WO1998033831A1 - Emulsion polymers which provide scrub resistance and blocking resistance in high and low pvc paint formulations - Google Patents
Emulsion polymers which provide scrub resistance and blocking resistance in high and low pvc paint formulations Download PDFInfo
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- WO1998033831A1 WO1998033831A1 PCT/US1998/002188 US9802188W WO9833831A1 WO 1998033831 A1 WO1998033831 A1 WO 1998033831A1 US 9802188 W US9802188 W US 9802188W WO 9833831 A1 WO9833831 A1 WO 9833831A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
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- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
Definitions
- This invention relates to emulsion polymers and to paints containing emulsion polymers.
- paints and coatings based on emulsion polymers are well known and generally referred to as "latex" paints or coatings. These paints and coatings are water- based, having a continuous aqueous phase in which minute polymer particles are dispersed.
- the polymer particles are commonly polymers of acrylate, styrenic or ethylenic monomers such as methyl methacrylate, butyl acrylate, 2-ethyl hexyl acrylate, styrene, vinyl acetate, vinyl veova, or ethylene.
- VOCs volatile organic compounds
- the blocking problem can be overcome to some extent by using a high extender level, but this solution is only applicable to paints such as flat interior paints which have a relatively high pigment volume concentration (PVC). Paints having high extender levels are not suitable for satin and semi-gloss applications. Furthermore, at the binder levels used in high PVC paints, scrub resistance and gloss suffer.
- PVC pigment volume concentration
- low PVC paints tend to have good scrub resistance due to their relatively high binder content, but their blocking resistance suffers because the extender level is lower.
- blocking resistance and scrub resistance there is often a trade-off between blocking resistance and scrub resistance, and that it has proven difficult to provide a latex which provides for both good blocking resistance and good scrub resistance in both high and low PVC paints, particularly in low VOC formulations.
- this invention is an aqueous emulsion having an aqueous phase and a dispersed polymer phase, wherein at least 50 percent of the weight of the dispersed polymer phase comprises particles prepared in a multistage polymerization process.
- a "first stage" monomer or mixture thereof is polymerized in a first stage, wherein the first stage monomer or monomer mixture polymerizes to form a polymer having a T g of less than 25°C
- a "second stage" monomer or mixture thereof is polymerized in a second stage, wherein the second stage monomer or monomer mixture polymerizes to form a polymer having a T g of greater than 60°C.
- the monomers polymerized in said first stage constitute from 50 to 95 percent of the total weight of the monomers, and the monomers polymerized in said second stage constitute from 5 to 50 weight percent of the total weight of the monomers.
- Incorporated into either the first stage monomer mixture or the second stage monomer mixture, or both, is 0.1 to 2 percent by weight, based on the total weight of the monomers, of an addition polymerizable ethylenically unsaturated monomer containing at least two carboxyl or carboxylate groups and 0.5 to 3 percent by weight, based on the total weight of the monomers, of an addition polymerizable, ethylenically unsaturated monomer containing a single carboxyl or carboxylate group.
- this invention is an aqueous emulsion having an aqueous phase and a dispersed polymer phase, wherein at least 50 percent of the weight of the dispersed polymer phase comprises particles prepared in a multistage polymerization process.
- a "first stage" monomer or mixture thereof is polymerized in a first stage, wherein the first stage monomer or monomer mixture polymerizes to form a polymer having a T g of less than 25°C
- a "second stage" monomer or mixture thereof is polymerized in a second stage, wherein the second stage monomer or monomer mixture polymerizes to form a polymer having a T g of greater than 60°C.
- the monomers polymerized in said first stage constitute from 50 to 95 percent of the total weight of the monomers, and the monomers polymerized in said second stage constitute from 5 to 50 weight percent of the total weight of the monomers.
- Incorporated into either the first stage monomer mixture or the second stage monomer mixture, or both, is 0.85 to 2 percent by weight, based on the total weight of the monomers, of an addition polymerizable, ethylenically unsaturated monomer containing at least two carboxyl or carboxylate groups.
