ll
`
`Il
`
`lii
`
`111111
`
`OIl
`
`lOll
`
`1101
`
`liii
`
`1110
`
`100
`
`1101
`
`11111
`
`11111
`
`11111
`
`1O Patent No
`45 Date of Patent
`
`US006475632B1
`US 6475632 Bi
`Nov
`2002
`
`12 United States Patent
`Krieger et at
`
`54 DISPERSIONS FOR PRODUCING PAINT
`FOR CONCRETE ROOF TILES PAINT FOR
`CONCRETE ROOF TILES AND CONCRETE
`ROOF TILES COATED WITH SUCH PAINT
`
`75 Inventors
`
`Stephan Krieger Hofheim Klaus
`Zlmmerschled Wiesbaden Erhard
`Lupprich Frankfurt all of DE
`73 Assignee Clariant GmbH Frankfurt GB
`
`Notice
`
`Subject
`
`to any disclaimer the term of this
`is extended or adjusted under 35
`patent
`U.S.C 154b by
`days
`
`DE
`
`liP
`EP
`EP
`EP
`
`liP
`EP
`JP
`WO
`
`5215827
`5635566
`
`6/1993 Dotzaoer et al
`
`6/1997
`
`Gerharz et at
`
`428/500
`
`525/291
`
`FOREIGN PATENT DOCUMENTS
`
`124808
`0383002
`0469295
`492 210
`
`630 920
`
`694 557
`
`773 245
`
`4025502
`WO 92/00335
`
`3/1977
`8/1 990
`
`2/1992
`
`7/1992
`
`12/1994
`
`1/1996
`
`5/1997
`
`1/1992
`
`1/1992
`
`OTHER PUBLICATIONS
`
`21 App No
`22 PCT Filed
`86 PCT No
`371 c1
`
`09/646236
`
`Mar 17 1999
`
`PCT/EP99/01746
`
`Sep 11 2000
`Date
`87 PCT Pub No WO99/48841
`PCT Pub Date Sep 30 1999
`
`30
`Foreign Application Priority Data
`Mar 20 1998 DE
`51 Int Cl.7
`52 U.S Cl
`
`428/500
`525/328.5
`
`19812143
`
`B32B 27/00
`428/505
`
`428/507
`524/457
`524/460
`428/500 507
`524/457 460
`
`58 Field of Search
`
`428/509
`
`525/326.5
`
`56
`
`References Cited
`
`U.S PATENT DOCUMENTS
`
`English abstract of JP 4025502 Jan 29 1992
`PCT Search Report
`Derwent Patent Family Abstract
`Dcrwent Patcnt Family Abstract
`Derwent Patent Family Abstract
`Derwent Patent Family Abstract
`Derwent Patent Family Abstract
`Derwent
`Patent Family Abstract
`XP002108591
`
`694 577
`for EP
`773 245
`for EP
`469 295
`for EP
`for DD 124808
`for EP
`630 920
`JP 61
`174
`
`for
`
`279
`
`cited by examiner
`
`Primary ExaminerLeszek Kiliman
`74 Attorney Agent or FirmAnthony
`57
`ABSTRACT
`
`Bisulca
`
`The present
`composi
`provides copolymcr-based
`invention
`tions which are used to produce point
`for roof tiles in order
`to prevent algal vegetation crack formation increased water
`the paint more
`as well
`as chippipg off of
`absorption
`particularly on concrete
`roof tiles
`
`5047295
`
`9/1991 Dotzauer
`
`et at
`
`428/500
`
`15 Claims No Drawings
`
`O7O41
`
`

`

`US 6475632 Bi
`
`10
`
`loses of
`
`20
`
`to
`
`to
`
`DISPERSIONS FOR PRODUCING PAINT
`FOR CONCRETE ROOF TILES PAINT FOR
`CONCRETE ROOF TILES AND CONCRETE
`ROOF TILES COATED WITH SUCH PAINT
`
`The present invention relates to dispersions for preparing
`roof tile paints to roof tile paints and to roof tiles
`coated
`with roof tile paints
`In the course of the production of concrete roof tiles
`mortar mass is shaped
`and then generally colored usually
`prior to curing by coating with an emulsion paint i.e in the
`form of
`dispersion Subsequent curing then takes place
`togcther with the drying of the paint at temperatures of from
`second
`40 to 1000
`After curing there may be
`coating
`with an emulsion paint or with
`clearcoat and subsequent
`drying
`the paint does not coagulate on the uncured
`In order that
`concrete which is referred to as green concrete the binder
`certain degree
`of stability e.g
`required to possess
`is
`cement compatibility and heightened salt stability This is
`generally achieved
`through the use of ionic and/or nonionic
`emulsifiers and also by using functional monomers such as
`acid acrylic
`acid maleic acid acrylamide
`methacrylic
`methacrylamide
`ethenesulfonate
`and/or
`sulfoxyethyl
`for example
`In addition
`to coloring the
`methacrylate
`emulsion paint has the function of preventing lime effiores
`roof tiles core Another
`function is to
`as the concrete
`cencc
`prevent or reduce soil pickup and in particular
