CA1159178A - Blends of acrylic microgel and acrylic resin solutions - Google Patents
Blends of acrylic microgel and acrylic resin solutionsInfo
- Publication number
- CA1159178A CA1159178A CA000351710A CA351710A CA1159178A CA 1159178 A CA1159178 A CA 1159178A CA 000351710 A CA000351710 A CA 000351710A CA 351710 A CA351710 A CA 351710A CA 1159178 A CA1159178 A CA 1159178A
- Authority
- CA
- Canada
- Prior art keywords
- microgel
- acrylic
- emulsion
- resin
- acrylic resin
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S524/916—Hydrogel compositions
Abstract
ACRYLIC RESIN COMPOSITIONS
ABSTRACT OF THE DISCLOSURE
A method of making an acrylic microgel resin which comprises preparing an aqueous microgel emulsion of an acrylic resin which is crosslinked with a multifunctional crosslinking agent, removing water from the emulsion by coagulation and/or azeotropic distillation with an organic solvent in which the microgel is insoluble and which forms an azeotrope with water, and incorporating the thus dehydrated microgel into an acrylic resin which has been prepared by solution polymerization in organic solvent.
ABSTRACT OF THE DISCLOSURE
A method of making an acrylic microgel resin which comprises preparing an aqueous microgel emulsion of an acrylic resin which is crosslinked with a multifunctional crosslinking agent, removing water from the emulsion by coagulation and/or azeotropic distillation with an organic solvent in which the microgel is insoluble and which forms an azeotrope with water, and incorporating the thus dehydrated microgel into an acrylic resin which has been prepared by solution polymerization in organic solvent.
Description
1 15917~
ACRYLIC RESIN CC)MT~OSITIONS
The present invention is concerned with acrylic resin compositions conta:inins polymeric microparticles, called "microgels" for convenience, which are par~icularly use~ul as resinous, film-forming vehicles ~or high solids pai~t~.
For present purposes, a ~microgeln may ~e described as a s~able dispersion of micropar~icles (usu~lly 0O05-10 microns in size) composed of a 10 polymer which is crosslinked to the extent that it is insoluble in an organic sol~ent in which ~he particles are dispersed.
Microgels of various types have been kncwn for ~uite a long while but recently a great 15 daal of wor~ has gone lnto the preparation of such products because they appear to ofer a way of obtaining high solids (low solvent) composi~ions for use in paints or coating compositions.
Nicrcgels are currently of particular interest in 20 ~he indu~trial paint area where governmental regulations are re~uiring higher and hisher solids coatin~ systems.
As representative of the prio~ work on micro~els, there may be mentioned ~.S. Patents 25 3,830,796, 4,025,474, 4,05~,607 and 4,075,141; and Briti5h Patents 957,051 and l,538,1510 Also of interest are articles by Funke ~The Possible ~s~s of Reactive Microgels in Paint Formulation~ JOC~A, 1977, 60, pa5es 438-445 and by Shashoua et al 30 ~ic~ogel: An Idealized Polymer Moleculan, Journal of Polymer Science, Vol. XXXITI, pages 101-117 (1958)..
An advantage in using micr~gels in paint systems is that they make it possible to obtain a 35 higher solids content than would otherwise be ~.
~ 7~
possible without concurrently eausing an increase in viscosity compared to systems withcut mi~r~gels. FurthermQre, the microgels seem to improve pigment orientation. E~or instance when 5 alumi~un flakes are used as the pigment, the microgel appear~ to ~ake the aluminum flakes lie flat, s~mething which is very ~ifficult to do in known high solid~ ~ystems. Additionally~ it has been noted that microyels can give a remarkably 10 high le~el of sag resista~ce when used in hi~h s~lids coating systems. It i5 ~I so possible, depending on the type and amount of crosslinker u~ed, to make the microgel particles reac~ive with the resin or resin-forming materials if included 15 with these material~ in a cooking or curing cycle ~or these other materials, thus providing a convenient means for varying the properties of the resinous coating ~ys~em or ccmpositions ultimately s~btained.
While ~uite a variety of meth~ds have pre~iously been propased to make microgels, the pre~ent invention is directed towards a new meth~d which is very convenient and advantageous while giving a microgel product that may be effectively 25 used in high solids paint systems to provide coatings of excellen~ aluminum orientation and sag resistance.
One unique aspect of the invention is that the microgel is prepared by first making an 30 aquecus emulsion of an acrylic resin which is crosslinked with a multifunctional ( 22) .
crosslinklng agent and then dehydrating the system by azeotropically distilling of~ the water in the emulsion. The resulting very f ine crosslinked 35 resin particles can then ~e a2ded to a 1 15~17~
conventional acrylic paint resin in organic solvent solution.
Alternatively, the micro emulsion can be dehydrated simultaneously with the preparation or cooking of the acrylic paintresin. In that event, -the microgel particles may also react with the acrylic resin or resin componen-ts as the resin is being prepared. For example, the microgel as prepared may include unrea-ted vinyl groups which did not react for some reason (such as rigidity of the crosslinking and resulting s-teric effects) in the preparation of the microgel. However, the addition of other monomers to the microgel for the purpose of preparing -the acrylic paint resin simultaneously with -the microgel dehydration may well result in reaction between the vinyl groups of the microgel and acrylic monomers.
The microgel emulsion may be mixed with the pre-formed paint resin in organic solvent solution and then azeotropically distilled to remove the water from the microgel emulsion.
In a further alternative, the emulsion can be coagulated with organic solvent. The water layer and organic layer may then be separated from each other. Some water may remain in the organic layer, it may be removed by adding sufficient solvent and azeotropically distilling -the water.
In one broad aspect, the present invention relates to the method ofmaking an acrylic microgelresin composition for use in paint systems to provide coatingsof improved pigment orientation and sag resistance which comprises preparing an aqueousmicrogel emulsion by the emulsion polymerization in water of a mixture of ethylenically unsaturated monomers, at least one of said monomers, the amount of which is in 1 15917~
the range o:~ 10 to 90 weight percent o~ said microgel, being an acrylic or methacrylic acid, or an -Oll substituted alkyl ester thereof, and containing a -COOH or -Oll group, and at least another of said monomers, the amoun-t of which is in the range of 90 to 10 weight percent of said microgel, being selected from an alkyl ester of an acrylic or methacrylic acid, styrene and alpha-methyl styrene, and being free from -COOH and -OH groups, and a multifunctional crosslinking agent con-taining at least two ethylenically unsaturated double bands present in an amount of 5 - 70 percent by weight of the total weight of said ethylenically unsaturated monomers and crosslinking agent, removing water from the emulsion by coagulation and/or azeotropic distillation with an organic solvent in which the microgel is insoluble and which forms an azeotrope with water, and incorporating the microgel into an acrylic resin prepared by polymerizing two or more ethylenically unsaturated monomers in an organic solvent solution wherein at least one of said monomers is an -OH substituted alkyl ester of an acrylic or methacrylic acid and optionally a monomer containing a -COOH group selected from an acrylic or methacrylic acid, and another of said monomers being selected from an alkyl ester of an acrylic or methacrylic acid, styrene and alpha-methyl styrene, and being free from -COOH and -OH groups to provide said acrylic microgel resin wherein the amount of microgel solids is in the range of 5 to 15 percent by weight of the total resin solids.
Broadly described, therefore, the acrylic resin composition of the invention is made up of two essential components which, for ease of reference, may be called (1) the microgel -3a-, emulsion and (2) the acrylic resin. rrhe combination of these components, within the variants mentioned herein, yives a resin composition which, for ease of reference, is called an acrylic microgel resin.
3b-The microgel emulsion (1) is prepared bythe emulsian polymerization in water of a mixture of ethylenically unsaturated monomers, pre~erably including at least one such manomer which contains a -C00~ or -a~ group and at least one such monomer which i~ free frcm -S00~ and ~0~ groups, and a ~ultifunctional crosslinking agent.
The acrylic re~in (~) is prepared by p~lymerizins two or more ethylenically unsaturated mon~mer~ in orsanic solvent solution. ~n the preferred embodiment, the microgel emulsion (1) is pre~ent during the preparation of the acrylic resin and the acrylic polymerization is carried out at a temperature such that the water of the microgel emulsion is aze~tropically distilled.
~cwe~er,.as indicated earlier, an alternative ~nvolves azeotropically distilling off the water of the microgel emulsion by adding thereto an organic s~lvent which forms an azeotrope with water but which does not dissolve or swell the microgel solids, after which the completely or partially dehydrated microgel is blended with previously ~ormed a¢rylic paint resin.
Alternatively, as noted, the acrylic resin ~5 c~mponent (2) ~s prepared in organic solven~
solution and the microgel emulsion component is dehydrated in the presence of the preform~d acrylic resin solution~ Each embodiment, however, involves preparing an aq-~eous microgel emulsion containing solid cro~slinked polymer particles, aze~tropically remo~ing water from the emulsion and combining the microgel polymer with acrylic pclymer in organic solution, the acrylic polymer being either preformed or prepared in si~u, i.e., in the presenc~ of the microg~l polymer.
! 15917~
An alternate method is to coagulate the emulsion with a portion or organic solvent, then ~eparate the layer~ The oryanic layer, a mixture of acrylic emulsion, water and organic solvent, can be substituted for the microgel emulsion and incorporated into acrylic resin component (2).
As noted, the microgel emulsion, accordlng to the invention, is pr~pared by aqueous polymerization of two or more ethylenically unsaturated monomers, one of which preferably includes an -~H or -COO~ group and at least one of which is free frcm such groups, and a multi-fun~tional crosslinking agent. Typically the moncmer containing the -a~ or -C~O~ group is acsylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxYPropy1 acrylate, hydroxye~hyl methacrylate ~r hydroxypropylmethacrylate. The ethylenic~lly unsaturated monomers which are free from -0~ and -COO~ groups may be, for eæample, the alkyl esters of acrylic or methacrylic acid, particularly those having from 1 to 4 car~ons in the atkyl~ e.g. methyl, ethyl, propyl or butyl acrylate; and methyl, ethyl, propyl-or butyl methacrylate. Other suitable monomers include styrene or alpha-methyl styrene.
The crosslinking agent may be any such agent which contains at least two ethylenically unsaturated double bonds and will give a crosslinked polxmer in aqueous emulsion polymerization that is insoluble in the organic solvent which is ultimately used ~o make up the acrylic resin compasitions. As e~amples of suitable crosslinking agents there may be mentioned the following although it is noted that ~he invention is not limitPd thereto:
ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate t methylene bisacrylamide, methylene bismethac~ylamide, dlvinyl ~enzene~
vinyl methacrylate, vinyl cro~onate, vinyl acrylate, divinyl acetylene, ~rivinyl benzene, glyce~ine trimethacrylate, p*ntaerythritol tetramethacrylate, triallyl cyanurate, divinyl ethane, divinyl sulfide, divinyl sulf~ne, hexatriene, triethylene glyc~l dimethacrylate, diallyl cyanamide, glycol diacrylate, ethylene glycol divinyl ether, diallyl phthalate, divinyl dimethyl silane glycerol ~ri~inyl ether, trimethylolpropane triacrylate, trimethyloleth2ne triacrylate, trimethylolprapane trimethacrylate, trimethylolethane trimethacrylate, tetramethyl~ne glycol dimet~acrylate, triethylene glycol di~ethacrylate, tetraethylene glycol diacrylate, tetraethylene ~lycol dimethacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, ~entaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexacrylate, tripentaerythritol octoacrylate, pentae~ythritol dimethacrylate, pent2erythritol tr~methacrylate, aipentaerythritol dimethacrylate, dipen~aerythritol tetramethacrylate, tripentaerythritol octamethacrylate, pentaerythrikol diitaconate, dipentaerythritol trisitaconate, dipentaerythritol pentaitaconate, dipentaerythritol hexaitaconate, 1,3-butanediol diacryla~e, 1,3-butanediol dimethacrylate, 1,4-butanediol aiitaconate, sor~itol triacrylate, sor~itol tetraacrylate, sor~itol 3159~
tetrame~hacrylate, sorbitol pentaacryla~e, sorbitol hexacrylate, modifiec1 l,4-butylene diacrylate, 1,6 hexc~nediol diacrylate, modified trimethylolpropane triacrylate!, modified s penta~rythritol triacrylate, poly functional i~ocyana~es with hydro~y monomers (isophorone diisocyanate plus hydr~xy ethyl acrylate), methacrylated epoxy re~in, and the like, and mistures and prepol~mers thereof.
The amount of ethylenically unsaturated moncmers u~ed to make up the microgel can be widely varied. Typical amounts will fall in the range af la 90% by weigh~ of mon~mer or monomers containing -0~ sr -C00~ groups and 9~-10% by 15 weight o~ monomer or monomers which are free rom such groups.
The amount of crosslinking agent that is used is im~ortan~ although this can be varied o~er a relatively large range. Desirably the amount of crosslinking agent constitutes at least about 0.5%
and up to 20% by ~eight of the total amount of all materials used for the emulsion polymerization.
In the normal situation this is roughly e~quivalent to a r~nge of 5-70%, preferably 8-50%, by weight 25 of the total weight of ethylenically unsatura~ed ncmomers and crosslinking agent.
Conventional emulsifiers or surfact,~nts and initiators for emulsion polymerizatic~n are used to pr~pare the ~icrogel emulsion. r~ypical 30 emulsi~iers tor surfac~ants) include such anionic alkali metal salts of orsanic ~arboxylic acids or soaps, e.~., potassium oleate or stear2te. Alkyl sulfates and ,1kyl- or alkylarylsulfonat~s may also be used~~ Preferre~ for use are the sodium 115g17~
alkyl sulfosuccinamates, e.g.,, disodium N-octadecyl sulfosuccinamate an~l sodium diamyl sulfosuccinæmate. Advantageously, two or more such surfactants are used to~ether since this seems to give an emulsion of better stability.
- Sui~able initiators are the free radical yielding peroxides and persal~s eg., benzoyl peroxide, lauroyl pero~ide, ammonium, potas~ium or ~odlum persulfate, etc~
AdYantageously the emulsion polymerization is carried out by adding the monomers gradually to heated water containing the emulsifier and initiator. Preferahly tbe system is heated to, for example, 75-90 C during the moncmer addition and for a short time afterwards although it will be a.ppreciated that the poly-merization conditions c~n be widely varied and will depend on other factors , e.~., the monomers involved. It is, in any case, important to obtain a stable emulsion in which the polymer par~icles have sizes in the order of about 0.05 to 10 micr~ns .