- the emulsions of this invention can be formulated into paints and coatings which have good scrub resistance even when formulated into low or no VOC formulations and over a wide range of pigment volume concentrations. Typically, paints and coatings formulated with these compositions have a good combination of blocking and scrub resistance. Accordingly, another aspect of this invention is a coating comprising the aqueous emulsion of the first or second aspect of this invention.
- the aqueous emulsion of this invention includes a continuous aqueous phase and a dispersed polymer phase.
- the dispersed polymer phase is in the form of particles of a size such that they can remain stably dispersed in the aqueous phase.
- a suitable size range for the particles is from 80 nm to 300 nm in diameter ("diameter” here referring to the longest dimension of the particle).
- the dispersed particles comprise a polymer which is prepared in a multistaged process.
- monomers are polymerized which form a polymer having a T g of at least 60°C, preferably at least 80°C.
- the dispersed polymer particles contain from 0.1 to 2 weight percent of repeating units formed by ' polymerizing an addition polymerizable ethylenically unsaturated monomer containing at least two carboxyl or carboxylate groups and from 0.5 to 3 weight percent of repeating units formed by polymerizing an addition polymerizable, ethylenically unsaturated monomer containing a single carboxyl or carboxylate group.
- These acid-containing monomers can be polymerized in either the first or second polymerization stage, or both.
- references to T g are those obtained by dynamical mechanical thermal analysis (DMTA) on a polymer made by pouring 15 to 20 gm of the latex into a three-inch diameter tetrafluoroetylene fluorocarbon-coated O-ring which is heated at
- Samples of 1 to 2 mm thickness are evaluated on a Rheometrics RDS-II spectrometer using the 7.9 mm parallel plate geometry. A frequency of 1 rad/sec is used, and the temperature range is from below the expected T g to approximately 150°C. The percent strain is chosen so that the properties are determined in the linear viscoelastic regime.
- the T g of the polymer formed in each stage can be determined by polymerizing the monomer or monomer mixture alone in a single-stage polymerization process and measuring the T g of the resulting polymer in the manner just described.
- the T g of a styrene/2-ethylhexyl acrylate mixture can be determined by polymerizing that mixture in a single-stage polymerization and measuring the T g of the resulting polymer.
- A, B and N represent individual monomers in the mixture containing N monomers
- wA, wB and wN represent the weight fractions of monomers A, B and N, respectively
- T g AN represents the T g of the polymer formed
- T g A, T g B and T g N represent the T g of homopoiymers of monomers A, B and N, respectively.
- Suitable monomers which are useful for polymerization in either or both of the first and second polymerization stages include styrene, -methyl styrene, vinyl toluene, and vinyl naphthalene, t-butyl styrene, o- or p-methyl styrene and o-p-dimethyl styrene, any of which can be inertly-substituted, such as with alkyl, alkoxyl or halogen groups; nitriles such as acrylonitrile and methacrylonitrile; vinyl and vinylidene halides such as vinyl chloride and vinylidene chloride; vinyl acetate; acrylic and methacrylic esters in which the ester group is C C 20 alkyl, preferably C 2 -C 8 alkyl, such as methyl acrylate, ethyl acrylate, n- or i-propyl acrylate, n-, t-,
- an emulsion polymer having desirable properties can be made using those of the foregoing monomers which are commonly available and, in most cases, relatively inexpensive. Those having halogen groups are disfavored because they are sometimes considered to be less environmentally friendly.
- At least one monomer having at least two carboxyl or carboxylate groups is at least one monomer having at least two carboxyl or carboxylate groups.
- This monomer constitutes from 0.1 to 2 percent, preferably from 0.25 to 1 of the total weight of all monomers. However, when no monomer containing a single carboxyl or carboxylate group is also present, then this monomer containing multiple carboxyl or carboxylate groups constitutes at least 0.85, preferably at least 0.9 percent of the total weight of all monomers.
- Suitable such monomers include itaconic acid, maleic acid, fumaric acid, and succinic acid, and the corresponding carboxylates.
- the counter-ion is preferably a monovalent cation, preferably an alkali metal or a fugitive base, as described below.
- One or both of the monomer mixtures advantageously and preferably contains one or more addition polymerizable, ethylenically unsaturated monomers containing a single carboxyl or carboxylate group.
- Acrylic acid and methacrylic acid are examples of these.