`of algae on the finished roof tiles
`The use of dispersions based
`on methacrylic
`esters
`and/or styrene for preparing roof tile paints is already known
`from DD 124808 EP-A-0 492 210 describes the use of
`certain monomers for reducing the soil pickup tendency of
`roof
`tile For the purpose of reducing lime
`the concrete
`EP-A-0 469 295 claims the use of emulsificrs
`cffiorcscencc
`based on sulfonated diaryl ethers
`For the purpose of stabilization the dispersions include
`such as emulsifiers and functional
`hydrophilic constituents
`monomers such as methacrylic
`acid acrylic acid maleic
`acid acrylamide methacrylamide
`ethenesulfonate or sul
`for example Owing to the hydro
`foxyethyl methacrylate
`films exhibit
`the corresponding paint
`constituents
`phobic
`heightened water absorption which may lead to increased
`algal growth on the concrete
`roof tiles and under conditions
`of freeze/thaw cycling to cracking and flaking of the paint
`owing to the water absorbed
`For the purpose of preventing algal growth DE-A-39 01
`073 describes the use of copolymerizablc
`tin compounds
`Like the subsequent addition of algicides however
`
`the growth
`
`this is
`
`ecologically
`objectionable
`It has now surprisingly been found that by using car
`as protective colloid it
`is possible to
`boxymethylcellulose
`prepare dispersions which as binders in roof
`tile paints
`exhibit sufficient cement stability but
`low water absorption
`in the paint film leading to reduced algal growth improved
`freeze/thaw stability of the coating and enhanced protection
`against effiorescence
`The present invention provides for the use for preparing
`dispersion prepared using from 0.1 to
`roof tile paints of
`preferably from 0.1 to 1.5 percent by weight based on the
`total monomer cootent of carboxymcthylccllulosc
`as pro
`monomer com
`tective colloid in connection with which
`
`position comprising
`from 85 to 99.8% by weight of acrylic esters with C1
`esters with C1 to C12
`to C12 alkanols methacrylic
`vinylaromatic monomers
`ailcannls and/or
`from 0.2 to 5% by weight of copolymcrizablc
`carboxy
`sulfates and/or sulfooates and
`lie acids carboxamides
`
`from to 10% by weight of other monomers
`in the form of an aqueous emulsion
`is polymerized
`The
`used preferably comprises
`carboxymethylcellulose
`water-soluble carboxymctbylcelluloscs
`degree of
`having
`substitution of from 0.4 to 2.9 with particular prefercoce
`from 0.4 to 1.5 and in particular
`from 0.6 to 1.4 the degree
`of substitution referring to the average number of carboxym
`ethyl groups introduced per anhydroglucose unit
`is pre
`whose 2% strength
`ferred to use carboxymetbylcelluloses
`Brookfleld viscosity 20 rpm at
`aqueous solutions possess
`25
`of less than 2000 with spindle
`with particular
`preference less than 500 with spindle
`and in particular
`mPas The earboxymethyl
`100 with spindle
`less than
`cellulose is used preferably in the form of its ammnnium salt
`is or alkali metal salt Examples of suitable commercial prod
`ucts are Blanose 7M Blanose 7UL Blanose 7EL and
`Ambergum 3021 from Aqualoo The earboxymethylcellu
`the invention may also
`comprise further
`radicals hay-
`constituents especially alkyl or bydroxyallcyl
`carbon atoms alkyloxyallcyl
`radicals having
`ing
`carbon atoms or dialkylamino radicals having
`total of
`carbon atoms Examples of suitable compounds are
`me th ylcarboxymetbyleellulose
`ethylearboxymethylcellulose
`25 hydroxyethylcarboxymetbylcellulose
`hydroxypropylcarboxymetbylcellulose
`methoxyethylearbuxymethyleellulnse
`ethnxyethylear
`and diethylaminocarboxymethyleel
`
`It
`
`to
`
`boxymethyleellulose
`
`lulose
`
`30
`
`Monomers
`
`esters of C1
`
`used
`
`and metbacrylic
`comprise acrylic
`to C12 monoalcobols
`such as ethyl acrylate
`
`butyl acrylate n-oetyl aerylate 2-etbylbexyl acrylate