The aque~us ~icrogel emulsion may be azeotropic~lly distilled using any convenient organic solvent which forms an azeotrope with water but does not dissolve or swell the microgel sol~ds. TXpically suitable solvents include cellosolve acetate, butanol, naphtha, mineral spirits and the like. The amount of solvent used 30 can be varied but should be enoush to facilitate azeotropic removal of the water. All of the water of the microgel emulsion may be removed or only a portion the~eof. ~sually at least 50~ by weight of the water should be removed.
1 ~5917~ .
An additional al~ern,~tive is to coagulate the emulsion with an organic solvent. The coagulum can be physically separated from a water layer. ~he coagulated portion can then be dryed urther by azeotropic distillation or com~ined with the solution acrylic.
~ bile the microgel emul-Rion ~ay be eparately 3ubjected to azeotropic di~tillation, the prefere~ce, a~ n~ted earlier, i~ to carry out the dlstillation either conc~rrently with the preparat~on (cook) of the acrylic paint resin or ln the presence of the previously pre~ared acrylic resin. In this way, it is possible, if desir~d, to ef~ect reaction between the acrylic resin and the ~icrogel polymer particles~ This may involve further gr~t or copolymerization via double bonds r~main~ng in the micr~gel to the linear a:rylic polymer which is formed or being formed.
The acrylic polymer used herein may be 20 made in convention~l fashion in orga~ic solvent solution using usual polymerization conditions except for the option of including the microgel emulsion in the reaction mixture an~
azeotropically removing the microgel water during the acrylic polymer preparation or cook. If the acrylic resin is prepared in the presence of the micro~el, the orqanic solvent whicb is employed should meet the indicated re~uir~ents for azeotropically distilling the water from the 30 microyel emulsion, i.e., the solvent ~hould form an azeo~rope with water at the ~emperat~re used t~
prepare or cook the acsylic resin and it should not dissolve or swell the microgel particles. Any of the monomers referred to a~ove in connec~ion 35 with the preparation of the microgel may b~ used ~917 to make the acrylio resin. PreferaDly the acrylic resin includes an ethylenically unsaturated monomer which contains either an -a~ or -COO~
group and another such monomer which is free from such groups. E~cept as indicated, the reac~ion conditions for the acrylic resin cook, i.e., temperature, monomer~, proportions, initiators and temperature~ are those conventionally employed ~n preparing acryllc resins by polymerization in organic solvent solu~ions.
The amount of m~cro~el solids to acrylic resin solids in the final acrylic resin/microgel compositionr whether the microgel is included in the preparation of the acrylic resin or subsequently added thereto, will usually be in the range of 5 to 15% by weight of the total resin solids. N~r~ally the total solids content of the final acrylic resin/mi~rogel composition as used will be in the order of 40-60~ by weight. The acrylic resin/micro~el composition may be mixed with alkylated melamine-formaldehyde preconden~ates or polyesters and pigments, e.g., aluminum flake, to provide highly useful paints in coating compositions. As indicated, paints based 25 on ~he present acrylic resin/microgel preparations with and without aluminum flaXe, on application and curing, are characterized by the orientation o~ the pigment ~nd improved sag resistance.
1 lSgl78 The invention is illust:rated by the following examples wherein parts, percentages and ratios are by weight unless othe~rwise indicated:
E:~AMPLE 1 5 A. MIC~OG~L E~SION PRE~ARATION
~ e~n~
A 3.00% Ae~osol 18* ~American Cyanamid) l~50~ Aerosol AY-65*~ (American Cyanamid) .25~ Sodium Bicar~onate 40.2S~ Deionized Water .25% Ammonium Persulfate 14.75% Deionized Water 4.00% ~ydroxypropyl Methacrylate 32.00% 2-Ethylhe~yl Acrylate 4.00~ Divinyl Benzene *Disodium N-octadecyl sulfosuc~inamate *~5Odium diamyl sul~o~uccinamate To a five liter, three neck reaction fla~k e~uipped with a condenser, thermometer and 20 agitator, the Aeros~l 18, Aerosol AY-~5, sodiu~
bicar~onate and first deionized water are charged. The ammonium peEsulfate and second deionized water are premixed and added to a small addi~ioQ funnel. The hydro~ypropyl methacrylate, 25 2-ethylhexyl acrylate and divinyl benzene were premixed and added to a separate additian funnel. The surfactants and water are heat~d to 87 ~ 2~C at which time 10% o~ the ammonium 1 1$917 persulfate solution is added. T~e acrylic monomers are added to the reaction flask continuously over 2 1/2 hours, At the same time, the remaining a~monium persulfate ~olution is 5 added continuously over 3 hours. The temperature o~ the reaction i~ ~eld ak 87 * 2C thsoughout the ~onomer add. Thirty minutes after the ammonium persulfate 5~lution is added, the emulsion is cooled to roam tem~erature and discharged.
10 ~. ACgYLIC ~IC~OG~h RESI~ PRE~ARATION
17.67% n-ButanoL ~ ~ p ~D~) A 17.67% Cellosolv~ Acetate (~nion Carbide) 12.32~ ~icrogel Emulsion .36~ t-Butyl Per~enzcate (50 in Mineral Spirits~
12~69% Styrene 11.66% Butyl Methacrylate
ACRYLIC RESIN CC)MT~OSITIONS
The present invention is concerned with acrylic resin compositions conta:inins polymeric microparticles, called "microgels" for convenience, which are par~icularly use~ul as resinous, film-forming vehicles ~or high solids pai~t~.
For present purposes, a ~microgeln may ~e described as a s~able dispersion of micropar~icles (usu~lly 0O05-10 microns in size) composed of a 10 polymer which is crosslinked to the extent that it is insoluble in an organic sol~ent in which ~he particles are dispersed.
Microgels of various types have been kncwn for ~uite a long while but recently a great 15 daal of wor~ has gone lnto the preparation of such products because they appear to ofer a way of obtaining high solids (low solvent) composi~ions for use in paints or coating compositions.
Nicrcgels are currently of particular interest in 20 ~he indu~trial paint area where governmental regulations are re~uiring higher and hisher solids coatin~ systems.
As representative of the prio~ work on micro~els, there may be mentioned ~.S. Patents 25 3,830,796, 4,025,474, 4,05~,607 and 4,075,141; and Briti5h Patents 957,051 and l,538,1510 Also of interest are articles by Funke ~The Possible ~s~s of Reactive Microgels in Paint Formulation~ JOC~A, 1977, 60, pa5es 438-445 and by Shashoua et al 30 ~ic~ogel: An Idealized Polymer Moleculan, Journal of Polymer Science, Vol. XXXITI, pages 101-117 (1958)..
An advantage in using micr~gels in paint systems is that they make it possible to obtain a 35 higher solids content than would otherwise be ~.
~ 7~
possible without concurrently eausing an increase in viscosity compared to systems withcut mi~r~gels. FurthermQre, the microgels seem to improve pigment orientation. E~or instance when 5 alumi~un flakes are used as the pigment, the microgel appear~ to ~ake the aluminum flakes lie flat, s~mething which is very ~ifficult to do in known high solid~ ~ystems. Additionally~ it has been noted that microyels can give a remarkably 10 high le~el of sag resista~ce when used in hi~h s~lids coating systems. It i5 ~I so possible, depending on the type and amount of crosslinker u~ed, to make the microgel particles reac~ive with the resin or resin-forming materials if included 15 with these material~ in a cooking or curing cycle ~or these other materials, thus providing a convenient means for varying the properties of the resinous coating ~ys~em or ccmpositions ultimately s~btained.
While ~uite a variety of meth~ds have pre~iously been propased to make microgels, the pre~ent invention is directed towards a new meth~d which is very convenient and advantageous while giving a microgel product that may be effectively 25 used in high solids paint systems to provide coatings of excellen~ aluminum orientation and sag resistance.
One unique aspect of the invention is that the microgel is prepared by first making an 30 aquecus emulsion of an acrylic resin which is crosslinked with a multifunctional ( 22) .
crosslinklng agent and then dehydrating the system by azeotropically distilling of~ the water in the emulsion. The resulting very f ine crosslinked 35 resin particles can then ~e a2ded to a 1 15~17~
conventional acrylic paint resin in organic solvent solution.
Alternatively, the micro emulsion can be dehydrated simultaneously with the preparation or cooking of the acrylic paintresin. In that event, -the microgel particles may also react with the acrylic resin or resin componen-ts as the resin is being prepared. For example, the microgel as prepared may include unrea-ted vinyl groups which did not react for some reason (such as rigidity of the crosslinking and resulting s-teric effects) in the preparation of the microgel. However, the addition of other monomers to the microgel for the purpose of preparing -the acrylic paint resin simultaneously with -the microgel dehydration may well result in reaction between the vinyl groups of the microgel and acrylic monomers.
The microgel emulsion may be mixed with the pre-formed paint resin in organic solvent solution and then azeotropically distilled to remove the water from the microgel emulsion.
In a further alternative, the emulsion can be coagulated with organic solvent. The water layer and organic layer may then be separated from each other. Some water may remain in the organic layer, it may be removed by adding sufficient solvent and azeotropically distilling -the water.
In one broad aspect, the present invention relates to the method ofmaking an acrylic microgelresin composition for use in paint systems to provide coatingsof improved pigment orientation and sag resistance which comprises preparing an aqueousmicrogel emulsion by the emulsion polymerization in water of a mixture of ethylenically unsaturated monomers, at least one of said monomers, the amount of which is in 1 15917~
the range o:~ 10 to 90 weight percent o~ said microgel, being an acrylic or methacrylic acid, or an -Oll substituted alkyl ester thereof, and containing a -COOH or -Oll group, and at least another of said monomers, the amoun-t of which is in the range of 90 to 10 weight percent of said microgel, being selected from an alkyl ester of an acrylic or methacrylic acid, styrene and alpha-methyl styrene, and being free from -COOH and -OH groups, and a multifunctional crosslinking agent con-taining at least two ethylenically unsaturated double bands present in an amount of 5 - 70 percent by weight of the total weight of said ethylenically unsaturated monomers and crosslinking agent, removing water from the emulsion by coagulation and/or azeotropic distillation with an organic solvent in which the microgel is insoluble and which forms an azeotrope with water, and incorporating the microgel into an acrylic resin prepared by polymerizing two or more ethylenically unsaturated monomers in an organic solvent solution wherein at least one of said monomers is an -OH substituted alkyl ester of an acrylic or methacrylic acid and optionally a monomer containing a -COOH group selected from an acrylic or methacrylic acid, and another of said monomers being selected from an alkyl ester of an acrylic or methacrylic acid, styrene and alpha-methyl styrene, and being free from -COOH and -OH groups to provide said acrylic microgel resin wherein the amount of microgel solids is in the range of 5 to 15 percent by weight of the total resin solids.
Broadly described, therefore, the acrylic resin composition of the invention is made up of two essential components which, for ease of reference, may be called (1) the microgel -3a-, emulsion and (2) the acrylic resin. rrhe combination of these components, within the variants mentioned herein, yives a resin composition which, for ease of reference, is called an acrylic microgel resin.
3b-The microgel emulsion (1) is prepared bythe emulsian polymerization in water of a mixture of ethylenically unsaturated monomers, pre~erably including at least one such manomer which contains a -C00~ or -a~ group and at least one such monomer which i~ free frcm -S00~ and ~0~ groups, and a ~ultifunctional crosslinking agent.
The acrylic re~in (~) is prepared by p~lymerizins two or more ethylenically unsaturated mon~mer~ in orsanic solvent solution. ~n the preferred embodiment, the microgel emulsion (1) is pre~ent during the preparation of the acrylic resin and the acrylic polymerization is carried out at a temperature such that the water of the microgel emulsion is aze~tropically distilled.
~cwe~er,.as indicated earlier, an alternative ~nvolves azeotropically distilling off the water of the microgel emulsion by adding thereto an organic s~lvent which forms an azeotrope with water but which does not dissolve or swell the microgel solids, after which the completely or partially dehydrated microgel is blended with previously ~ormed a¢rylic paint resin.
Alternatively, as noted, the acrylic resin ~5 c~mponent (2) ~s prepared in organic solven~
solution and the microgel emulsion component is dehydrated in the presence of the preform~d acrylic resin solution~ Each embodiment, however, involves preparing an aq-~eous microgel emulsion containing solid cro~slinked polymer particles, aze~tropically remo~ing water from the emulsion and combining the microgel polymer with acrylic pclymer in organic solution, the acrylic polymer being either preformed or prepared in si~u, i.e., in the presenc~ of the microg~l polymer.
! 15917~
An alternate method is to coagulate the emulsion with a portion or organic solvent, then ~eparate the layer~ The oryanic layer, a mixture of acrylic emulsion, water and organic solvent, can be substituted for the microgel emulsion and incorporated into acrylic resin component (2).
As noted, the microgel emulsion, accordlng to the invention, is pr~pared by aqueous polymerization of two or more ethylenically unsaturated monomers, one of which preferably includes an -~H or -COO~ group and at least one of which is free frcm such groups, and a multi-fun~tional crosslinking agent. Typically the moncmer containing the -a~ or -C~O~ group is acsylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxYPropy1 acrylate, hydroxye~hyl methacrylate ~r hydroxypropylmethacrylate. The ethylenic~lly unsaturated monomers which are free from -0~ and -COO~ groups may be, for eæample, the alkyl esters of acrylic or methacrylic acid, particularly those having from 1 to 4 car~ons in the atkyl~ e.g. methyl, ethyl, propyl or butyl acrylate; and methyl, ethyl, propyl-or butyl methacrylate. Other suitable monomers include styrene or alpha-methyl styrene.