- These monomers provide for improved paint stability when small quantities (that is,. 0.5 to 3 weight percent of all monomers) are used in conjunction with the monomer having multiple carboxyl or carboxylate groups. When these monomers are present, a lesser quantity of the monomer containing multiple carboxyl or carboxylate groups can be used.
- either of the monomer mixtures may contain one or more functional monomers such as ethyleneureamethacrylate (Nourycryl® MA-123-50, a product of Akzo Chemie or Plex 6844-0, a product of Rohm & Haas).
- functional monomers such as ethyleneureamethacrylate (Nourycryl® MA-123-50, a product of Akzo Chemie or Plex 6844-0, a product of Rohm & Haas).
- Other monomers of the same type include methacrylamido ethyleneurea, which is sold by Rhone- Poulenc under the trade name Sipomer WAMII.
- Another useful functional monomer is sold under the trade name Sipomer WAM, and contains an alkyl group, an amine functionality, and a ureido ring.
- the monomers used in the first polymerization stage contain a predominant amount (that is, more than 50 weight percent) of an alkyl acrylate having one or more, preferably four or more carbons in the alkyl group, such as methyl acrylate, n-butyl acrylate or hexyl acrylate.
- an alkyl acrylate having one or more, preferably four or more carbons in the alkyl group, such as methyl acrylate, n-butyl acrylate or hexyl acrylate.
- Quantities of a "hard” monomer preferably styrene, methyl acrylate, or acrylonitrile, may be copolymerized with the "soft" monomer in the first polymerization stage, provided that the T g of the resulting copolymer is within the aforementioned ranges.
- the monomer be predominantly (that is, more than 50 weight percent) a vinyl aromatic, preferably styrene; acrylonitrile; methyl methacrylate; or a mixture of two or more thereof.
- a quantity of a "soft" monomer may be employed in the second stage monomer mixture, provided that the T g requirement is met.
- the first stage monomer or mixture of monomers constitutes from 50 to 95, preferably from 60 to 95, more preferably from 60 to 0 percent of the weight of all monomers used in the preparation of the multistage particles.
- the second stage monomer or mixture of monomers constitutes from 5 to 50, preferably 5 to 40, more preferably 20 to 40 percent of the total weight of all monomers.
- the emulsion of this invention is conveniently prepared by polymerizing the monomers just described in a two-stage emulsion polymerization in an aqueous phase. Suitable polymerization methods are well known and are described, for example, in Emulsions: Theory and Practice, by P. Becher Reinhold, New York (1959), High Polymer Latices, by D. C. Blackley, Pamerton Publishing Co., New York (1966); and Emulsion Polymer Technology, by Robert D. Athey, Jr. Marcel Dekker, Inc., New York (1991 ).
- the emulsion polymerization process includes adding the first stage monomers into a continuous aqueous phase under agitation.
- One or more surfactants are typically present in order to help form a stable emulsion having discrete droplets of desirable size.
- a free radical initiator or redox catalyst is usually employed to provide a commercially acceptable rate of polymerization and a high conversion of monomers to polymer.
- the first stage monomers may be added to the aqueous phase all at once in a batchwise operation, or all or a portion may be added continuously or in increments as the polymerization proceeds.
- the second stage monomers are added after the first stage monomers are added and are generally polymerized to at least 70 weight percent conversion, preferably at least 80 weight percent conversion.
- first and second stage polymerization are used herein, those terms are not intended to imply that the stages are conducted in any particular way. What is important is that the monomers(s) being polymerized at the end of the polymerization process give rise to a high T g polymer, while those used earlier in the process give rise to a low T g polymer.
- the monomers may be added continuously to the reaction vessel (under polymerization conditions), with the transition from the first stage to the second being marked by a change in monomer composition (or ratios of monomers). The change in monomer composition or ratios may itself be abrupt or gradual.
- the change in monomer composition may be due to the addition of a monomer stream, such as in the case where the first stage monomer includes n-butyl acrylate, and the second stage monomer includes a styrene/n-butyl acrylate mixture.
- the n-butyl acrylate may be added without interruption throughout the first and second stages, and the beginning of the second stage is marked by the commencement of a styrene stream.