`cyclohexyl metb
`methyl metbacrylate
`butyl methacrylate
`acrylate and isobomyl metbacrylate
`and/or vinylaromatic
`35 monomers such as styrene or vinyltoluene for example Use
`is made of those combinations
`known to the skilled worker
`of softening monomers
`such as butyl acrylate
`and
`for example with hardening
`acrylate
`2-etbylhexyl
`monomers such as metbyl methacrylate
`and styrene for
`40 example so that
`the glass transition temperature of
`the
`corresponding copolymer
`is situated preferably in the range
`from 10 to 60
`with particular preference in the range
`to 50
`from
`in the range from to
`and in particular
`40
`If operating by the technique of multistage
`polymerization the hardening and softening monomers and
`the ratio of the phases should preferably be combined such
`minimum film-forming tem
`that the dispersion possesses
`perature in the range from to 50
`and the corresponding
`so dispersion films possess an elongation at break of more than
`film thickness of 100 cm
`150% for
`As far
`as copolymerizable carboxylic acids
`earbnxamides
`are concerned
`sulfates and/or sulfonates
`preference is given to the use of acrylic acid methacrylic
`ss acid itaconic acid acrylamide methacrylamide
`sulfoalkyl
`methacrylates
`such as the potassium salt of sulfopropyl
`
`45
`
`emulsion
`
`metbacrylate SPM from Rosehig and/or sulfoallcylmetb
`sodium salt of acrylamido-2-
`as the
`acid A1vIPS from Lubrixol
`for
`
`aerylamides
`
`such
`
`metbylpropanesulfonic
`
`60 example
`Monomers which pay be used as said other monomers
`such as monomers
`are monomers containing keto groups
`acetoaeetoxy groups for example
`containing
`being aeetoaeetoxyethyl methacrylate
`acetoacetoxybutyl
`and vinyl
`65 metbacrylate acrylamidomethylaeetylacetooe
`derivatives of diacetone
`and polymerixable
`acetoacetate
`and diaeetonemetbacrylamide
`such as diacctoneaerylamide
`
`examples
`
`

`

`least
`
`It
`
`Further compounds which may be used as monomers
`hydroxyalkylmethacrylates glycidylmethacrylates
`alkoxyvinylsilanes methacryloyloxyalkylsilanes meth
`and polymerizable ethyl
`phosphates
`acryloyloxyalkyl
`eneurea derivatives such as N-3-methacrylozyethyl-N
`N-ethyleneurea and N--acrylamidoethyl-NN
`for example
`ethyleneurea
`In order to improve the soil pickup behavior dispersions
`whose other monomers
`include monomers containing
`keto grnups may be admixed with polyfunctional carbohy
`two hydrazide groups such as
`drazides containing at
`and
`oxalohydrazide isophthalohydrazide
`adipohydrazide
`polyacrylopolyhydrazide for example It
`is preferred to use
`an equimolar
`ratio of hydrazide groups to keto groups
`The polymerization is conducted in accordance with the
`common techniques of emulsion polymerization in which
`the monomers are emulsified in the aqueous phasc
`in thc
`presence of emulsifiers initiators and the protective colloid
`and are polymerized at temperatures from 60 to 95
`The
`emulsion polymerization may be conducted in accordance
`with the common techniques
`known to the skilled worker
`as batch monomer metering or emulsion
`feed tech
`such
`niques
`with the
`is preferred to operate in accordance
`emulsion feed technique
`in which
`small amount of the
`monomers is prepolymerized
`and then the remaining amount
`of monomers
`is metered in as an aqueous emulsion If
`desired two or more different monomer emulsions may also
`Like the emulsifier the protec
`be metered in successively
`tive colloid may be included in part
`in the initial
`charge to
`the reactor and/or metered in together with the monomer
`emulsion
`the polymerization is con
`An essential
`ducted at pH
`with particular preference in
`preferably
`this purpose the monomer
`range from to
`the p11
`emulsion comprising
`the 35
`the protective eolloid and also
`carboxamides