The crosslinking agent may be any such agent which contains at least two ethylenically unsaturated double bonds and will give a crosslinked polxmer in aqueous emulsion polymerization that is insoluble in the organic solvent which is ultimately used ~o make up the acrylic resin compasitions. As e~amples of suitable crosslinking agents there may be mentioned the following although it is noted that ~he invention is not limitPd thereto:
ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate t methylene bisacrylamide, methylene bismethac~ylamide, dlvinyl ~enzene~
vinyl methacrylate, vinyl cro~onate, vinyl acrylate, divinyl acetylene, ~rivinyl benzene, glyce~ine trimethacrylate, p*ntaerythritol tetramethacrylate, triallyl cyanurate, divinyl ethane, divinyl sulfide, divinyl sulf~ne, hexatriene, triethylene glyc~l dimethacrylate, diallyl cyanamide, glycol diacrylate, ethylene glycol divinyl ether, diallyl phthalate, divinyl dimethyl silane glycerol ~ri~inyl ether, trimethylolpropane triacrylate, trimethyloleth2ne triacrylate, trimethylolprapane trimethacrylate, trimethylolethane trimethacrylate, tetramethyl~ne glycol dimet~acrylate, triethylene glycol di~ethacrylate, tetraethylene glycol diacrylate, tetraethylene ~lycol dimethacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, ~entaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexacrylate, tripentaerythritol octoacrylate, pentae~ythritol dimethacrylate, pent2erythritol tr~methacrylate, aipentaerythritol dimethacrylate, dipen~aerythritol tetramethacrylate, tripentaerythritol octamethacrylate, pentaerythrikol diitaconate, dipentaerythritol trisitaconate, dipentaerythritol pentaitaconate, dipentaerythritol hexaitaconate, 1,3-butanediol diacryla~e, 1,3-butanediol dimethacrylate, 1,4-butanediol aiitaconate, sor~itol triacrylate, sor~itol tetraacrylate, sor~itol 3159~
tetrame~hacrylate, sorbitol pentaacryla~e, sorbitol hexacrylate, modifiec1 l,4-butylene diacrylate, 1,6 hexc~nediol diacrylate, modified trimethylolpropane triacrylate!, modified s penta~rythritol triacrylate, poly functional i~ocyana~es with hydro~y monomers (isophorone diisocyanate plus hydr~xy ethyl acrylate), methacrylated epoxy re~in, and the like, and mistures and prepol~mers thereof.
The amount of ethylenically unsaturated moncmers u~ed to make up the microgel can be widely varied. Typical amounts will fall in the range af la 90% by weigh~ of mon~mer or monomers containing -0~ sr -C00~ groups and 9~-10% by 15 weight o~ monomer or monomers which are free rom such groups.
The amount of crosslinking agent that is used is im~ortan~ although this can be varied o~er a relatively large range. Desirably the amount of crosslinking agent constitutes at least about 0.5%
and up to 20% by ~eight of the total amount of all materials used for the emulsion polymerization.
In the normal situation this is roughly e~quivalent to a r~nge of 5-70%, preferably 8-50%, by weight 25 of the total weight of ethylenically unsatura~ed ncmomers and crosslinking agent.
Conventional emulsifiers or surfact,~nts and initiators for emulsion polymerizatic~n are used to pr~pare the ~icrogel emulsion. r~ypical 30 emulsi~iers tor surfac~ants) include such anionic alkali metal salts of orsanic ~arboxylic acids or soaps, e.~., potassium oleate or stear2te. Alkyl sulfates and ,1kyl- or alkylarylsulfonat~s may also be used~~ Preferre~ for use are the sodium 115g17~
alkyl sulfosuccinamates, e.g.,, disodium N-octadecyl sulfosuccinamate an~l sodium diamyl sulfosuccinæmate. Advantageously, two or more such surfactants are used to~ether since this seems to give an emulsion of better stability.
- Sui~able initiators are the free radical yielding peroxides and persal~s eg., benzoyl peroxide, lauroyl pero~ide, ammonium, potas~ium or ~odlum persulfate, etc~
AdYantageously the emulsion polymerization is carried out by adding the monomers gradually to heated water containing the emulsifier and initiator. Preferahly tbe system is heated to, for example, 75-90 C during the moncmer addition and for a short time afterwards although it will be a.ppreciated that the poly-merization conditions c~n be widely varied and will depend on other factors , e.~., the monomers involved. It is, in any case, important to obtain a stable emulsion in which the polymer par~icles have sizes in the order of about 0.05 to 10 micr~ns .
The aque~us ~icrogel emulsion may be azeotropic~lly distilled using any convenient organic solvent which forms an azeotrope with water but does not dissolve or swell the microgel sol~ds. TXpically suitable solvents include cellosolve acetate, butanol, naphtha, mineral spirits and the like. The amount of solvent used 30 can be varied but should be enoush to facilitate azeotropic removal of the water. All of the water of the microgel emulsion may be removed or only a portion the~eof. ~sually at least 50~ by weight of the water should be removed.
1 ~5917~ .
An additional al~ern,~tive is to coagulate the emulsion with an organic solvent. The coagulum can be physically separated from a water layer. ~he coagulated portion can then be dryed urther by azeotropic distillation or com~ined with the solution acrylic.
~ bile the microgel emul-Rion ~ay be eparately 3ubjected to azeotropic di~tillation, the prefere~ce, a~ n~ted earlier, i~ to carry out the dlstillation either conc~rrently with the preparat~on (cook) of the acrylic paint resin or ln the presence of the previously pre~ared acrylic resin. In this way, it is possible, if desir~d, to ef~ect reaction between the acrylic resin and the ~icrogel polymer particles~ This may involve further gr~t or copolymerization via double bonds r~main~ng in the micr~gel to the linear a:rylic polymer which is formed or being formed.
The acrylic polymer used herein may be 20 made in convention~l fashion in orga~ic solvent solution using usual polymerization conditions except for the option of including the microgel emulsion in the reaction mixture an~
azeotropically removing the microgel water during the acrylic polymer preparation or cook. If the acrylic resin is prepared in the presence of the micro~el, the orqanic solvent whicb is employed should meet the indicated re~uir~ents for azeotropically distilling the water from the 30 microyel emulsion, i.e., the solvent ~hould form an azeo~rope with water at the ~emperat~re used t~
prepare or cook the acsylic resin and it should not dissolve or swell the microgel particles. Any of the monomers referred to a~ove in connec~ion 35 with the preparation of the microgel may b~ used ~917 to make the acrylio resin. PreferaDly the acrylic resin includes an ethylenically unsaturated monomer which contains either an -a~ or -COO~
group and another such monomer which is free from such groups. E~cept as indicated, the reac~ion conditions for the acrylic resin cook, i.e., temperature, monomer~, proportions, initiators and temperature~ are those conventionally employed ~n preparing acryllc resins by polymerization in organic solvent solu~ions.
The amount of m~cro~el solids to acrylic resin solids in the final acrylic resin/microgel compositionr whether the microgel is included in the preparation of the acrylic resin or subsequently added thereto, will usually be in the range of 5 to 15% by weight of the total resin solids. N~r~ally the total solids content of the final acrylic resin/mi~rogel composition as used will be in the order of 40-60~ by weight. The acrylic resin/micro~el composition may be mixed with alkylated melamine-formaldehyde preconden~ates or polyesters and pigments, e.g., aluminum flake, to provide highly useful paints in coating compositions. As indicated, paints based 25 on ~he present acrylic resin/microgel preparations with and without aluminum flaXe, on application and curing, are characterized by the orientation o~ the pigment ~nd improved sag resistance.
1 lSgl78 The invention is illust:rated by the following examples wherein parts, percentages and ratios are by weight unless othe~rwise indicated:
E:~AMPLE 1 5 A. MIC~OG~L E~SION PRE~ARATION
~ e~n~
A 3.00% Ae~osol 18* ~American Cyanamid) l~50~ Aerosol AY-65*~ (American Cyanamid) .25~ Sodium Bicar~onate 40.2S~ Deionized Water .25% Ammonium Persulfate 14.75% Deionized Water 4.00% ~ydroxypropyl Methacrylate 32.00% 2-Ethylhe~yl Acrylate 4.00~ Divinyl Benzene *Disodium N-octadecyl sulfosuc~inamate *~5Odium diamyl sul~o~uccinamate To a five liter, three neck reaction fla~k e~uipped with a condenser, thermometer and 20 agitator, the Aeros~l 18, Aerosol AY-~5, sodiu~
bicar~onate and first deionized water are charged. The ammonium peEsulfate and second deionized water are premixed and added to a small addi~ioQ funnel. The hydro~ypropyl methacrylate, 25 2-ethylhexyl acrylate and divinyl benzene were premixed and added to a separate additian funnel. The surfactants and water are heat~d to 87 ~ 2~C at which time 10% o~ the ammonium 1 1$917 persulfate solution is added. T~e acrylic monomers are added to the reaction flask continuously over 2 1/2 hours, At the same time, the remaining a~monium persulfate ~olution is 5 added continuously over 3 hours. The temperature o~ the reaction i~ ~eld ak 87 * 2C thsoughout the ~onomer add. Thirty minutes after the ammonium persulfate 5~lution is added, the emulsion is cooled to roam tem~erature and discharged.
10 ~. ACgYLIC ~IC~OG~h RESI~ PRE~ARATION
17.67% n-ButanoL ~ ~ p ~D~) A 17.67% Cellosolv~ Acetate (~nion Carbide) 12.32~ ~icrogel Emulsion .36~ t-Butyl Per~enzcate (50 in Mineral Spirits~
12~69% Styrene 11.66% Butyl Methacrylate
2.31~ n-Dodecyl Mercaptan 20 9.75~ 2-Ethylhe~yl Acrylate 11.72~ ~ydro~ypropyl Methacryla~e .99~ Acrylic Acid 2.31~ -~utyl Perbenzoate (50 in Mineral Spirits) .12~ t-~utyl Perbenzoate (50 in ~ineral Spiri~s) .43 Cellosolve Aceta~e To ~ five liter, four neck reaction flask equipped with a condenser, Barrett water trap, 30 thPrmometer and agitator, he n-~utanol, CPllosolYe Acetate, micros21 emulsion and t-~utyl perbenzoate are charged. The styrene, butyl methacrylate and n~dodecyl mercaptan are premixed and added to an addition funnel (Premix I~ The 2-ethylhexyl acrylate, hydroxypropyl methacrylate, acrylic acid and second t-~utyl perbenzoate are premixed and char.ged to a second addition ~unnel (Premis II). The solvents, emulsion and t-~utyl perbenzoate are heated to re1u~, approximately 95C. When reflux is obtained, Premix I and II
are a~ded simultaneously and continuously over a four hour period of time. During the monomer add, water fro~ the emulsion is continuously removed by azeotropic distillation through the Barrett trap. Immediately following the Premix ~ and II
addition, a mi~ture of t-~utyl perbenzoate and Cellosolve Acetate is added over one hour. The resin is allowed to reflux until all of the theoretical water is removed. The resin is then cooled and filtered. Ihis resin contains lOg microgel based on total resin solids. The physical characteristics of ~his resin are 58.3%
non-volatiles, ~ viscosity and 31.7 acid number~
EXA~Er.~ 2 The monomer ratio of the microgel emulsion in Example 1 is 10/80/I0, by wei~ht, hydroxypropyl methacrylate/2-ethylhexyl acrylate/divinyl benzene. ~sing the same ccokin~
p~ocedures of the e~ulsion in Example 1, a ~icrogel emulsion is prepare~ using a monomer ratio of 10/70/20, hydro~ypropyl methacrylate/2-ethyIhe~yl acrylate/divinyl ~enzene.
A. MICRO OE L E~hSION PREPARATIC)N
are a~ded simultaneously and continuously over a four hour period of time. During the monomer add, water fro~ the emulsion is continuously removed by azeotropic distillation through the Barrett trap. Immediately following the Premix ~ and II
addition, a mi~ture of t-~utyl perbenzoate and Cellosolve Acetate is added over one hour. The resin is allowed to reflux until all of the theoretical water is removed. The resin is then cooled and filtered. Ihis resin contains lOg microgel based on total resin solids. The physical characteristics of ~his resin are 58.3%
non-volatiles, ~ viscosity and 31.7 acid number~
EXA~Er.~ 2 The monomer ratio of the microgel emulsion in Example 1 is 10/80/I0, by wei~ht, hydroxypropyl methacrylate/2-ethylhexyl acrylate/divinyl benzene. ~sing the same ccokin~
p~ocedures of the e~ulsion in Example 1, a ~icrogel emulsion is prepare~ using a monomer ratio of 10/70/20, hydro~ypropyl methacrylate/2-ethyIhe~yl acrylate/divinyl ~enzene.
A. MICRO OE L E~hSION PREPARATIC)N
3.00~ Ae~Qsol 18 1.50~ Aerosol A~-65 50.25% Deionized Water .25~ ~odium ~icarbonate .2S~ Ammonium Persulfate 14.75~ Deio~ized Water 3.0Q~ ~ydsoxypropyl Methacrylate 21.00% 2-E~hylhexyl Acrylate 6.00~ Divinyl benzene B. ACRY~IC MICROG~L RESIN PREPARATION
16.3 % n-Butanol 16.3 % Cellosolve Acetate 19.15~ Microgel E~ulsion .33% toButyl Perbenzoate (50 i~ Mineral Spirits) 11.70% Styrene 10.75~ Butyl ~ethacrylate 2~15~ n-Dodceyl Mercaptan 8.~g% 2- thylhexyl Acrylate 10.81% ~ydroxypropyl Methacrylate .91% Acrylic Acid 2013% t-Butyl Perbenzoate (50 in M~neral Spirits) 25~ t-Butyl Perbenzoate t~O~
in ~ineral Spirits~
.37~ Cellosolve Asetate l 15~17~
li The procedure for the preparation o~ this acrylic microgel resin is the same as stated in Exam~le l-B. The amount of microgel in the ~crylic re~in is 10~ based on total solids. The 5 physical characteristics of this resin are X-Y
viqcosity at 58.3 ~on-volatiles and 30.7 acid number.
EXaMPLE 3 ~sing the same surfactants, level and 10 procedure for the microgel emulsion in Example 1-a, an emulsion is prepared with a 10/88~2 monomer ratio of hydroxypropyl methacrylate/methylmeth-acrylate/divinyl ben~ene.