- the change in monomer composition may be due to the discontinuance of a monomer stream, such as in the case where the first stage monomers include a mixture of n-butyl acrylate and styrene and the second stage monomer includes styrene, but not n-butyl acrylate.
- the second stage begins when the n-butyl acrylate stream ends.
- first and second stages are separated is by varying the ratios of the monomers in the streams.
- a styrene/butyl acrylate mixture rich in n-butyl acrylate may be added in the first stage, and the second stage can be begun simply by increasing the amount of styrene in the stream, relative to the amount of n- butyl acrylate.
- the first and second stages can be separated by a complete discontinuation of the first stage monomer followed by the start of an entirely different monomer stream.
- Yet another way to conduct the polymerization in stages is to feed all of the first stage monomers at once, followed by polymerization to a conversion of at least 70 percent, followed by the addition of the second stage monomers, either at once or gradually.
- seed particles at the start of the polymerization.
- their weight is preferably no greater than 2 percent than the weight of the monomer mixture; in such a case, the composition of the seed particles is ignored when calculating the amounts of the various monomer types in the monomer mixture.
- water, surfactant and optional seed particles are initially charged to a suitable reactor and heated to the desired polymerization temperature.
- the desired polymerization temperature depends on the particular catalyst and monomers employed, and typically ranges from 30°C to 100°C, preferably from 50°C to 100°C, more preferably from 60°C to 100°C. Higher temperatures can be used under special conditions, such as the use of superatmospheric pressure.
- the initial charge to the reactor may include all or a portion of the first stage monomer mixture, which may include the monomer having multiple carboxyl or carboxylate groups as well as the monomer containing a single carboxyl or carboxylate group.
- one or more streams is fed to the reactor.
- One of those streams contains the free radical initiator. Any portion of the first stage monomer mixture which is not added to the initial charge may be added in one or more separate streams.
- the monomers may be pre-emulsified, but it is not critical to do so.
- Additional surfactant may also be added, either as a separate stream or mixed with the catalyst or one or more of the monomers.
- the monomers can be added as two or more separate streams.
- the reactor contents are typically heated for a period to polymerize the monomers to a conversion of at least 70 weight percent, preferably at least 80 weight percent.
- the second stage monomer(s) are added. Again, this second stage monomer mixture may contain all or a portion of the monomer having multiple carboxyl or carboxylate groups as well as the monomer containing a single carboxyl or carboxylate group. This may be done all at once, or the second stage monomer mixture may be added continuously or intermittently over a period of time.
- additional surfactant and/or free radical initiator may also be fed into the reaction vessel.
- the reactor contents are typically heated for a period to complete polymerization. Often, this post addition heating is conducted at a higher temperature than the main polymerization, preferably 80°C to 100°C.
- the amount of monomers added and polymerized is selected so that the resulting polymer emulsion has a desired solids content, and the copolymer particles have a desired size.
- the resulting emulsion has a solids content from 10 to 70 percent by weight, more preferably from 40 to 55 percent by weight, and the copolymer particles have a volume average diameter from 80 nm to 300 nm.
- the surfactant may be of the nonionic, anionic or amphoteric type.
- exemplary surfactants include alkali metal alkyl carboxylates, polyoxyethylene alkyl phenols, linear alkyl sulfonates, alkyl aryl sulfonates, alkylated sulfosuccinates, C 6 -C 20 amine oxides, or N,N- bis(carboxyl alkyl) C 6 -C 20 alkyl amines.
- the surfactant is advantageously used in an amount from 0.1 to 2 percent, preferably from 0.1 to 0.5 percent, based on the total weight of the monomers.
- Suitable free radical initiators include peroxy compounds such as peroxydisulfates (commonly known as persulfates), perphosphates, t-butyl hydroperoxide, 2,2-azobis-isobutyronitrile, cumene hydroperoxide and hydrogen peroxide. Ammonium persulfate, sodium persulfate and potassium persulfate are preferred initiators. Redox catalysts, which are activated in the water phase through a water-soluble reducing agent can also be used. For example, the free radical initiators just mentioned can be used combined with sodium formaldehyde sulfoxylate, sodium bisulfite, ascorbic acid or ferric nitrate.