`sulfates
`
`feature is that
`
`For
`
`copolymerizable
`
`carboxylic
`
`acids
`
`ably
`
`reactor charge are/is
`and/or sulfonates
`and/or
`the initial
`adjusted using an aqueous ammonia alkali metal and/or
`pH
`alkaline earth metal hydroxide solution to
`prefer
`pH in the rahge from 40
`with particular preference to
`An alternative option is to use an appropriate buffer
`to
`The preparation of high-quality dispersions in accordance
`with the present inventirn presuppnses the applieatinn nf the
`existing experiences in the field of emulsion polymerization
`even where they are not described here Failure to properly
`observe the rules known to the skilled emulsion polymer
`ization worker may therefore
`affect
`adversely
`important
`resistance of
`properties an example being the water
`dispersion films Based on the polymer content
`therefore
`the com
`exceed
`should not substantially
`the dispersions
`monly used amounts of up to 3% by weight preferably up
`to 2% by weight of ionic emulsifiers and respectively
`up
`to 6% by weight preferably up to 4% by weight of nonionic
`
`45
`
`50
`
`the
`
`55
`
`emulsifiers
`Particular preference is given to the use of ionic emulsi
`fiers only in an amount of 2% by weight
`Examples of nonionic emulsifiers which may be used are
`alkyl polyglycol ethers such
`as ethoxylation
`products of
`alcohol
`or of mixtures such
`as
`lauryl oleyl or stearyl
`fatty alcohol alkylphenol polyglycol ethers such as 60
`coconut
`of octylpheool or nonylphenol
`ethoxylation products
`triisopropylphenol or of di- or tri-tert
`diisopropylphenol
`products of polypropylene
`butylphenol
`or ethoxylatioo
`oxide
`Suitable ionic emulsifiers are primarily anionic emulsifi- 65
`ers These may comprise the alkali metal salts or ammonium
`salts of alkyl- aryl- or alkylaryl-sulfonates
`
`or
`
`US 6475632 Bi
`
`are
`
`10
`
`15
`
`20
`
`25
`
`30
`
`-phosphonates alkyl aryl or alkylaryl sulfates or
`phosphates or compounds with other aoiooic end groups
`oxide
`oxide or polyethylene
`the presence of oligoethylene
`units bctwecu thc hydrucarbou radical aud the anionic group
`arc sodium lauryl
`examples
`also being possible Typical
`sulfate sodium undecyl glycol ether sulfate sodium lauryl
`diglycol sulfate sodium tetradecyl
`triglycol sulfate sodium
`ether sulfate sodium
`octylphenol
`glycol
`ammonium tri-tert-butylphenol
`dodecylbeozenesulfonate
`pentaglycol or octaglycol sulfate
`To start and continue the polymerization use is made of
`ini
`free-radical
`oil-soluble and/or preferably water-soluble
`tiators or redox systems Suitable compounds
`include for
`example hydrogen peroxide potassium sodium or ammo
`nium peroxodisulfate dibeuzoyl peroxide lauryl peroxide
`alone or
`peroxide bisazodiisobutyronitrilc
`tri-tert-butyl
`examples being sodium
`together with reducing components
`ascorbic acid and other com
`bisulflte Rongalit glucose
`pounds possessing reductive activity Preference is given to
`the use of peroxodisulfates
`is also possible to use regulators such as mercaptans
`
`It
`
`especially n-dodecylmercaptan
`thiophenol and/or 2-methyl-
`5-tert-butylthiophenol Usually amounts of from to
`by
`weight preferably from to 0.5% by weight are used and
`with particular preference the dispersion is prepared without
`
`using
`regulator
`pH of from 6.5
`The dispersions are usually adjusted to
`to 10 preferably from 7.0 to 9.0 using aqueous ammonia
`alkali metal and alkaline earth metal hydroxide solutions
`If desired the dispersion may further
`comprise film-
`as white spirit Texanol butyl
`forming auxiliaries such
`diglycol and butyl dipropyleoe glycol plasticizers such as
`dimethyl phthalate and dibutyl phthalate dispersants such as
`polyacrylic acids
`and corresponding
`copolymers such
`Lopon 890 Dispex G40 thickeners based on polyacry