The acrylic microgel resin is prepared 15 from the formulati~n siven below:
~ 17.67% n-8utanol 17.67% Cellosolve Acetate 12.32% ~icrogel Emulsion .36% t-Butyl Perbenzoate -(50%
20in Mineral Spirits) 12.69~ Styrene 11.66~ Butyl ~thacrylate 2.31% n-Dadecyl Mercaptan ~.7S% 2-Ethylhexyl Acrylate 11.72% ~ydroxypropyl Methacrylate .99~ Acrylic Acid 2~31~ t-~utyl Perbenz~ate (50 in ~ineral Spirits) .12% t-Butyl Perbenzoate (S0 ~n Minera:L Spiri~s) .43~ Cellosolve Acetate The procedure for the preparation of the 5 acrylic ~icrogel resin i~ the same as stated in Example l-B. The amount of micro~el in this re~in i~ 10% based on total solids. The physical charact~ri3tics of this resin are ~-X viscosity at 59.2~ non-volatiles and 31.8 acid numker.
EX~MPhE 4 An alternate procedure for the acrylic microgel resin preparation a~ given in Example 2, i8 to ~irqt prepare an acrylic resin s~lution, then dehydrate the microgel em~lsion in the 15 presencs o~ the acrylic resin. The formulation for tbe acrylic resin is given below:
Solution Acrylic ~esin 25.3% Cellosolve Aceta~e .5% Cumene ~ydroperoxide 19.0% Styrene 170 4% Butyl ~ethacrylate 14.7~ 2-Ethylhexyl Acrylate 17.5% ~ydroxypropyl Methacrylate 1.4~ Acrylic Acid 2.4% Cumene ~ydroperoxide ~2~ di-~-Butyl Peroxide .6~ Cellosolve Acetate 1 15~178 T~ prepare this resin a five liter reaction flask, e~uipped with a thermometer conden er and agitator, was charged with the Cellosolve Acetate and first c~mene hydroperoxide. This mixture was then brought to reflux, 144 ~ 1 C. ~ mixture comprising the s~yrene, butyl methacrylate, 2-ethylhexyl acrylate, hydroxypropyl methacrylate, acrylic acid a~d the second c~mene hydroperoxide, was added lo continuou.~ly over four hours to the refluxing solvent. Immediately af~er the mono~ers were adde~ r the mixture of di~ utyl peroxide and Cellosc~lve Acetate was added over a per iod of one hour. ~he resulting acrylic resin has a Z2 15 vi~cosity at 6~.4~ non-volatiles with a 25.1 acid number .
The acrylic microgel resin was then prepared by blending 66.9 parts acrylic resin, 19.18 l?artS microgel emulsion (Example 2A) and 20 13.92 parts n-~utanol in a reaction flas~ and removing the water by azeotropic distillation~
~rhe level of microgel in this resin was 10% based on total solids . The physical character istics were Z3 viscosity at 61. 4 non-volatiles and 2~. 2 25 acid number.
~ PI.E 5 Another procedure for incorporating the microgel resin in an acrylic resin is to first dehydrat~ the emulsion in an organic solvent, ~hen 30 blend it with the acrylic resin.
A ive lit~r reaction flask equipped with a condenser, ~arrett trap and agitator was charged with 626 gr~ms of microgel e~ulsian from Example l 15~3:~7 2-A. To this was added 950 grams cf n-butanol and 50 grams of ~lene. The mixture was heated to reflux and the wate~ removed by azeotropic di~tillation. To the dehydrated microgel is added 5 2042 grams of acrylic resin from Example 4. The mixture was again heated to reflux and 500 grams of s~lvent removed. This resin contains 12.2%
microgel based on total resin solids The physical characteristics of this acrylic microgel lo resin was a J~ cosity 2t 56.4% non-volatiles and a 2~.4 acid number.
.
E~AMPr,ES 6-14 Microgel emulsions I-IV were prepared with materials as shawn on Table I. The procedure 15 for the preparati~n ~f these emulsions is as follows:
~ 3 a five liter, three neck reaction flask, equipped with a condenser, thermometer and agi~ator, charg~the first deionized water and 20 Surfactant 501E. Premi~ the ammonium persulfate and second portion of deionized watPr ~nd charge to a small addition funnel. A premix of styrene, butyl methacrylate, 2-ethylhexyl acrylate, hydroxypropyl methacrylate, acrylic acid, 25 ~rimethylolpropane triacrylate, COPS I, the second 510E and deionized water is prepared and charged ~o a sec~nd addition ~unnel. This mixture of monomers, wate~ and surfactant, called a pre-e~ulsiont was held under constant asitation to 30 maintain a uniform mixture. The c~ntents o~ the reaction flask was heated to 72 2C at which time 17% of the a~monium persulfate solution was added. The monomer pre-emulsion was then added ? D 4/f r f~ ; Jf~ c rf~ r J- LJ / f~D ~ h t ~
15~3~78 continuously over 2 1~2 hours. ~he remaining ~monium persulfate solution was added continuously over ~ 3/4 hours. One half hour after the la~t addition was made, the emulsion was cooled to 30C and discharged from the ~lask~
~ icrogel emulsions V-VII were prepared according to the pro edure in Example l-A.
The acrylic microgel resins in ~xamples 6, 7, 8, 10, 11, 12, and 13, as shown in Table II, ~ere ~repared by the same procedure as in Example l-B.
Esample 9 was prepared i~ a manner similar to Example 1-~ except 75% of the theoretical water was removed by azeotropic dlstillation prior to the addition of acrylic moncmar~. Example 14 was also prepared like Example 9 except only 50% of the theoretical water was re~oved prior to the addition of the acrylic monomers.
1 7 ~
_ABLE I
I II III
_ __ Aerosol ]8 Aerosol AY-65 Sodium Bicarbonate Surfactant 501E* 1.25 1.25 1.25 Deionized Water15.7515.75 15.75 Ammonium Persulfate .25 .25 .25 Deionized Water7.257.25 7.25 Styrene 12.95 12.85 12.7 Butyl Methacrylate12.025 11.875 11.75 2-Ethylhexyl10.075 9.95 9.85 Acrylate Hydroxypropyl12.0011.875 11.75 Methacrvlate Acrylic Acid .95 .975 .975 Trimethylolpropane .475 .975 Triacrylate Surfactant 501E1.251.25 1.25 ~20 COPS I** 1.25 1.25 1.25 Deionized Water25.0025.00 25.00 TOTAL 100.00 100.00 100.00 *Monoalkyldisodium Sulfosuccinate (American Cyanamid~
C~ JVD ~ R~)~ m ~
** ea~s - ~ Proprietary Copolymerizable Surfactants ~Alcolac) ~ ~5?~178 TABLE I (Continued) IV V VI
Aerosol 18 ¦3.00 3.00 Aerosol AY-6S ¦1.50 1.50 5 Sodium Bicarbonate .25 .25 Surfactant 501E*1.25 Deionized Water15.75 39.7539.75 Ammonium Persulfate .25 .25 .25 Deionized Water7.25 7.25 7.25 10 Styrene 12.47511.975 11.55 Butyl Methacrylate 11.525 11.050 10.55 2-Ethylhexyl 9.60 9.125 8.65 Acrylate Hydroxypropyl 11.52511.050 10.55 Methacrylate Acrylic Acid .95 .95 .95 Trimethylolpropane 1.925 3.85 5.75 Triacrylate Surfactant 501E1.25 20 COPS I** 1.25 Deionized Water25.00 TOTAL 100.00100.00 100.00 *Monoalkyldisodium Sulfosuccinate (American Cyanamid) ** COPS I Proprietary Copolymerizable Surfactants (Alcolac) ~1~9178 2?
_ABLE I (Continued) VII
Aerosol 18 3.00 Aerosol AY-65 1.50 5 Sodium Bicarbonate .25 Surfactant 501E*
Deionized Water57.75 Ammonium Persulfate .25 Deionized Water7.25 10 Styrene 6.60 Butyl Methacrylate 6.00 2-Ethylhexyl 4.80 Acrylate Hydroxypropyl6.00 Methacrylate Acrylic Acid .60 Trimethylolpropane 6.00 Triacrylate Surfactant 501E
COPS I**
Deionized Water TOTAL 100.00 *Monoalkyldisodium Sulfosuccinate (American Cyanamid) ** COPS I Proprietary Copolymerizable Surfactants (Alcolac) 1 15~178 TABLE II
Example -- 6 7 8 _ Butyl Alcoho3 17.6017.56 17.56 Cellosolve Acetate17.6017.5617.56 Emulsion* 11.37 11.5511.37 tert-Butyl Peroctoate.71 .70 .70 (50~ in Mineral Spirits) Styrene 13.34 13.3213.32 Butyl Methacrylane11.5011.4811.48 10 n-Dodecyl Mercaptan1.70 1.70 1.70 2-Ethylhexyl Acrylate10.7610.7410.74 Hydroxyethyl Acrylate9.259.239.23 Acrylic Acid .97 .97 .97 tert-Butyl Peroctoate4.544.54 4.54 (50~ in Mineral Spirits) t-Butyl Peroctoate .23 .23 .23 (50% in Mineral Spirits) Cellosolve Acetate .43 .43 .43 *Microgel Emulsion From Table I I II III
Level of Crosslinking Monomer in Microgel (%) 0 1 2 Level of Microgel ~mulsion (%) 11 11 11 Physical Characteristics Non-volatiles 56.9 56.6 57.1 Viscosity X hy M J
Acid Number 19.9 20.- 18.2 1 159~78 TABLE II (Continued) , Example -- 9_ 10 11 Buty 1 Alcohol17.6017.6016.99 Cellosolve Acetate17.6017.6016.99 Emulsion* 11.3711.3714.45 tert Butyl Peroctoate.71 .71 .68 (50~ in Mineral Spirits) Styrene 13.3413.3412.88 Butyl Methacrylane11.5011.5011.10 10 n-Dodecyl Mercaptan1.701.701.64 2-Ethylhexyl Acrylate10.7610.76 10.38 Hydroxyethyl Acrylate9.259.25 8.93 Acrylic Acid .97 .97 .94 tert-Butyl Peroetoate4.54 4.54 4.39 (50~ in Mineral Spirits) t-Butyl Peroctoate .23 .23 .22 (50% in Mineral Spirits) Cellosolve Acetate .43 .43 .41 *Mierogel Emulsion From Table I IV V V
Level of Crosslinking Monomer in Mierogel (%) 4 8 8 Level of Microgel Emulsion (%) 11 11 14 Physieal Charaeteristies Non-volatiles 56.8 ;7.6 57.2 Viseosity I K L
Aeid Number 19.0 23.4 19.2 7 ~
TABLE II (Continued) Example -- 12 _ 13 14 Butyl Alcoho].16.:3817.6016.538 Cellosolve Acetate16.:3817.60 16.538 Emulsion* 17.51 11.3716.712 tert-Butyl Peroctoate .66 .71 .665 (50% in Mineral Spirits) Styrene 12.42 13.3412.539 Butyl Methacrylane10.7011.5010.807 10 n-Dodecyl Mercaptan1.591.701.601 2-Ethylhexyl Acrylate10.0110.76 10.110 Hydroxyethyl Acrylate8.619.25 8.694 Acrylic Acid .91 .97.915 tert-Butyl Peroctoate 4.234.54 4.271 (50~ in Mineral Spirits) t-Butyl Peroctoate.22 .23.218 (50% in Mineral Spirits) Cellosolve Acetate.39 .43.392 *Microgel Emulsion From Table I V VI VII
Level of Crosslinking Monomer in Microgel (%) 8 12 20 Level of Microgel Emulsion (~) 17 11 11 PhYsical Characteristics Non-volatiles 58.2 56.457.1 Viscosity R-S I H
Acid Number 19.8 18.820.3 3 ~59178 The following two microgel emulsions were prepared for conversion to acrylic microgel resins. The procedure ~or preparing these emulsions was the same as shown in Example 1-A.
Example 15 Example 16 Surfactant 501E2.450% 2.500%
COPS I 1.250~ 1.250%
Deionized Water45.975~ 42.825%
10 Ammonium Persulfate.175~ .175%
Deionized Water7.249~ 7.225%
Methyl Methacrylate13.300~ 14.250%
Ethyl Acrylate24.453% 26.225%
Acrylic Acid 1.715% 1.850 15 Pentaerythritol3.433% ~~~
Triacrylate Diethylene Glycol --- 3.700%
Diacrylate The acrylic microgel resins were then prepared from the microgel emulsion by the same procedure as stated in Example l-B. The formulations for these resins are given below.
Example 15 Example 16 n-Butanol 17.67% 17.67%
25 Cellosolve Acetate17.67% 17.67%
Microgel Emulsion12.32~ -12.32%
T-Butyl Perbenzoate.36% .36%
(50% in Mineral Spirits) Styrene 13.86% 12.69%
30 Butyl Methacrylate11.66% 11.66 n-Dodecyl Mercaptan2.31% 2.31~
2-EthylhexYl Acrylate10.92% 9.75%
Hydroxypropyl --- 11.72%
Methacrylate 35 Hydroxyethyl Acrylate 9.38% ---Acrylic Acid .99% .99%
t-Butyl Per~enzoate2.31% 2.31%
(50% in Mineral Spirits) 1 15gl78 Cellosolve Acetate .43% .43%
t-Butyl Perbenzoate .:12Q~ .12%
(50% in Mineral Spirits) 5 Physical Characteristics Non-Volatiles 59.5% 61~0%
Viscosity Zl-Z2 Y-Z
Acid Number 35.1 30.8 The level of microgel present in each example is 10% based on total solids.
~ ~S9178 ~g Microgel emulsions I-X were prepared with materials as shown in Table III. Emulsions I, III
and rx were prepared according to the procedure used for emulsion I-rV of examples 6-9. Emulsions II, rV-VI and X were prepared in a manner similar to Example l-A. Emulsion VII was prepared like example l-A with the following changes. The premix of water and ammonium pe~sulfate was added over four hauss. The premi~ of methyl methacrylate, 29% o~ the hydroxyethyl acrylate and hexanediol diacrylate was added o~er 2 hours. The reaction was held at 80 ~ 2C for 1~2 hour, th n a second premi~ of the ~tyrene, butyl methacrylate, 2-ethylhexyl acrylate, 71% of the hydroxyethyl acrylate and the acrylic acid was added over 1 1/2 hours.
The acrylic microgel compositions for examples 17-26 are illustrated in Table IV.
E~amples 18 and 25 were prepared by the same procedure as in Example l-B. Examples 1~, 1g-24, and 26 were p~epared by th~ same p~ocedur2 as in - Example 14.
