline inorganic hardened body utilizing the same
US 5616645 AAbstract
The present invention relates to a gelled fluoride resin fine particle dispersion for use as a coating, to a method of production thereof, and to a method using this gelled fluoride resin fine dispersion to protect an alkaline inorganic hardened body.
1. An aqueous dispersion of particles of gelled fluoride resin prepared from a fluoro-olefin, other monomers and a crosslinking monomer, characterized in that said fluoride resin is obtained by mixing together and copolymerizing, in an aqueous medium and in the presence of an emulsifier, a fluoro-olefin, a second monomer, and, as a crosslinking monomer, a monomer containing a hydrolyzable silyl group.
The present invention relates to a gelled fluoride resin fine particle dispersion for use as a coating, to a method of production thereof, and to a method using this gelled fluoride resin fine particle dispersion to protect an alkaline inorganic hardened body.
In contrast, the manufacture of a coating material that uses an aqueous dispersion of a fluoro-olefin polymer such as polytetrafluoroethylene, polyvinylidene fluoride or polyhexafluoropropylene has been disclosed. However, this kind of coating, which uses this type of aqueous dispersion, requires high temperature heating for film forming. For example, in spite of a low molecular weight, such that the intrinsic viscosity (η) is 0.1˜0.5, heating at high temperature of 180�˜230� C. is still necessary for the aqueous dispersion using a copolymer of vinylidene fluoride and hexafluoropropylene disclosed in Japanese Patent Application, laid open number SHO 57-38845.
However, in Japanese Patent Application, laid open number SHO 61-261367, an emulsion copolymer based resin composition has disclosed for use as a coating to resolve the above various problems. This copolymer is composed from fluoro-olefin, alkyl vinyl ether and carboxylic acid vinyl ester. This resin composition can be applicable for use in protecting an alkaline inorganic hardened body. However, this resin composition is not satisfactory with respect to its adherence to the substrate, pigment dispersibility, nor to its dirt picking resistance. Additionally, when polymerization is carried out under acidic or basic conditions for the vinyl ether monomer, the vinyl ether monomer itself breaks down, and side reactions occur. For this reason, a disadvantage is presented in that reaction will only take place within a limited pH range, specifically around pH 4˜8. Thus, in the art up to now, it was necessary to add a large quantity of buffer to adjust pH. As a result, a fundamental problem exists in that, in association with water, the ability of coating film obtained is not sufficiently waterproof, alkaline resistant, etc.
Accordingly, it is the object of the present invention to provide an aqueous resin to be used as a coating having a wide variety of applications. This coating forms a film that excels with respect to its prevention of the leaching out of the alkaline substance from an alkaline inorganic hardened body, and to weatherability, water resistance, and resistance to chemicals and dirt picking resistance.
In other words, the present invention is a gelled fluoride fine particle dispersion, the characteristic feature of which is that the fluoride resin is a gelled fine particle dispersion, and that the degree of gellation of the dispersion constitutes 20˜100% by weight.
The gelled fine particles according to the present invention indicates particles that have been partially or completely internally gelled through the utilization of a cross linking monomer as the essential component at polymerization. The degree of gellation is approximately 20˜100% by weight, and preferably 40˜100% by weight. The degree of gellation is defined by the formula (1).
Accordingly, the preferable monomer combination used in the present invention is a fluoro-olefin, a carboxylic acid vinyl ester containing a straight alkyl chain or an alkyl branch or ring alkyl structure that composed from 5 or more carbon atoms, and a cross linking monomer. In particular, the preferable monomer composition for use as a coating material is 5˜20% by weight ethylene (monomer weight standard, liquid conversion, as below), 40˜60% by weight fluoro-olefin, 30˜50% by weight carboxylic acid vinyl ester containing a straight alkyl chain or an alkyl branch or ring alkyl structure which composed from 5 or more carbon atoms, 0.5˜3% by weight of a monomer containing an acid group, and 0.1˜2% by weight of a crosslinking monomer.
As for the quantity of these emulsifier used, combining the anion type and nonion type emulsifiers, weight ratios in the range of 0.5˜10% of the total monomer weight are appropriate.