`such as Borchigel L75 and Tafigel
`lates or polyurethanes
`PUR 40 preservatives
`defoamers
`such as mineral oil or
`
`as
`
`for example wetting
`silicone defoamers
`agents such
`aminomethylpropanol and other additives customary in the
`
`as
`
`fillers
`
`formulation of coatiog compositions
`The dispersion is suitable for coating roof files preferably
`are prepared
`green roof tiles Suitable coating compositions
`known manner by incorporating
`and
`in
`inorganic
`into the dispersion it being possible to
`color pigments
`establish the desired viscosity of the paint by adding water
`by using thickeners Examples of suitable inorganic
`and/or
`include calcite chalk quartz flour and/or heavy spar
`as red
`Suitable pigments include inorganic pigments such
`iron oxide for example and black pigments and
`also
`organic pigments
`invention is described in more detail below
`The present
`though without being
`with reference to working examples
`
`fillers
`
`restricted thereby
`
`EXAMPLE
`First of all monomer emulsion is prepared This is done
`by adjusting mixture of
`
`507
`121
`
`pbw of water
`pbw of Ambergum 3021
`36% strength
`aolutioo of C12 io C14 alkyl polyglycol
`39.3 pbw of
`ether autfate cootaioiog
`oxide units
`approximately
`ethylene
`
`iod
`
`11.0 pbw of meihacrytic acid
`
`to
`
`pH of
`incorporating
`
`using
`
`12.5% strength ammonia solution
`
`

`

`US 6475632 Bi
`
`572.0 pbw
`28.0 pbw
`2.75 pbw
`
`of methyl mcthacrylatn
`of
`and
`
`botyl acrytote
`of ammoniom peroxodisulfate
`
`by stirring with
`and continuing stirring
`high-speed stirrer
`stabte emulsion is formed Then in an appropriate
`reaction vessel
`
`until
`
`22.5 pbw
`of water
`8.65 pbw of Ambnrgum 3021
`solution of C2 to C14 atkyt polyglycol
`38% strength
`2.0 pbw
`of
`ether sulfate containing
`oxide
`approximately
`ethylene
`
`66.0 pbw
`
`units and
`of the monomer
`
`emnlsion
`
`EXAMPLE
`
`First of all monomer emulsion is prepared This is done
`by adjusting mixture of
`
`517.65 phw of water
`ULC
`75 pbw of Blanose
`38% strength
`solution of C2 to C4 atkyl potyglycol
`39.3 phw
`of
`oxide
`ether aulfale
`containing
`approximately
`
`ethylene
`
`anitn and
`
`11.0 phw
`
`of methacrytie
`
`acid
`
`to
`
`pH of
`incorporating
`
`using
`
`12.5% strength ammonia solution
`
`10
`
`15
`
`are heated to 80
`and admixed with solution of 0.55 pbw
`of ammonium peroxodisulfate in 15 pbw of water
`the remaining monomer emulsion is metered
`Subsequently
`in over the course of 3.5 hours Heating is continued for 60
`minutes and then the mixture is cooled The pH is adjusted
`12.5% strength ammonia solution The solids
`to 9.0 using
`content of the dispersion is 48.8% by weight and the MFT 25
`is 12
`
`20
`
`EXAMPLE
`
`First of all monomer emulsion is prepared This is done
`by adjusting mixture of
`
`30
`
`572.0 pbw
`pbw
`525
`
`2.75 pbw
`
`of methyl methacrylntr
`of butyl acrytate
`and
`of ammontum pnroxodisutfate
`
`and continuing stirring
`by stirring with
`high-speed stirrer
`stable emulsion is formed Fheo in an appropriate
`reaction vessel
`
`until
`
`522.5 phw of water
`IJLC
`1.1 pbw of Blanoan
`38% strength
`4.0 phw of
`ether sulfate containing
`and
`66.0 pbw of the monomer
`
`solution of
`
`C12
`
`to
`
`approximately
`
`emulsion
`
`nlkyl potyglycol
`oxide units
`
`ethylene
`
`508.2 pbw
`17.3 pbw
`39.3 pbw
`
`11.0 pbw
`
`of water
`
`of Ambnrgum 3021
`38% strength solution of C1 alkyl potyglycol ether
`of
`nulline containing
`ethylene oxide units
`of mnthncrylic
`acid and
`
`approximately
`
`5.5 pbw
`
`of amytic acid
`
`to
`
`pH of
`incorporating
`
`using
`
`12.5% strength ammonia solution
`
`40
`
`are heated to 80
`solution of 0.55 pbw
`and admixed with
`of ammonium peroxodisulfate in 15 pbw of water
`the remaining monomer emulsion is metered
`Subsequently
`in over the course of 3.5 hours Heating is continued for 60