~ 15~7~
TABI,E III
I II III
Surfactant 501E ¦ 2.50 COPS I 1.25 Aerosol MA-80* .275 .275 Aerosol 18 Aeosol AY-65 Deionized Water 52.1568.75 52.15 Ammonium Persulfate 10 Ammonium Persulfate 0.025 0.25 0.025 Deionized Water 0.475 7.25 0.475 Surfactant 501E
COPS I
Aerosol 22** .60 .60 15 Aerosol MA-80* .25 .25 Deionized Water 25.00 25.00 Hexanediol 10.5010.00 10.50 Diacrylate Methyl Methacrylate 8.00 Hydroxypropyl Methacrylate Butyl Acrylate Ethylhexyl Acrylate 8.40 Hydroxyethyl 2.10 2.00 2.10 Acrylate Butyl Methacrylate 8.40 Styrene Ethyl Acrylate Acrylic Acid Methyl Acrylate Isobutyl Acrylate Isobutyl Methacrylate Ammonium .225 .225 Persulfate 100 .00100 . 00100 . 00 * Sodium dihexyl sulfosuccinate ~American Cyanamid) ** Tetrasodium N-(1,2-dicarboxy ethyl)-N-octadecyl sulfosuccinamate (American Cyanamid) 1 1~9178 TABLE III (Continued~
IV V Vl Surfactant 501E2.50 ¦2.50 COPS I 1.25 ¦1.25 S ~erosol MA-80*
Aerosol 18 3.00 Aeosol AY-65 1.50 Deionized Water68~75 68.7567.75 Ammonium Persulfate 0.25 10 Ammonium Persulfate 0.25 0.25 0.25 Deionized Water7.25 7.25 7.25 Surfactant 50lE
COPS I
Aerosol 22**
Aerosol MA-80*
Deionized Water Hexanediol 10.00 10.0010.00 Diacrylate Methyl Methacrylate Hydroxypropyl Methacrylate Butyl Acrylate Ethylhexyl Acrylate Hydroxyethyl 2.00 2.00 2.00 Acrylate Butyl Methacrylate Styrene 8.00 Ethyl Acrylate Acrylic Acid Methyl Acrylate Isobutyl Acrylate 8.00 Isobutyl 8.00 Methacrylate Ammonium 3S Persulfate 100.00 100.00100.00 * Sodium dihexyl sulfosuccinate (American Cyanamid) ** Tetrasodium N-(1,2-dicarboxy ethyl)-N-octadecyl sulfosuccinamate (American Cyanamid) 5~17 TABLE III (Continued) VII VIII IX
_ Surfactant 501E 2.50 2.50 1.25 COPS I 1.25 1.25 5 Aerosol MA-80*
Aerosol 18 Aeosol AY-65 Deionized Water 68.7548.75 43.75 Ammonium Persulfate 10 Ammonium Persulfate 0.25 0.25 0.25 Deionized Water 7.25 7.25 7.25 Surfactant 501E 1.25 COPS I 1.25 Aerosol 22**
Aerosol MA-80*
Deionized Water 25.00 Hexanedio]. 10.0010.00 10.00 Diacrylate Methyl Methacrylate 8.00 20 Hydroxypropyl 2.00 Methacrylate Butyl Acrylate 8.00 Ethylhexyl Acrylate 4.20 Hydroxyethyl 2.00 7.00 Acrylate Butyl Methacrylate 5.00 Styrene 5.40 Ethyl Acrylate Acrylic Acid 0.40 30 Methyl Acrylate 8.00 Isobutyl Acrylate Isobutyl Methacrylate Ammonium Persulfate 100.0 b - loo.oo loo.oo * Sodium dihexyl sulfosuccinate (American Cyanamid) ** Tetrasodium N-~1,2-dicar~oxy ethyl)-N-octadecyl sulfosuccinamate (American Cyanamid) ~ 1S~7~3 TABLE III (Continued) X
Surfactant 501E2.50 COPS I 1.25 5 Aerosol MA-80*
Aerosol 18 Aeosol AY-65 Deionized Water68.75 Ammonium Persulfate 10 Ammonium Persulfate 0.25 Deionized Water7.25 Surfactant 50lE
COPS I
Aerosol 22**
15 Aerosol MA-80*
Deionized Water Hexanediol 10.00 Diacrylate Methyl Methacrylate 20 Hydroxypropyl Methacrylate Butyl Acrylate Ethylhexyl Acrylate Hydroxyethyl 2.00 Acrylate Butyl Methacrylate Styrene Ethyl Acrylate 8.00 Acrylic Acid Methyl Acrylate Isobutyl Acrylate Isobutyl Methacrylate Ammonium Persulfate 100 . O O
* Sodium dihexyl sulfosuccinate (American Cyanamid) ** Tetrasodium N-(1,2-dicarboxy ethyl)-N-octadecyl sulfosuccinamate (American Cyanamid) l 15917~
TABLE IV
Butanol 16 ~ 4 415 ~ 32 Cellosolve Acetate16.44 15.32 Emulsion* 16.09 24.00 Tert-Butyl Peroctoate.67 (50% in Mineral Spirits) tert-But~L Perbenzoate .31 n-Dodecyl Mercaptan1.61 2.00 Styrene 12 ~ 87 11~ 00 Butyl Methacrylate10.89 10.11 2-Ethylhexyl acrylate10.248 ~ 45 Hydroxyethyl Acrylate8 ~ 7 2 Acrylic Acid .92 o86 15 Hydroxypropyl lO.lh Methacrylate tert-Butyl Peroctoate4.29 (50% in Mineral Spirits) tert-Butyl Perbenzoate 2.00 20 tert-Butyl Peroctoate0.43 (50% in Mineral Spirits) Butanol 0.39 Cellosolve Acetate 0. 37 tert-Butyl Perbenzoate 0.10 100 ~ 00100 ~ 00 *Microgel Emulsion From Table III I II
Physical Characteristics Non-volatiles 59 ~1 60.2 30 Viscosity H-I Z
Acid Number 20.6 40.4 1 15gl7~
TABLE IV (Continue _ Butanol 16.44 ~ 16.44 Cellosolve Acetate16.44 j 16.44 S Emulsion~ 16.09 ¦ 16.09 Tert-Butyl Peroctoate.67 1 .67 (50~ in Mineral Spirits) tert-Butyl Perbenzoate n-Dodecyl Mercaptan1.61 ¦ 1.61 Styrene 12.87 112.87 Butyl Methacrylate10.89 10.89 2-Ethylhexyl acrylate10.24 10.24 Hydroxyethyl Acrylate 8.72 8.72 Acrylic Acid .92 .92 Hydroxypropyl Methacrylate tert-Butyl Peroctoate4.29 4.29 (50% in Mineral Spirits) tert-Butyl Perbenzoate tert-Butyl Peroctoate0.43 0.43 (50% in Mineral Spirits) Butanol 0.39 0.39 Cellosolve Acetate tert-Butyl Perbenzoate 100.00 100.00 *Microgel Emulsion From Table III III IV
Physical Characteristics Non-volatiles 58.6 58.0 30 Viscosity H-I X
Acid Number 20.8 19.3 1 15917~
TA~LE IV (ContLnued) ~ 22 Butanol :L6.4A 16.44 Cellosolve AcetateL6.44 16.44 Emulsion* :L6.09 16.09 Tert-Butyl Peroctoate.67 .67 (50% in Mineral Spirits) tert-Butyl Perbenzoate n-Dodecyl Mercaptan1.61 1.61 Styrene 12.87 12.87 Butyl Methacrylate10.89 10.89 2-Ethylhexyl acrylate10.2410.24 ~ydroxyethyl Acrylate 8.72 8.72 Acrylic Acid .92 .92 Hydroxypropyl Methacrylate tert-Butyl Peroctoate4.29 4.29 (50% in Mineral Spirits) tert-Butyl Perbenzoate tert-Butyl Peroctoate0.43 0.43 (50% in Mineral Spirits) Butanol 0-39 0.39 Cellosolve Acetate tert-Butyl Perbenzoate 100.00 100.00 *Microgel Emulsion From Table III V VI
PhYsical Characteristics Non-volatiles 56.9 57.0 30 Viscosity I H-I
Acid Number 18.5 - 17.5 ~ 15~17~
TABLE IV (Contlnued) 23__ 24 Butanol 16.44 17.88 Cellosolve Acetate1~.44 17.88 Emulsion* 16.09 8.73 Tert-Butyl Peroctoate.67 .73 (50% in Mineral Spirits) tert-Butyl Perbenzoate n-Dodecyl Mercaptan1.61 1.75 Styrene 12.87 14.Od Butyl Methacrylate10.89 11.84 2-Ethylhexyl acrylate10.2411.14 Hydroxyethyl Acrylate8.729.48 Acrylic Acid .92 1.00 Hydroxypropyl Methacrylate tert-Butyl Peroctoate4.29 4 67 (50~ in Mineral Spirits) tert-Butyl Perbenzoate tert-Butyl Peroctoate0.43 0.47 (50% in Mineral Spirits) Butanol 0.39 0.43 Cellosolve Acetate tert-Butyl Perbenzoate 100.00 100.00 *Microgel Emulsion From Table III VII VIII
Physical Characteristics Non-volatiles 57.3 56.2 30 Viscosity Q J
Acid Number 19.4 17.8 l 15~17~
TABLE IV (Cont.inued) _ ?5 _ 26 Butanol 15.32 16.44 Cellosolve Acetate15.32 16.44 5 Emulsion* 24.00 16.09 Tert-Butyl Peroctoate ¦.67 (50% in Mineral Spirits) tert-Butyl Perbenzoate.31 n-Dodecyl Mercaptan 2.0 1.61 10 Styrene 11.0 12.87 Butyl Methacrylate10.11 10.89 2-Ethylhexyl acrylate8.45 10.24 Hydroxyethyl Acrylate 8.72 Acrylic Acid .86 .92 15 Hydroxypropyl 10.16 Methacrylate tert-Butyl Peroctoate 4.29 (50% in Mineral Spirits) tert-Butyl Perbenzoate 2.00 20 tert-Butyl Peroctoate 0.43 (50% in Mineral Spirits) Butanol 0.39 Cellosolve Acetate0.37 tert-Butyl Perbenzoate 10 100.00 100.00 *Microgel Emulsion From Table III IX X
Physical Characteristics Non-volatiles 60.8 57.7 30 Viscosity V-W J
Acid Number 32.7 19.9 l 159178 EX~MPL$ 27 (A) Microgel Emulsion Preparation .27~% Aerosol MA-80 5 2 .15 0 DP ionized Water s .~50% ~mmonium persulfate
16.3 % n-Butanol 16.3 % Cellosolve Acetate 19.15~ Microgel E~ulsion .33% toButyl Perbenzoate (50 i~ Mineral Spirits) 11.70% Styrene 10.75~ Butyl ~ethacrylate 2~15~ n-Dodceyl Mercaptan 8.~g% 2- thylhexyl Acrylate 10.81% ~ydroxypropyl Methacrylate .91% Acrylic Acid 2013% t-Butyl Perbenzoate (50 in M~neral Spirits) 25~ t-Butyl Perbenzoate t~O~
in ~ineral Spirits~
.37~ Cellosolve Asetate l 15~17~
li The procedure for the preparation o~ this acrylic microgel resin is the same as stated in Exam~le l-B. The amount of microgel in the ~crylic re~in is 10~ based on total solids. The 5 physical characteristics of this resin are X-Y
viqcosity at 58.3 ~on-volatiles and 30.7 acid number.
EXaMPLE 3 ~sing the same surfactants, level and 10 procedure for the microgel emulsion in Example 1-a, an emulsion is prepared with a 10/88~2 monomer ratio of hydroxypropyl methacrylate/methylmeth-acrylate/divinyl ben~ene.
The acrylic microgel resin is prepared 15 from the formulati~n siven below:
~ 17.67% n-8utanol 17.67% Cellosolve Acetate 12.32% ~icrogel Emulsion .36% t-Butyl Perbenzoate -(50%
20in Mineral Spirits) 12.69~ Styrene 11.66~ Butyl ~thacrylate 2.31% n-Dadecyl Mercaptan ~.7S% 2-Ethylhexyl Acrylate 11.72% ~ydroxypropyl Methacrylate .99~ Acrylic Acid 2~31~ t-~utyl Perbenz~ate (50 in ~ineral Spirits) .12% t-Butyl Perbenzoate (S0 ~n Minera:L Spiri~s) .43~ Cellosolve Acetate The procedure for the preparation of the 5 acrylic ~icrogel resin i~ the same as stated in Example l-B. The amount of micro~el in this re~in i~ 10% based on total solids. The physical charact~ri3tics of this resin are ~-X viscosity at 59.2~ non-volatiles and 31.8 acid numker.
EX~MPhE 4 An alternate procedure for the acrylic microgel resin preparation a~ given in Example 2, i8 to ~irqt prepare an acrylic resin s~lution, then dehydrate the microgel em~lsion in the 15 presencs o~ the acrylic resin. The formulation for tbe acrylic resin is given below:
Solution Acrylic ~esin 25.3% Cellosolve Aceta~e .5% Cumene ~ydroperoxide 19.0% Styrene 170 4% Butyl ~ethacrylate 14.7~ 2-Ethylhexyl Acrylate 17.5% ~ydroxypropyl Methacrylate 1.4~ Acrylic Acid 2.4% Cumene ~ydroperoxide ~2~ di-~-Butyl Peroxide .6~ Cellosolve Acetate 1 15~178 T~ prepare this resin a five liter reaction flask, e~uipped with a thermometer conden er and agitator, was charged with the Cellosolve Acetate and first c~mene hydroperoxide. This mixture was then brought to reflux, 144 ~ 1 C. ~ mixture comprising the s~yrene, butyl methacrylate, 2-ethylhexyl acrylate, hydroxypropyl methacrylate, acrylic acid a~d the second c~mene hydroperoxide, was added lo continuou.~ly over four hours to the refluxing solvent. Immediately af~er the mono~ers were adde~ r the mixture of di~ utyl peroxide and Cellosc~lve Acetate was added over a per iod of one hour. ~he resulting acrylic resin has a Z2 15 vi~cosity at 6~.4~ non-volatiles with a 25.1 acid number .
The acrylic microgel resin was then prepared by blending 66.9 parts acrylic resin, 19.18 l?artS microgel emulsion (Example 2A) and 20 13.92 parts n-~utanol in a reaction flas~ and removing the water by azeotropic distillation~
~rhe level of microgel in this resin was 10% based on total solids . The physical character istics were Z3 viscosity at 61. 4 non-volatiles and 2~. 2 25 acid number.