As for the polymerization initiator used at the polymerization stage, provided that it is a substance generally used in an emulsion polymerization, no particular limitations are present. As an example, aqueous inorganic peroxides like hydrogen peroxide; persulfate salt like ammonia persulfate, potassium persulfate and sodium persulfate; organic peroxides like cumene hydroperoxide, benzolyperoxide, and t-butylhydroperoxide; azo type initiators like azobisisobutyronitrile, and azobisisocyanovaleric acid are available, and may be used singularly or in combination. As the quantity used, a weight ratio in the range of 0.1˜2% of the total weight of the monomer is preferable. Additionally, the so called redox polymerization method, through the combined use of these polymerization initiators (except azo type initiators), a metal ion and a reducing agent is acceptable.
In an aqueous medium and in the presence of an emulsifier, the monomers may be introduced into a reaction vessel to polymerize. Then the gelled fluoride resin fine particle dispersion can be obtained. As the aqueous medium, ion exchanged water is preferable. The monomers may be dropped in as is, or in an emulsified state. Additionally, the introducing of the monomers may be carried out all at once, in portions or continuously. The preferable conditions for polymerization are at a gage pressures of approximately 1 kg/cm2 ˜100 kg/cm2 and at a reaction temperature of approximately 50�˜150� C. Depending on the situation, polymerization can be carried out at pressure greater than the above, or at temperatures lower than these. For the ratio between the total monomer quantity and the aqueous medium, it may be set up that the final solid content constitutes 1˜60% by weight, with the preferable range being 15˜55% by weight. Furthermore, at emulsion polymerization, to enlarge or control the diameter of the particles, the seed polymerization method wherein polymerization is performed while in the presence of emulsion particles in an aqueous medium, may be used.
The polymerization reaction can be carried out in a pH range of approximately 1.0˜6.0. The pH may be adjusted using such pH buffer agents as disodium phosphate, borax, sodium bicarbonate, ammonia or the like. At higher pHs, defects arise in the water resistance and alkaline resistance properties of a film that has been applied as described above.
When the gelled fluoride resin fine particle dispersion obtained according to the present invention is converted to a state containing no cross linking monomers, its number average molecular weight corresponds to 5,000˜1,000,000, the weight average molecular weight also corresponds to 10,000˜3,000,000. The minimum film forming temperature of the dispersion according to the present invention is approximately 10�˜60� C. Additionally the particle diameter is approximately 0.02˜0.5 microns.
The material that is to be coated with the composition containing the obtained gelled fluoride resin fine particle dispersion may be metal, plastic, wood, glass, paper, textile, or the like. As a coating method, applications by brush, spray, roll or flow coater painting, or by dipping are all applicable. After coating, in addition to extending the setting time if necessary, high heat forced drying or ambient-temperature drying may be used to obtain the coating film as conditions required. In the case of high heat forced drying, drying may be carried out for an optional period at 60�˜200� C.
What follows below is an explanation of the present invention through the provision of representative examples. Moreover, "part" shall be taken herein to indicate "parts by weight".
(synthesis of gelled fluoride resin fine particle dispersion)
(synthesis of gelled fluoride resin fine dispersion)
(synthesis of a gelled fluoride resin fine particle dispersion)
Other than removing decadiene from Example 1, a dispersion not containing any crosslinking monomer was obtained, being produced in the same manner as in Example 1. It will be referred hereafter as (B-1).
Other than removing decadiene from Example 3, a dispersion not containing any crosslinking monomer was obtained, being produced in the same manner as in Example 3. It will be referred hereafter as (B-2).
(synthesis of the gelled fluoride resin fine particle dispersion of the present invention utilizing a carboxylic acid vinyl ester type monomer having less than 5 carbon atoms)
Following the completion of the reaction of Example 1, the reaction mixture was cooled to room temperature. After cooling, without addition of 14% aqueous ammonium, there was a large quantity of an aggregated emulsion generated, and the sample could not be used as a coating composition.
Following the completion of the reaction of Example 1, the reaction mixture was cooled to room temperature. After cooling, without addition of a silicon type defoaming agent (Nopco 8034L produced by Sun Nopco Manufacturing), considerable bubbling from the emulsion particles occurred with the result that there was a large quantity of an aggregated emulsion generated, and the sample could not be used as a coating composition.