`minutes and then the mixture is cooled The pH is adjusted
`12.5% strength ammonia solution The solids
`to 9.0 using
`content of the dispersion is 49.9% by weight and the MFT
`is 10
`
`EXAMPLE
`
`572.0 pbw
`528.0 pbw
`2.75 pbw
`
`of methyl methncrylate
`of hutyl acrylntc and
`of ammonium peroxodisulfatc
`
`45
`
`First of all monomer emulsion is prepared This is done
`by adjusting mixture of
`
`aod continuing stirring
`by stirring with
`high-speed stirrer
`stable emulsion is formed Then in an appropriate
`until
`reaction vessel
`
`522.5 pbw
`12.0 pbw
`4.0 pbw
`
`of water
`of Amhnrgum 3021
`38% strength solution of
`of
`
`66
`
`phw
`
`uilfnte cnntnining
`of the monomer
`
`opproximatety
`
`emulsion
`
`alkyt potyglycot
`oxide units and
`
`ether
`
`ethylene
`
`520.3 pbw of water
`
`5.5 pbw of Blanose ULC
`38% strength solution of C2 to
`39.3 pbw of
`ether sulfate
`containing
`npproximntrly
`
`and
`11.0 pbw of mnthncrylic acid
`
`50
`
`55
`
`alkyl polyglycol
`oxide units
`
`ethylene
`
`to
`
`pH of
`incorporating
`
`using
`
`12.5% strength ammonia solution
`
`are heated to 80
`aod admixed with solution of 0.55 pbw 60
`of ammonium peroxodisulfate in 15 pbw of water
`the remaining monomer emulsion is metered
`Subsequently
`in over the course of 3.5 hours Heating is continued for 60
`minutes and then the mixture is cooled The pH is adjusted
`12.5% streogth ammonia solution The solids
`to 9.0 using
`content of the dispersion is 49.5% by weight and the MFT
`is 9C
`
`572.0 pbw
`528.0 pbw
`
`2.75 pbw
`
`of mnlhyl mnlhncrytntc
`of botyl acrylate and
`of ammonium pcroxodisulfate
`
`65 by stirring vith high-speed stirrer and continuing stirring
`stable emulsion is formed Then in an appropriate
`reaction vessel
`
`uotil
`
`

`

`US 6475632 Bi
`
`522.50 pbw uf water
`uLC
`of Blanose
`38% strength solution of
`ether sulfate containing
`
`1.1 pbw
`4.0 pbw
`
`of
`
`C12 to C54 slkyl polyglycol
`oxide
`
`ethylene
`
`approximately
`
`66.0 pbw
`
`unite and
`of the monomer emulsion
`
`and admixed with solution of 0.55 pbw 10
`are heated to 800
`of ammonium peroxodisulfate in 15 phw of water
`the remaining monomer emulsion is metered
`Subsequently
`in over the course of 3.5 hours Heating is continued for 60
`minutes and then the mixture is cooled The pH is adjusted
`12.5% strength ammonia solution The solids
`to 9.0 using
`and the MFT
`content of the dispersion is 49.9% by weight
`is 13
`
`is
`
`-continued
`
`2.75 pbw uf ammonium peeoxodisslfate
`
`until
`
`by stirring with
`high-speed stirrer and continuing stirring
`stable emulsion is formed Then in an appropriate
`reaction vessel
`
`522.5 phw of water
`38% strength solution of
`19.7 phw of
`ether sulfate containing
`
`C12
`
`to C54 alkyl polyglycol
`ethylene oxide unite
`
`approximately
`
`and
`660 pbw of the monomer emulsion
`
`are heated to 80
`and admixed with solution of 0.55 pbw
`of ammonium peroxodisulfate in 15 pbw of water
`the remaining monomer emulsion is metered
`Subsequently
`in over the course of 3.5 hours Heating is continued for 60
`minutes and then the mixture is cooled The pH is adjusted
`12.5% strength ammonia solution The solids
`to 9.0 using
`content of the dispersion is 50.4% by weight and the MFT
`is 10
`
`EXAMPLE
`
`20
`
`25
`
`Comparative Example
`
`First of all monomer emulsion is prepared This is done
`by preparing
`mixture of
`
`512.7 pbw
`39.3 pbw
`
`of water
`35% strength solution of C2 to C4 alkyl polyglycol
`of
`ether sulfate coataining
`units and
`
`approximately
`
`ethylene
`
`oxide
`
`11.0 pbw
`
`of methacrylic acid
`
`incorporating
`572.0 pbw
`
`of methyl methscrylate
`of butyl acrylate and
`528.0 pbw
`2.75 pbw of ammonium peroxodinulfate
`
`by stirring with
`high-speed stirrer and continuing
`stable emulsion is formed Then in an appropriate
`until