~ PI.E 5 Another procedure for incorporating the microgel resin in an acrylic resin is to first dehydrat~ the emulsion in an organic solvent, ~hen 30 blend it with the acrylic resin.
A ive lit~r reaction flask equipped with a condenser, ~arrett trap and agitator was charged with 626 gr~ms of microgel e~ulsian from Example l 15~3:~7 2-A. To this was added 950 grams cf n-butanol and 50 grams of ~lene. The mixture was heated to reflux and the wate~ removed by azeotropic di~tillation. To the dehydrated microgel is added 5 2042 grams of acrylic resin from Example 4. The mixture was again heated to reflux and 500 grams of s~lvent removed. This resin contains 12.2%
microgel based on total resin solids The physical characteristics of this acrylic microgel lo resin was a J~ cosity 2t 56.4% non-volatiles and a 2~.4 acid number.
.
E~AMPr,ES 6-14 Microgel emulsions I-IV were prepared with materials as shawn on Table I. The procedure 15 for the preparati~n ~f these emulsions is as follows:
~ 3 a five liter, three neck reaction flask, equipped with a condenser, thermometer and agi~ator, charg~the first deionized water and 20 Surfactant 501E. Premi~ the ammonium persulfate and second portion of deionized watPr ~nd charge to a small addition funnel. A premix of styrene, butyl methacrylate, 2-ethylhexyl acrylate, hydroxypropyl methacrylate, acrylic acid, 25 ~rimethylolpropane triacrylate, COPS I, the second 510E and deionized water is prepared and charged ~o a sec~nd addition ~unnel. This mixture of monomers, wate~ and surfactant, called a pre-e~ulsiont was held under constant asitation to 30 maintain a uniform mixture. The c~ntents o~ the reaction flask was heated to 72 2C at which time 17% of the a~monium persulfate solution was added. The monomer pre-emulsion was then added ? D 4/f r f~ ; Jf~ c rf~ r J- LJ / f~D ~ h t ~
15~3~78 continuously over 2 1~2 hours. ~he remaining ~monium persulfate solution was added continuously over ~ 3/4 hours. One half hour after the la~t addition was made, the emulsion was cooled to 30C and discharged from the ~lask~
~ icrogel emulsions V-VII were prepared according to the pro edure in Example l-A.
The acrylic microgel resins in ~xamples 6, 7, 8, 10, 11, 12, and 13, as shown in Table II, ~ere ~repared by the same procedure as in Example l-B.
Esample 9 was prepared i~ a manner similar to Example 1-~ except 75% of the theoretical water was removed by azeotropic dlstillation prior to the addition of acrylic moncmar~. Example 14 was also prepared like Example 9 except only 50% of the theoretical water was re~oved prior to the addition of the acrylic monomers.
1 7 ~
_ABLE I
I II III
_ __ Aerosol ]8 Aerosol AY-65 Sodium Bicarbonate Surfactant 501E* 1.25 1.25 1.25 Deionized Water15.7515.75 15.75 Ammonium Persulfate .25 .25 .25 Deionized Water7.257.25 7.25 Styrene 12.95 12.85 12.7 Butyl Methacrylate12.025 11.875 11.75 2-Ethylhexyl10.075 9.95 9.85 Acrylate Hydroxypropyl12.0011.875 11.75 Methacrvlate Acrylic Acid .95 .975 .975 Trimethylolpropane .475 .975 Triacrylate Surfactant 501E1.251.25 1.25 ~20 COPS I** 1.25 1.25 1.25 Deionized Water25.0025.00 25.00 TOTAL 100.00 100.00 100.00 *Monoalkyldisodium Sulfosuccinate (American Cyanamid~
C~ JVD ~ R~)~ m ~
** ea~s - ~ Proprietary Copolymerizable Surfactants ~Alcolac) ~ ~5?~178 TABLE I (Continued) IV V VI
Aerosol 18 ¦3.00 3.00 Aerosol AY-6S ¦1.50 1.50 5 Sodium Bicarbonate .25 .25 Surfactant 501E*1.25 Deionized Water15.75 39.7539.75 Ammonium Persulfate .25 .25 .25 Deionized Water7.25 7.25 7.25 10 Styrene 12.47511.975 11.55 Butyl Methacrylate 11.525 11.050 10.55 2-Ethylhexyl 9.60 9.125 8.65 Acrylate Hydroxypropyl 11.52511.050 10.55 Methacrylate Acrylic Acid .95 .95 .95 Trimethylolpropane 1.925 3.85 5.75 Triacrylate Surfactant 501E1.25 20 COPS I** 1.25 Deionized Water25.00 TOTAL 100.00100.00 100.00 *Monoalkyldisodium Sulfosuccinate (American Cyanamid) ** COPS I Proprietary Copolymerizable Surfactants (Alcolac) ~1~9178 2?
_ABLE I (Continued) VII
Aerosol 18 3.00 Aerosol AY-65 1.50 5 Sodium Bicarbonate .25 Surfactant 501E*
Deionized Water57.75 Ammonium Persulfate .25 Deionized Water7.25 10 Styrene 6.60 Butyl Methacrylate 6.00 2-Ethylhexyl 4.80 Acrylate Hydroxypropyl6.00 Methacrylate Acrylic Acid .60 Trimethylolpropane 6.00 Triacrylate Surfactant 501E
COPS I**
Deionized Water TOTAL 100.00 *Monoalkyldisodium Sulfosuccinate (American Cyanamid) ** COPS I Proprietary Copolymerizable Surfactants (Alcolac) 1 15~178 TABLE II
Example -- 6 7 8 _ Butyl Alcoho3 17.6017.56 17.56 Cellosolve Acetate17.6017.5617.56 Emulsion* 11.37 11.5511.37 tert-Butyl Peroctoate.71 .70 .70 (50~ in Mineral Spirits) Styrene 13.34 13.3213.32 Butyl Methacrylane11.5011.4811.48 10 n-Dodecyl Mercaptan1.70 1.70 1.70 2-Ethylhexyl Acrylate10.7610.7410.74 Hydroxyethyl Acrylate9.259.239.23 Acrylic Acid .97 .97 .97 tert-Butyl Peroctoate4.544.54 4.54 (50~ in Mineral Spirits) t-Butyl Peroctoate .23 .23 .23 (50% in Mineral Spirits) Cellosolve Acetate .43 .43 .43 *Microgel Emulsion From Table I I II III
Level of Crosslinking Monomer in Microgel (%) 0 1 2 Level of Microgel ~mulsion (%) 11 11 11 Physical Characteristics Non-volatiles 56.9 56.6 57.1 Viscosity X hy M J
Acid Number 19.9 20.- 18.2 1 159~78 TABLE II (Continued) , Example -- 9_ 10 11 Buty 1 Alcohol17.6017.6016.99 Cellosolve Acetate17.6017.6016.99 Emulsion* 11.3711.3714.45 tert Butyl Peroctoate.71 .71 .68 (50~ in Mineral Spirits) Styrene 13.3413.3412.88 Butyl Methacrylane11.5011.5011.10 10 n-Dodecyl Mercaptan1.701.701.64 2-Ethylhexyl Acrylate10.7610.76 10.38 Hydroxyethyl Acrylate9.259.25 8.93 Acrylic Acid .97 .97 .94 tert-Butyl Peroetoate4.54 4.54 4.39 (50~ in Mineral Spirits) t-Butyl Peroctoate .23 .23 .22 (50% in Mineral Spirits) Cellosolve Acetate .43 .43 .41 *Mierogel Emulsion From Table I IV V V
Level of Crosslinking Monomer in Mierogel (%) 4 8 8 Level of Microgel Emulsion (%) 11 11 14 Physieal Charaeteristies Non-volatiles 56.8 ;7.6 57.2 Viseosity I K L
Aeid Number 19.0 23.4 19.2 7 ~
TABLE II (Continued) Example -- 12 _ 13 14 Butyl Alcoho].16.:3817.6016.538 Cellosolve Acetate16.:3817.60 16.538 Emulsion* 17.51 11.3716.712 tert-Butyl Peroctoate .66 .71 .665 (50% in Mineral Spirits) Styrene 12.42 13.3412.539 Butyl Methacrylane10.7011.5010.807 10 n-Dodecyl Mercaptan1.591.701.601 2-Ethylhexyl Acrylate10.0110.76 10.110 Hydroxyethyl Acrylate8.619.25 8.694 Acrylic Acid .91 .97.915 tert-Butyl Peroctoate 4.234.54 4.271 (50~ in Mineral Spirits) t-Butyl Peroctoate.22 .23.218 (50% in Mineral Spirits) Cellosolve Acetate.39 .43.392 *Microgel Emulsion From Table I V VI VII
Level of Crosslinking Monomer in Microgel (%) 8 12 20 Level of Microgel Emulsion (~) 17 11 11 PhYsical Characteristics Non-volatiles 58.2 56.457.1 Viscosity R-S I H
Acid Number 19.8 18.820.3 3 ~59178 The following two microgel emulsions were prepared for conversion to acrylic microgel resins. The procedure ~or preparing these emulsions was the same as shown in Example 1-A.
Example 15 Example 16 Surfactant 501E2.450% 2.500%
COPS I 1.250~ 1.250%
Deionized Water45.975~ 42.825%
10 Ammonium Persulfate.175~ .175%
Deionized Water7.249~ 7.225%
Methyl Methacrylate13.300~ 14.250%
Ethyl Acrylate24.453% 26.225%
Acrylic Acid 1.715% 1.850 15 Pentaerythritol3.433% ~~~
Triacrylate Diethylene Glycol --- 3.700%
Diacrylate The acrylic microgel resins were then prepared from the microgel emulsion by the same procedure as stated in Example l-B. The formulations for these resins are given below.
Example 15 Example 16 n-Butanol 17.67% 17.67%
25 Cellosolve Acetate17.67% 17.67%
Microgel Emulsion12.32~ -12.32%
T-Butyl Perbenzoate.36% .36%
(50% in Mineral Spirits) Styrene 13.86% 12.69%
30 Butyl Methacrylate11.66% 11.66 n-Dodecyl Mercaptan2.31% 2.31~
2-EthylhexYl Acrylate10.92% 9.75%
Hydroxypropyl --- 11.72%
Methacrylate 35 Hydroxyethyl Acrylate 9.38% ---Acrylic Acid .99% .99%
t-Butyl Per~enzoate2.31% 2.31%
(50% in Mineral Spirits) 1 15gl78 Cellosolve Acetate .43% .43%
t-Butyl Perbenzoate .:12Q~ .12%
(50% in Mineral Spirits) 5 Physical Characteristics Non-Volatiles 59.5% 61~0%
Viscosity Zl-Z2 Y-Z
Acid Number 35.1 30.8 The level of microgel present in each example is 10% based on total solids.
~ ~S9178 ~g Microgel emulsions I-X were prepared with materials as shown in Table III. Emulsions I, III
and rx were prepared according to the procedure used for emulsion I-rV of examples 6-9. Emulsions II, rV-VI and X were prepared in a manner similar to Example l-A. Emulsion VII was prepared like example l-A with the following changes. The premix of water and ammonium pe~sulfate was added over four hauss. The premi~ of methyl methacrylate, 29% o~ the hydroxyethyl acrylate and hexanediol diacrylate was added o~er 2 hours. The reaction was held at 80 ~ 2C for 1~2 hour, th n a second premi~ of the ~tyrene, butyl methacrylate, 2-ethylhexyl acrylate, 71% of the hydroxyethyl acrylate and the acrylic acid was added over 1 1/2 hours.
The acrylic microgel compositions for examples 17-26 are illustrated in Table IV.
E~amples 18 and 25 were prepared by the same procedure as in Example l-B. Examples 1~, 1g-24, and 26 were p~epared by th~ same p~ocedur2 as in - Example 14.