Application Example (formulation of aqueous coating composition)
Each of the gelled fluoride resin fine particle dispersion obtained in examples 1˜5 (resin number A-1˜A-5) and the dispersion obtained in reference examples 1˜2 (resin member B-1˜B-2) was diluted to a 45% solid content, texanol was added in the amount of 2% was added as the coalescent, and an aqueous composition was obtained. Each of the obtained compositions was dip coated to a slate plate as a base material and dried for 20 minutes at 60� C. Next, these were allowed to dry at room temperature for 7 days, and each of the following experiments was performed. Additionally, in test (8), testing long term resistance to boiling water at high temperature, a glass plate was used as the base material.
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KnowltonMethod and composition for treating fibrous substrates to impart oil, water and dry soil repellencyUS6689854 *Aug 23, 2001Feb 10, 20043M Innovative Properties CompanyWater and oil repellent masonry treatmentsUS7429295Jun 6, 2002Sep 30, 2008Radi Al-RashedAqueous chemical mixture to mitigate water associated problems in concrete pavementsUS8030376Jul 12, 2007Oct 4, 2011Minusnine Technologies, Inc.Processes for dispersing substances and preparing composite materialsUS8124699 *Aug 4, 2006Feb 28, 2012Arkema Inc.Polymerization of fluoropolymers using alkyl phosphonate surfactantsUS8268189 *May 24, 2006Sep 18, 2012Akzo Nobel N.V.Storage-stable accelerator solutionUS8338518 *Dec 8, 2006Dec 25, 2012Arkema Inc.Aqueous process for making a stable fluoropolymer dispersionUS8513351 *Jun 22, 2005Aug 20, 2013Solvay Solexis S.P.A.Fluoroelastomer gelsUS8697822 *Jun 26, 2006Apr 15, 2014Arkema Inc.Polymerization of fluoropolymers using non-fluorinated surfactantsUS8729175 *Jul 9, 2013May 20, 2014Solvay Solexis S.P.A.Fluoroelastomer gelsUS20030083448 *Aug 23, 2001May 1, 20033M Innovative Properties CompanyWater and oil repellent masonry treatmentsUS20040186254 *Jan 28, 2004Sep 23, 20043M Innovative Properties CompanyWater and oil repellent masonry treatmentsUS20050282955 *Jun 22, 2005Dec 22, 2005Marco ApostoloFluoroelastomer gelsUS20060048670 *Jun 6, 2002Mar 9, 2006Radi Al-RashedAqueous chemical mixture to mitigate water associated problems in concrete pavementsUS20070032591 *Aug 4, 2006Feb 8, 2007Mehdi DuraliPolymerization of fluoropolymers using alkyl phosphonate surfactantsUS20070082993 *Dec 8, 2006Apr 12, 2007Ramin Amin-SanayeiAqueous process for making a stable fluoropolymer dispersionUS20080207841 *May 24, 2006Aug 28, 2008Akzo Nobel N.V.Storage-Stable Accelerator SolutionUS20080207860 *May 2, 2008Aug 28, 2008Daikin Industries, Ltd.Treating agent for masonryUS20090221776 *Jun 26, 2006Sep 3, 2009Arkema Inc.Polymerization of fluoropolymers using non-fluorinated surfactantsUS20100224480 *Feb 17, 2010Sep 9, 2010Stephan BloessMethod for Photocatalytic Separation from Surfactant-Containing DispersionsUS20130296464 *Jul 9, 2013Nov 7, 2013Marco ApostoloFluoroelastomer gelsEP1568721A1 *Nov 7, 2003Aug 31, 2005Daikin Industries, Ltd.Treating agent for masonry* Cited by examinerClassifications U.S. Classification524/546, 524/760, 524/455, 524/3, 523/340, 524/545, 524/761, 524/747, 524/456, 524/805, 524/7, 524/544, 524/745, 428/421, 524/794, 523/328, 524/762, 524/457International ClassificationC09D127/12, C08F218/10, C08F214/18Cooperative ClassificationC09D127/12, C08F218/10, C08F214/186, Y10T428/3154European ClassificationC09D127/12, C08F218/10, C08F214/18FLegal EventsDateCodeEventDescriptionSep 21, 2000FPAYFee paymentYear of fee payment: 4Sep 16, 2004FPAYFee paymentYear of fee payment: 8Oct 6, 2008REMIMaintenance fee reminder mailedApr 1, 2009LAPSLapse for failure to pay maintenance feesMay 19, 2009FPExpired due to failure to pay maintenance feeEffective date: 20090401RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services