`reaction vessel
`
`stirring
`
`to examine the cpmpatibility with respect
`In order
`cement 10% by weight of cement based on the dispersion
`is incorporated by stirring
`into each of the dispersions of
`and of Comparative Examples
`30 Examples Ito
`and
`and
`is made of whether
`an assessment
`
`the dispersion remains
`hours
`stable or coagulates over the course of
`
`to
`
`35
`
`Dispersion
`
`Dispersion
`
`Dispersion
`
`Dispersion
`
`Cement compatibility finding
`
`Dispersion
`
`Dispersion
`
`Dispersion
`
`Dispersion
`
`stable
`
`is steble
`
`is stshle
`
`is stable
`
`522.5 pbw of water
`38% stresgth
`4.0 pbw of
`ether sulfate containing
`
`solution of
`
`C12
`
`to C5 sticyl potygtyeol
`oxide unite
`
`ethylene
`
`40
`
`approximately
`
`and
`66.0 pbw of the monomer emulsion
`
`are heated to 80
`and admixed with
`solution of 0.55 pbw
`of ammonium peroxodisulfate
`in 15 pbw of water
`the remaining monomer emulsion is metered
`Subsequently
`in over the course of 3.5 hours Heating is continued for 60
`minutes and then the mixture is cooled The pH is adjusted
`12.5% strength ammonia solution The solids
`to 9.0 using
`and the MET
`content of the dispersion is 49.2% by weight
`is 12
`
`Comparative Example
`
`First of all monomer emulsion is prepared This is done
`mixture of
`by preparing
`
`515.7 pbw
`
`19.7 pbw
`
`of water
`35% strength solution of
`ether sulfate containing
`approximately
`
`of
`
`C52 to C4 alkyl polyglycol
`
`ethylene
`
`oxide
`
`units and
`
`11.0 pbw
`
`of methacrylic acid
`
`incorporating
`572.0 pbw
`
`528.0 phw
`
`of methyl methactylste
`of butyl scrylsre sod
`
`of Example
`nispersion of Example
`of Example
`of Example
`of
`
`Dispersion
`
`Dispersion
`
`Comparative
`of Comparative
`
`Example
`Example
`
`Dispersion
`
`cosgulstes
`
`Dispersion
`
`coagulates
`
`EXAMPLE
`
`45
`
`roof tile paint paste is prepared by successive
`into
`incorporation
`
`stirred
`
`600 pbw
`of
`
`1200 pbw
`300 pbw
`
`of water
`
`of calcite
`
`filler
`
`and
`
`of red iron oxide pigment
`
`In order to prepare
`
`roof tile paint mixture nf
`
`120.0 pbw
`3.8 pbw
`1.0 pbw
`
`of the dispersion of Examples
`
`ito
`
`end
`of butyl diglycol
`defosmer
`of silicone
`
`50
`
`Sb
`
`60
`
`is added to 87.5 pbw of each paste paint preparation being
`by the stirred incorporation into the dispersion of
`preceded
`0.6 pbw of
`Example
`neutralized
`of an additional
`acid Lopon 890 as dispersant
`65 polyacrylic
`The
`cement compatibility and water absorption of the
`paints are determined
`as is the spotting on fiber cement
`
`

`

`US 6475632 B1
`
`slabs on exposure to moisture under hot conditions in order
`to simulate the efflorescence behavior
`
`Cement
`
`Paint based on
`
`of
`
`dispersion
`Example
`
`compatibility nf the
`with nddition
`
`pnint
`of 10% cement
`
`Water
`
`nbsorption
`the paint
`
`in
`
`of
`
`21
`
`Spotting
`
`minimal
`
`with addition of
`
`stabte
`
`0.6 pbw of Lopon
`890
`
`stable
`
`stable
`
`stable
`
`Comparative
`
`paint
`
`coagulntm
`
`Example
`
`Comparative
`
`paint eoagulntm
`
`Example
`
`10% cement are stirred into the roof tile paint
`saint is assessed
`400 jam thick paint
`
`in
`
`at 500
`
`is
`
`12
`
`none
`
`minimal
`
`minimal
`
`severe
`
`severe
`
`and then stability of the
`
`and dried over
`
`on 24-hoor stor
`
`thick
`
`at 500
`
`assessed for spotting
`
`film in applied by knife coating
`The water absorption
`drying cabinet
`night
`in then determined by differential weighing
`age in water
`400 jam
`The ettlorescesce
`behavior
`tested by knife-coating
`cement stab drying the paint
`film overnight
`for one week with the costed side over
`the stab
`The paist film is sobseqoently
`
`film onto
`paint
`sad then placing
`at 60
`
`waterbath
`
`fiber
`
`What
`
`is claimed is
`
`at
`
`roof tite paint comprising
`least one color pigment and