~ 15~7~
TABI,E III
I II III
Surfactant 501E ¦ 2.50 COPS I 1.25 Aerosol MA-80* .275 .275 Aerosol 18 Aeosol AY-65 Deionized Water 52.1568.75 52.15 Ammonium Persulfate 10 Ammonium Persulfate 0.025 0.25 0.025 Deionized Water 0.475 7.25 0.475 Surfactant 501E
COPS I
Aerosol 22** .60 .60 15 Aerosol MA-80* .25 .25 Deionized Water 25.00 25.00 Hexanediol 10.5010.00 10.50 Diacrylate Methyl Methacrylate 8.00 Hydroxypropyl Methacrylate Butyl Acrylate Ethylhexyl Acrylate 8.40 Hydroxyethyl 2.10 2.00 2.10 Acrylate Butyl Methacrylate 8.40 Styrene Ethyl Acrylate Acrylic Acid Methyl Acrylate Isobutyl Acrylate Isobutyl Methacrylate Ammonium .225 .225 Persulfate 100 .00100 . 00100 . 00 * Sodium dihexyl sulfosuccinate ~American Cyanamid) ** Tetrasodium N-(1,2-dicarboxy ethyl)-N-octadecyl sulfosuccinamate (American Cyanamid) 1 1~9178 TABLE III (Continued~
IV V Vl Surfactant 501E2.50 ¦2.50 COPS I 1.25 ¦1.25 S ~erosol MA-80*
Aerosol 18 3.00 Aeosol AY-65 1.50 Deionized Water68~75 68.7567.75 Ammonium Persulfate 0.25 10 Ammonium Persulfate 0.25 0.25 0.25 Deionized Water7.25 7.25 7.25 Surfactant 50lE
COPS I
Aerosol 22**
Aerosol MA-80*
Deionized Water Hexanediol 10.00 10.0010.00 Diacrylate Methyl Methacrylate Hydroxypropyl Methacrylate Butyl Acrylate Ethylhexyl Acrylate Hydroxyethyl 2.00 2.00 2.00 Acrylate Butyl Methacrylate Styrene 8.00 Ethyl Acrylate Acrylic Acid Methyl Acrylate Isobutyl Acrylate 8.00 Isobutyl 8.00 Methacrylate Ammonium 3S Persulfate 100.00 100.00100.00 * Sodium dihexyl sulfosuccinate (American Cyanamid) ** Tetrasodium N-(1,2-dicarboxy ethyl)-N-octadecyl sulfosuccinamate (American Cyanamid) 5~17 TABLE III (Continued) VII VIII IX
_ Surfactant 501E 2.50 2.50 1.25 COPS I 1.25 1.25 5 Aerosol MA-80*
Aerosol 18 Aeosol AY-65 Deionized Water 68.7548.75 43.75 Ammonium Persulfate 10 Ammonium Persulfate 0.25 0.25 0.25 Deionized Water 7.25 7.25 7.25 Surfactant 501E 1.25 COPS I 1.25 Aerosol 22**
Aerosol MA-80*
Deionized Water 25.00 Hexanedio]. 10.0010.00 10.00 Diacrylate Methyl Methacrylate 8.00 20 Hydroxypropyl 2.00 Methacrylate Butyl Acrylate 8.00 Ethylhexyl Acrylate 4.20 Hydroxyethyl 2.00 7.00 Acrylate Butyl Methacrylate 5.00 Styrene 5.40 Ethyl Acrylate Acrylic Acid 0.40 30 Methyl Acrylate 8.00 Isobutyl Acrylate Isobutyl Methacrylate Ammonium Persulfate 100.0 b - loo.oo loo.oo * Sodium dihexyl sulfosuccinate (American Cyanamid) ** Tetrasodium N-~1,2-dicar~oxy ethyl)-N-octadecyl sulfosuccinamate (American Cyanamid) ~ 1S~7~3 TABLE III (Continued) X
Surfactant 501E2.50 COPS I 1.25 5 Aerosol MA-80*
Aerosol 18 Aeosol AY-65 Deionized Water68.75 Ammonium Persulfate 10 Ammonium Persulfate 0.25 Deionized Water7.25 Surfactant 50lE
COPS I
Aerosol 22**
15 Aerosol MA-80*
Deionized Water Hexanediol 10.00 Diacrylate Methyl Methacrylate 20 Hydroxypropyl Methacrylate Butyl Acrylate Ethylhexyl Acrylate Hydroxyethyl 2.00 Acrylate Butyl Methacrylate Styrene Ethyl Acrylate 8.00 Acrylic Acid Methyl Acrylate Isobutyl Acrylate Isobutyl Methacrylate Ammonium Persulfate 100 . O O
* Sodium dihexyl sulfosuccinate (American Cyanamid) ** Tetrasodium N-(1,2-dicarboxy ethyl)-N-octadecyl sulfosuccinamate (American Cyanamid) l 15917~
TABLE IV
Butanol 16 ~ 4 415 ~ 32 Cellosolve Acetate16.44 15.32 Emulsion* 16.09 24.00 Tert-Butyl Peroctoate.67 (50% in Mineral Spirits) tert-But~L Perbenzoate .31 n-Dodecyl Mercaptan1.61 2.00 Styrene 12 ~ 87 11~ 00 Butyl Methacrylate10.89 10.11 2-Ethylhexyl acrylate10.248 ~ 45 Hydroxyethyl Acrylate8 ~ 7 2 Acrylic Acid .92 o86 15 Hydroxypropyl lO.lh Methacrylate tert-Butyl Peroctoate4.29 (50% in Mineral Spirits) tert-Butyl Perbenzoate 2.00 20 tert-Butyl Peroctoate0.43 (50% in Mineral Spirits) Butanol 0.39 Cellosolve Acetate 0. 37 tert-Butyl Perbenzoate 0.10 100 ~ 00100 ~ 00 *Microgel Emulsion From Table III I II
Physical Characteristics Non-volatiles 59 ~1 60.2 30 Viscosity H-I Z
Acid Number 20.6 40.4 1 15gl7~
TABLE IV (Continue _ Butanol 16.44 ~ 16.44 Cellosolve Acetate16.44 j 16.44 S Emulsion~ 16.09 ¦ 16.09 Tert-Butyl Peroctoate.67 1 .67 (50~ in Mineral Spirits) tert-Butyl Perbenzoate n-Dodecyl Mercaptan1.61 ¦ 1.61 Styrene 12.87 112.87 Butyl Methacrylate10.89 10.89 2-Ethylhexyl acrylate10.24 10.24 Hydroxyethyl Acrylate 8.72 8.72 Acrylic Acid .92 .92 Hydroxypropyl Methacrylate tert-Butyl Peroctoate4.29 4.29 (50% in Mineral Spirits) tert-Butyl Perbenzoate tert-Butyl Peroctoate0.43 0.43 (50% in Mineral Spirits) Butanol 0.39 0.39 Cellosolve Acetate tert-Butyl Perbenzoate 100.00 100.00 *Microgel Emulsion From Table III III IV
Physical Characteristics Non-volatiles 58.6 58.0 30 Viscosity H-I X
Acid Number 20.8 19.3 1 15917~
TA~LE IV (ContLnued) ~ 22 Butanol :L6.4A 16.44 Cellosolve AcetateL6.44 16.44 Emulsion* :L6.09 16.09 Tert-Butyl Peroctoate.67 .67 (50% in Mineral Spirits) tert-Butyl Perbenzoate n-Dodecyl Mercaptan1.61 1.61 Styrene 12.87 12.87 Butyl Methacrylate10.89 10.89 2-Ethylhexyl acrylate10.2410.24 ~ydroxyethyl Acrylate 8.72 8.72 Acrylic Acid .92 .92 Hydroxypropyl Methacrylate tert-Butyl Peroctoate4.29 4.29 (50% in Mineral Spirits) tert-Butyl Perbenzoate tert-Butyl Peroctoate0.43 0.43 (50% in Mineral Spirits) Butanol 0-39 0.39 Cellosolve Acetate tert-Butyl Perbenzoate 100.00 100.00 *Microgel Emulsion From Table III V VI
PhYsical Characteristics Non-volatiles 56.9 57.0 30 Viscosity I H-I
Acid Number 18.5 - 17.5 ~ 15~17~
TABLE IV (Contlnued) 23__ 24 Butanol 16.44 17.88 Cellosolve Acetate1~.44 17.88 Emulsion* 16.09 8.73 Tert-Butyl Peroctoate.67 .73 (50% in Mineral Spirits) tert-Butyl Perbenzoate n-Dodecyl Mercaptan1.61 1.75 Styrene 12.87 14.Od Butyl Methacrylate10.89 11.84 2-Ethylhexyl acrylate10.2411.14 Hydroxyethyl Acrylate8.729.48 Acrylic Acid .92 1.00 Hydroxypropyl Methacrylate tert-Butyl Peroctoate4.29 4 67 (50~ in Mineral Spirits) tert-Butyl Perbenzoate tert-Butyl Peroctoate0.43 0.47 (50% in Mineral Spirits) Butanol 0.39 0.43 Cellosolve Acetate tert-Butyl Perbenzoate 100.00 100.00 *Microgel Emulsion From Table III VII VIII
Physical Characteristics Non-volatiles 57.3 56.2 30 Viscosity Q J
Acid Number 19.4 17.8 l 15~17~
TABLE IV (Cont.inued) _ ?5 _ 26 Butanol 15.32 16.44 Cellosolve Acetate15.32 16.44 5 Emulsion* 24.00 16.09 Tert-Butyl Peroctoate ¦.67 (50% in Mineral Spirits) tert-Butyl Perbenzoate.31 n-Dodecyl Mercaptan 2.0 1.61 10 Styrene 11.0 12.87 Butyl Methacrylate10.11 10.89 2-Ethylhexyl acrylate8.45 10.24 Hydroxyethyl Acrylate 8.72 Acrylic Acid .86 .92 15 Hydroxypropyl 10.16 Methacrylate tert-Butyl Peroctoate 4.29 (50% in Mineral Spirits) tert-Butyl Perbenzoate 2.00 20 tert-Butyl Peroctoate 0.43 (50% in Mineral Spirits) Butanol 0.39 Cellosolve Acetate0.37 tert-Butyl Perbenzoate 10 100.00 100.00 *Microgel Emulsion From Table III IX X
Physical Characteristics Non-volatiles 60.8 57.7 30 Viscosity V-W J
Acid Number 32.7 19.9 l 159178 EX~MPL$ 27 (A) Microgel Emulsion Preparation .27~% Aerosol MA-80 5 2 .15 0 DP ionized Water s .~50% ~mmonium persulfate
4.475 Deionized Water 8~400~ ~ethyl methacrylate 2~100~ ~ydroxypropyl methacrylate 10.000~ 1,6-~exanediol diacrylate .250~ A~rosol ~A-80 .600% Aerosol 22 21.500% Deionized Water Procadure:
To a fi~e liter, three neck reaction flask equipped with a condenser, thermometer and agit tor, charge the first Aerosol ~A-80 and deionized water. Premi~ the ammonium persulfate and second portion of deionized water and chasge to a small addition funnel. A premix o~ methyl 20 methacrylate, hydroxypropyl methacrylate, 1,6-hexanediol diacrylate, Aerosol ~A~80, Aerosol 22, and the third portion of deionized water is prepared and charged to a second addition ~unnel. This m~nomer pre-emulsion is held under 25 constant agitation to maintain a uniform mixture. The contents of the reaction flask are heat~d to 80~2C at which time 10~ of the ammonium persulfate solutio~ is added. The monomer pre-emulsion and 80% of the ammonium persulfate 30 solution is added simultane~usly and continuously 1;15~ 78 over 2-i/2 hours. The remaining 10~ of the ammonium persulfate solution is added over the next 20 minutes. The emulsion is h~ld 1~2 hour, cooled, and discharged from ~he flask.
~ 1 5 ~
tB) Acrylic ~licrogel Resin Preparation 23. 0~% ~icrogel emulsion (A)
To a fi~e liter, three neck reaction flask equipped with a condenser, thermometer and agit tor, charge the first Aerosol ~A-80 and deionized water. Premi~ the ammonium persulfate and second portion of deionized water and chasge to a small addition funnel. A premix o~ methyl 20 methacrylate, hydroxypropyl methacrylate, 1,6-hexanediol diacrylate, Aerosol ~A~80, Aerosol 22, and the third portion of deionized water is prepared and charged to a second addition ~unnel. This m~nomer pre-emulsion is held under 25 constant agitation to maintain a uniform mixture. The contents of the reaction flask are heat~d to 80~2C at which time 10~ of the ammonium persulfate solutio~ is added. The monomer pre-emulsion and 80% of the ammonium persulfate 30 solution is added simultane~usly and continuously 1;15~ 78 over 2-i/2 hours. The remaining 10~ of the ammonium persulfate solution is added over the next 20 minutes. The emulsion is h~ld 1~2 hour, cooled, and discharged from ~he flask.
~ 1 5 ~
tB) Acrylic ~licrogel Resin Preparation 23. 0~% ~icrogel emulsion (A)
5 . 79% n-Butanol 14.4~ Cellosolve ~cetate ll.71~ n-Butanol .59% t-~utyl peroctoate 1.42% n-Dodecyl mercaptan 3.69% Styrene ~.57% Bu~yl methacrylate 7.69% Methyl methacrylate 8.96% 2-E~hyihe~yl acrylate 7.96% ~ydroxyethyl acry}ate 0.8l% ~crylic acid 3.78% t-Butyl peroc~oate .19% ~-~utyl peroctoate .36% Cellosolve Acetate I~ a separatory funnel, equipped with an agitator, charge the microgel emulsion and the first n-~utanol. Agitate vigorously for five minutes. Allow the mixture to separatP into the organic layer and the water n-butanol layer.
Discard the water layer and char~e the organic layer to the five liter reaction flask.
~his coagulated and concentrated emulsion 2s can be used in place of the raw emulsion. The remaining procedure is the same as that used in l-B.
Paint Preparation anld Testing A silver metal paint was prepared by thoroughly mi~ing 2.25 parts nonleafing aluminum paste, ~03 par~s lecithin and 2.25 parts xylene.
To this mix~ure was added 1.75 parts acetone, 16.46 parts ~ethylated ~elamine-formaldehyde resin, a~d 4.11 pa~t~ isobutanol and the resulting ~ixture was thoroughly mixed.
73~15 parts acrylic microgel resin lo (ad~usted to 55 W.V. with a one to one mixture of n-~utanol and Cellosolve Acetate1 was added and well mixed. The paint wzs then reduced to spray viscosity, 2S seconds in a #4 Ford Cup, with a one to one mixture of xylene and ace~one. The paint was sprayed onto preprimed panels, baked at 265F. for 20 ~inutes, and observed Eor sprayability and alu~inum ccntrol.
A c~ntrol paint was prepared in an analogous manner with the solution acrylic resin described in Example 4, the only difference beins that this resin did no~ contain an emulsion of microgel.
The solids, sprayability, and aluminum orientation of the paints prepzred in ~xamples 1 through 27 are ta~ulated below:
1 1.5~17~
TABLE V
% Solids Sprayability and Example By~ Aluminum Control ~ontrol t.6 . 8 Poor 1 47 ~ 4 Fair 2 45 . 8 Çood 3 43 . 4 Fair 4 45 . O Gos~d 50. 0 Good lo 6 4Q . 2 . Poor 7 49. 2 Fair 8 48 . 6 Goc~d 9 48.9 Z~od 48 . B Very Good 11 47 . 8 ~Jery Good 12 47 . O Excellent 13 49.1 Excellent 14 50 . 5 Very ~od 42. 4 E~ccellent 16 44 . 2 ~ood 17 52. 0 Fair 18 45 . 4 Good 51. 7 Fair 22 50 ~ 5 ~oad 21 49 . 5 Good ~ 50 . 4 ~c~
23 50.1 Good 24 49 . û G~od 45 . 3 Fair 26 46 . 5 Fair 27 4g " 5 Very Good ~ 15g~
Table V illustrates that the aluminum control obtained with the controi paint is very poor in comparison to those paints containing micsogel emulsion. Poor sprayability and aluminum control were also obtained with the paint of Ex~ple E. This paint contained an emul~ion but the emul3ion did no~- contain any crosslinking ~onomer.
It ~ill be appreciated that various lo modif ications may be made in the invention as described a~ve. Accordingly, the scope of the inve~tion iR defined in the following clai~s wherein:
Discard the water layer and char~e the organic layer to the five liter reaction flask.
~his coagulated and concentrated emulsion 2s can be used in place of the raw emulsion. The remaining procedure is the same as that used in l-B.
Paint Preparation anld Testing A silver metal paint was prepared by thoroughly mi~ing 2.25 parts nonleafing aluminum paste, ~03 par~s lecithin and 2.25 parts xylene.
To this mix~ure was added 1.75 parts acetone, 16.46 parts ~ethylated ~elamine-formaldehyde resin, a~d 4.11 pa~t~ isobutanol and the resulting ~ixture was thoroughly mixed.
73~15 parts acrylic microgel resin lo (ad~usted to 55 W.V. with a one to one mixture of n-~utanol and Cellosolve Acetate1 was added and well mixed. The paint wzs then reduced to spray viscosity, 2S seconds in a #4 Ford Cup, with a one to one mixture of xylene and ace~one. The paint was sprayed onto preprimed panels, baked at 265F. for 20 ~inutes, and observed Eor sprayability and alu~inum ccntrol.
A c~ntrol paint was prepared in an analogous manner with the solution acrylic resin described in Example 4, the only difference beins that this resin did no~ contain an emulsion of microgel.
The solids, sprayability, and aluminum orientation of the paints prepzred in ~xamples 1 through 27 are ta~ulated below:
1 1.5~17~
TABLE V
% Solids Sprayability and Example By~ Aluminum Control ~ontrol t.6 . 8 Poor 1 47 ~ 4 Fair 2 45 . 8 Çood 3 43 . 4 Fair 4 45 . O Gos~d 50. 0 Good lo 6 4Q . 2 . Poor 7 49. 2 Fair 8 48 . 6 Goc~d 9 48.9 Z~od 48 . B Very Good 11 47 . 8 ~Jery Good 12 47 . O Excellent 13 49.1 Excellent 14 50 . 5 Very ~od 42. 4 E~ccellent 16 44 . 2 ~ood 17 52. 0 Fair 18 45 . 4 Good 51. 7 Fair 22 50 ~ 5 ~oad 21 49 . 5 Good ~ 50 . 4 ~c~
23 50.1 Good 24 49 . û G~od 45 . 3 Fair 26 46 . 5 Fair 27 4g " 5 Very Good ~ 15g~
Table V illustrates that the aluminum control obtained with the controi paint is very poor in comparison to those paints containing micsogel emulsion. Poor sprayability and aluminum control were also obtained with the paint of Ex~ple E. This paint contained an emul~ion but the emul3ion did no~- contain any crosslinking ~onomer.
It ~ill be appreciated that various lo modif ications may be made in the invention as described a~ve. Accordingly, the scope of the inve~tion iR defined in the following clai~s wherein:
Claims (8)
1. A method of making an acrylic microgel resin com-position for use in paint systems to provide coatings of improved pigment orientation and sag resistance which comprises preparing an aqueous microgel emulsion by the emulsion poly-merization in water of a mixture of ethylenically unsaturated monomers, at least one of said monomers, the amount of which is in the range of 10 to 90 weight percent of said microgel, being an acrylic or methacrylic acid, or an -OH substituted alkyl ester thereof, and containing a -COOH or -OH group, and at least another of said monomers, the amount of which is in the range of 90 to 10 weight percent of said microgel, being selected from an alkyl ester of an acrylic or methacrylic acid, styrene and alpha-methyl styrene, and being free from -COOH and -OH groups, and a multifunctional crosslinking agent containing at least two ethylenically unsaturated double bands present in an amount of 5 - 70 percent by weight of the total weight of said ethylenically unsaturated monomers and cross-linking agent, removing water from the emulsion by coagulation and/or azeotropic distillation with an organic solvent in which the microgel is insoluble and which forms an azeotrope with water, and incorporating the microgel into an acrylic resin prepared by polymerizing two or more ethylenically unsaturated monomers in an organic solvent solution wherein at least one of said monomers is an -OH substituted alkyl ester of an acrylic or methacrylic acid and optionally a monomer containing a -COOH group selected from an acrylic or methacrylic acid, and another of said monomers being selected from an alkyl ester of an acrylic or methacrylic acid, styrene and alpha-methyl styrene, and being free from -COOH and -OH groups to provide said acrylic microgel resin wherein the amount of microgel solids is in the range of 5 to 15 percent by weight of the total resin solids.
2. The acrylic microgel resin composition of claim 1.
3. The method of claim 1 wherein said ethylenically unsaturated monomer containing a -COOH or -OH group used to prepare said aqueous microgel emulsion is selected from acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydro-xypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
4. The method of claim 1 wherein the said -OH substituted alkyl ester of acrylic or methacrylic acid employed to prepare said acrylic resin is selected from hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydro-xypropyl methacrylate.
5. The method of claim 1 wherein the microgel emulsion is added to the components which are used to prepare the acrylic resin in organic solvent and water in the emulsion is azeotropically distilled concurrently with the preparation of the acrylic resin in the organic solvent.
6. The method of claim 1 wherein the emulsion is first dehydrated and then added to pre-formed acrylic resin in organic solvent.
7. The method of claim 1 wherein the emulsion is added to pre-formed acrylic resin in organic solvent and the emulsion is then dehydrated by azeotropic distillation in the presence of the pre-formed acrylic resin.
8. The method of claim 1 wherein the emulsion is de-hydrated to the extent of removing at least 50% by weight of the water, prior to either concurrently preparing the acrylic resin or the addition of the pre-formed acrylic resin and further water removal.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/098,115 US4290932A (en) | 1979-11-27 | 1979-11-27 | Acrylic resin-acrylic microgel compositions |
| US098,115 | 1979-11-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1159178A true CA1159178A (en) | 1983-12-20 |
Family
ID=22267243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000351710A Expired CA1159178A (en) | 1979-11-27 | 1980-05-12 | Blends of acrylic microgel and acrylic resin solutions |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4290932A (en) |
| EP (1) | EP0029637B1 (en) |
| JP (1) | JPS5676447A (en) |
| AU (1) | AU541266B2 (en) |
| BR (1) | BR8007767A (en) |
| CA (1) | CA1159178A (en) |
| DE (1) | DE3072165D1 (en) |
| ES (1) | ES495467A0 (en) |
| MX (1) | MX156299A (en) |
| ZA (1) | ZA806516B (en) |
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| US4413084A (en) * | 1980-10-23 | 1983-11-01 | Ford Motor Company | Paint composition comprising hydroxy functional film former and improved stabilized flow control additive |
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| US4415681A (en) * | 1980-10-23 | 1983-11-15 | Ford Motor Company | Stabilized crosslinked dispersion |
| DE3378722D1 (en) * | 1982-03-18 | 1989-01-26 | Basf Corp | A process for preparing a multilayer coating on a substrate and a coated substrate prepared thereby |
| US4546046A (en) * | 1983-03-10 | 1985-10-08 | Glasurit America, Inc. | Substrates with flexible coatings from epsilon-caprolactone modified acrylics |
| US4720528A (en) * | 1983-03-10 | 1988-01-19 | Basf Corporation-Inmont Division | Substrates with flexible coatings from epsilon-caprolactone modified acrylics |
| US4540740A (en) * | 1983-04-04 | 1985-09-10 | Ppg Industries, Inc. | Cross-linked polymeric microgel prepared from polymerizing epoxy-containing monomer in the presence of an acid |
| US4620993A (en) * | 1984-03-30 | 1986-11-04 | Ppg Industries, Inc. | Color plus clear coating system utilizing organo-modified clay in combination with organic polymer microparticles |
| US4620994A (en) * | 1984-03-30 | 1986-11-04 | Ppg Industries, Inc. | Color plus clear coating system utilizing organo-modified clay |
| US4558075A (en) * | 1984-03-30 | 1985-12-10 | Ppg Industries, Inc. | High-solids coating composition for improved rheology control containing organo-modified clay |
| US4569966A (en) * | 1984-04-19 | 1986-02-11 | Ppg Industries, Inc. | Polymeric microparticles |
| FR2564848B1 (en) * | 1984-05-25 | 1989-04-28 | Nippon Paint Co Ltd | COMPOSITION FOR TOPCOAT CONTAINING MICROGEL PARTICLES. |
| JPS6142580A (en) * | 1984-08-03 | 1986-03-01 | Nippon Paint Co Ltd | Topcoating composition |
| US4719132A (en) * | 1984-09-21 | 1988-01-12 | Ppg Industries, Inc. | Process for the preparation of multi-layered coatings and coated articles derived therefrom |
| JPH0676467B2 (en) * | 1984-12-18 | 1994-09-28 | 日本ペイント株式会社 | Composite resin particles and resin composition for paint |
| US4849480A (en) * | 1985-10-23 | 1989-07-18 | E. I. Du Pont De Nemours And Company | Crosslinked polymer microparticle |
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| CA1281454C (en) * | 1985-12-25 | 1991-03-12 | Teruhiko Sugimori | Method for producing thermoplastic resins |
| US4739004A (en) * | 1986-12-08 | 1988-04-19 | Desoto, Inc. | Cross-linked dispersion copolymers containing vinyl acetate |
| ATE91291T1 (en) * | 1987-06-04 | 1993-07-15 | Ciba Geigy Ag | LIGHT-STABILIZED EPOXY GROUP-CONTAINING POLYMER MICROPARTICLES. |
| US4839403A (en) * | 1987-07-28 | 1989-06-13 | Desoto, Inc. | Cross-linked emulsion copolymers in thermosetting aqueous coatings |
| JP2576586B2 (en) * | 1987-08-12 | 1997-01-29 | 日本油脂株式会社 | Method for producing polymer non-aqueous dispersion, polymer non-aqueous dispersion and coating composition |
| US4822685A (en) * | 1987-12-10 | 1989-04-18 | Ppg Industries, Inc. | Method for preparing multi-layered coated articles and the coated articles prepared by the method |
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| US4977208A (en) * | 1988-05-20 | 1990-12-11 | Mitsui-Cyanamid, Ltd. | Water-absorbent coating compositions |
| US5120796A (en) * | 1988-12-20 | 1992-06-09 | Toyo Ink Manufacturing Co., Ltd. | Process for the production of reactive microgel and resin composition containing the microgel |
| US5229434A (en) * | 1988-12-20 | 1993-07-20 | Toyo Ink Manufacturing Co., Ltd. | Process for the production of reactive microgel and resin composition containing the microgel |
| DE3915622A1 (en) * | 1989-05-12 | 1990-11-15 | Ppg Ind Deutschland Gmbh | Double protective layer against stones, for metal substrates - has protective layer based on urethane¨-acrylate¨ resin, acrylic monomers and hardener, and aq. filler layer applied wet-in-wet |
| US5244696A (en) * | 1990-12-17 | 1993-09-14 | E. I. Du Pont De Nemours And Company | Automotive coating composition comprising an organosilane polymer |
| US5244959A (en) * | 1990-12-17 | 1993-09-14 | E. I. Du Pont De Nemours And Company | Coatings comprising an organosilane solution polymer and a crosslink functional dispersed polymer |
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| US5250605A (en) * | 1990-12-17 | 1993-10-05 | E. I. Du Pont De Nemours And Company | Coating compositions comprising an organosilane polymer and reactive dispersed polymers |
| US5276075A (en) * | 1991-10-30 | 1994-01-04 | Binney & Smith Inc. | Washable acrylic paint |
| US5331025A (en) * | 1992-11-04 | 1994-07-19 | Rohm And Haas Company | Coating compositions incorporating composite polymer particles |
| DE4331805A1 (en) * | 1993-09-18 | 1995-03-23 | Basf Ag | Matt, transparent thermoplastic resins |
| US5494954A (en) * | 1994-04-04 | 1996-02-27 | Ppg Industries, Inc. | Non-aqueous dispersion polymerization and stabilization of polar polymeric microparticles |
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| EP1298174B1 (en) * | 2001-09-28 | 2006-08-02 | J.W. Ostendorf GmbH & Co. KG. | Waterborne coating composition |
| KR100880117B1 (en) * | 2004-11-29 | 2009-01-23 | 도꾸리쯔교세이호징 가가꾸 기쥬쯔 신꼬 기꼬 | Method for preparing composite fine particles |
| JP5035948B2 (en) * | 2006-04-26 | 2012-09-26 | 株式会社 資生堂 | Thickening composition and cosmetic |
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| US8461253B2 (en) * | 2010-01-15 | 2013-06-11 | Ppg Industries Ohio, Inc. | One-component, ambient curable waterborne coating compositions, related methods and coated substrates |
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| US9434828B2 (en) | 2010-12-08 | 2016-09-06 | Ppg Industries Ohio, Inc. | Non-aqueous dispersions comprising a nonlinear acrylic stabilizer |
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| US4075141A (en) * | 1975-10-09 | 1978-02-21 | Ppg Industries, Inc. | Carboxylic acid amide interpolymer-based coating compositions |
| GB1588976A (en) * | 1977-04-25 | 1981-05-07 | Ici Ltd | Coating composition containing metallic pigmentation |
-
1979
- 1979-11-27 US US06/098,115 patent/US4290932A/en not_active Expired - Lifetime
-
1980
- 1980-05-09 EP EP80301530A patent/EP0029637B1/en not_active Expired
- 1980-05-09 DE DE8080301530T patent/DE3072165D1/en not_active Expired
- 1980-05-12 CA CA000351710A patent/CA1159178A/en not_active Expired
- 1980-05-28 AU AU58843/80A patent/AU541266B2/en not_active Ceased
- 1980-09-10 ES ES495467A patent/ES495467A0/en active Granted
- 1980-10-02 MX MX184172A patent/MX156299A/en unknown
- 1980-10-09 JP JP14071180A patent/JPS5676447A/en active Granted
- 1980-10-23 ZA ZA00806516A patent/ZA806516B/en unknown
- 1980-11-27 BR BR8007767A patent/BR8007767A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ES8107274A1 (en) | 1981-10-01 |
| EP0029637A2 (en) | 1981-06-03 |
| ZA806516B (en) | 1981-10-28 |
| US4290932A (en) | 1981-09-22 |
| BR8007767A (en) | 1981-06-09 |
| AU541266B2 (en) | 1985-01-03 |
| AU5884380A (en) | 1981-06-04 |
| JPS5676447A (en) | 1981-06-24 |
| ES495467A0 (en) | 1981-10-01 |
| EP0029637B1 (en) | 1989-08-30 |
| DE3072165D1 (en) | 1989-10-05 |
| MX156299A (en) | 1988-08-09 |
| JPS6213992B2 (en) | 1987-03-30 |
| EP0029637A3 (en) | 1981-12-23 |
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| Date | Code | Title | Description |
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| MKEX | Expiry |