`dispersion prepared using from 0.1 to
`by
`percent
`weight based on the total monomer content of car
`protective colloid emulsion
`as
`boxymethylcellulosc
`polymerizcd in connection with monomer composi
`
`tion including
`from 85 to 99.8% by weight of acrylic esters with C1
`to C2 alkanols methacrylic esters with
`to C12
`ailcanols and/or vinylaromatic monomers and
`to 5% by weight of copolymerizable
`from 0.2
`sulfates and/or sul
`acids carboxamides
`
`carboxylic
`
`fonates
`
`The roof tile paint as claimed in claim
`is conducted
`emulsion polymerization
`The roof tile paint as claimed in claim
`water-soluble earboxymethylcellulose
`degree of
`having
`substitution of from 0.4 to 2.9 is used
`as said protective
`
`at
`
`pH
`or
`
`wherein
`
`wherein the 40
`
`eolloid
`
`least one of the
`
`as claimed in at
`
`The roof tile paint
`preceding claims wherein said protective colloid is water-
`soluble carboxymethyleellulose whose 2% strength aqueous
`Brookfield viscosity at 25
`and 20 rpm
`solutions possess
`of less than 2000 with spindle
`The roof tile paint
`least one of the
`as claimed in at
`preceding claims wherein the emulsion polymerization is
`using less than 1% by weight of
`conducted
`regulator
`The roof tile paint
`as claimed in at
`least one of the
`preceding claims wherein the dispersion comprises from 0.1
`to 2% by weight of
`dispersant
`roof tile composite comprising
`
`45
`
`50
`
`roof tile and
`
`10
`
`at
`
`on at least one surface of said
`paint composition coated
`roof tile said paint composition including
`least one color pigment and
`dispersion prepared using from 0.1 to
`percent by
`on the total monomer content
`weight based
`of
`prntective colloid emul
`as
`carboxymethyleellulose
`monomer
`sion polymerized
`in connection with
`
`composition
`including
`from 85 to 99.8% by weight of acrylic esters with
`
`Ca to C12 alkanois methacrylie esters with C1 to
`C2 alkanols and/or vinylaromatic monomers and
`from 0.2 to 5% by weight of eopnlymerizable
`acids earboxamides
`sulfates and/or
`earbnxylie
`
`sulfonates
`
`10
`
`15
`
`wherein 0.1
`The roof tile paint as claimed in claim
`to 1.5 percent by weight based on the total monomer content
`is used
`of said carboxymethylcellulose
`The roof tile paint as claimed in claim
`wherein said
`emulsion polymerization is in the form of an aqueous
`emulsion
`10 The roof tile composite as claimed in claim
`wherein
`said emulsion polymerization is in the form of an aqueous
`25 emulsion
`11 The roof tile composite of claim
`tile is concrete
`12 The
`
`roof tile
`
`wherein said roof
`
`wherein said
`
`composite of claim
`ih conducted
`emulsion polymerization
`13 method for making
`binder to
`step of adding
`binder includes
`
`20
`
`30
`
`at
`
`pH
`roof tile paint comprising the
`paint composition wherein said
`
`carboxymethylcellulose
`emulsion polymerized with
`
`as
`
`protective
`monomer
`
`colloid and
`
`is
`
`composition
`
`comprising
`from 85 to 99.8% by weight of acrylic esters with C1
`to C12 alkanols methacrylic esters with C1 to C12
`alkanols and/or vinylaromatic monomers and
`from 0.2 to 5% by weight of copolymerizable
`sulfates and/or sul
`earbnxylic acids carboxamides
`fonates
`14 The method as claimed in claim 11 wherein said
`pH
`emulsion polymerization is conducted
`15
`percent by weight
`dispersion comprising 0.1 to
`based on the total monomer content of carboxymethylcel
`lulose as
`protective colloid emulsion polymerized with
`monomer composition comprising
`from 85 to 99.8% by weight of acrylic esters with C1
`esters with C1 to Ca2
`to C12 alkanols methacrylie
`alkanols and/or vinylaromatic monomers and
`from 0.2 to 5% by weight of enpolymerizable earboxy
`carboxamides
`lie acids
`sulfates and/or
`suifonates
`wherein said emulsion polymerization is conducted at
`pH
`
`at
`
`