- a hydrogen peroxide/ferric nitrate mixture has been found to provide the polymer with excellent scrub resistance in some instances.
- the free radical initiator is advantageously used in an amount from 0.01 to 5 percent, preferably 0.1 to 2 percent, based on the weight of the monomers. If desired, an additional amount of catalyst in excess of the foregoing amounts may be added after the addition of the monomer streams in order to finish off the polymerization.
- a fugitive base for example, ammonia, dimethylamine, diethyl amine, aminopropanol, ammonium hydroxide or 2-amino-2-methyl-1 -propanol.
- an alkali such as sodium hydroxide, potassium hydroxide or sodium or potassium carbonate.
- This base may be added towards the end of the addition of the monomer stream(s), after all the monomer addition has been completed, or after the polymerization reaction is finished.
- the carbonates may be present throughout the polymerization.
- ingredients can also be used during the polymerization process as desired, such as chain transfer agents, buffers, or preservatives. Post-additions of these ingredients, or others which may be added for a specific purpose, can also be made.
- the resulting emulsion may be steam stripped or otherwise treated to remove impurities and unreacted monomers.
- paints and coatings formulated from the emulsion of this invention may tend to crack slightly, particularly when applied at low temperatures on porous surfaces.
- This problem is easily overcome by blending it with a small quantity of a second emulsion polymer in which the polymer particles have a T g of below 15°C, preferably below 10°C.
- the second emulsion can be prepared in a simple, single-stage polymerization, but may also be prepared in a multistage polymerization if the monomers used in each stage polymerize to form a polymer having a T g as just described.
- the monomers used in the second emulsion may be the same ones mentioned above with respect to the emulsion of this invention, provided that they are selected together as is known in the art to form a polymer having the requisite T .
- Polymers containing a predominant amount of alkyl acrylates are preferred.
- Particular polymers include copolymers of styrene and n-hexyl acrylate; styrene and n-butyl acrylate; styrene and 2-ethylhexyl acrylate. These copolymers may be modified with small amounts of a monomer having a carboxyl or carboxylate group, or a monomer having a sulfonate group.
- the emulsion of this invention and the second emulsion are advantageously mixed in proportions by weight of from 85:15 to 98:2 on a solids basis, preferably from 90:10 to 97:3.
- the emulsion of this invention can be formulated into a variety of paints and coatings.
- the formulation will generally contain a filler, opacifying agent or pigment, such as calcium carbonate, talc, silica, aluminum hydroxide, glass powder, titanium dioxide, red lead, zinc chromate, zinc phosphate, calcium molybdate, barium borate, red oxide, carbon black, Hansa Yellow, Benzidine Yellow, Phthalocyanine Blue, or Quinacridone Red.
- a filler such as calcium carbonate, talc, silica, aluminum hydroxide, glass powder, titanium dioxide, red lead, zinc chromate, zinc phosphate, calcium molybdate, barium borate, red oxide, carbon black, Hansa Yellow, Benzidine Yellow, Phthalocyanine Blue, or Quinacridone Red.
- PVC pigment volume concentrations
- the formulation may contain inorganic dispersants such as sodium hexametaphosphate or sodium tripolyphosphate, organic dispersants such as the polycarboxylic acid polymers (for example, NopcoperseTM 44c, from Summopco Co., Ltd.
- inorganic dispersants such as sodium hexametaphosphate or sodium tripolyphosphate
- organic dispersants such as the polycarboxylic acid polymers (for example, NopcoperseTM 44c, from Summopco Co., Ltd.
- Blocking resistance can be measured in different ways under different conditions.
- One measure of blocking resistance is the so-called Byk blocking resistance test, using a Byk blocking tester. In this test, 150 ⁇ m (wet thickness) films are drawn down on opacity charts or Leneta foil and dried at room temperature for 24 hours. 25 by 75 mm strips of film are cut and glued to the blocking tester's object carrier using joining tape. Two mounted films are placed in contact at an angle of 90 degrees to give an area of contact of 625 mm 2 . A 5 kg weight is applied for a predetermined period of time, and removed. The blocked specimens are then stored 15 minutes without load before operating the blocking tester to evaluate the deblocking force. Paints formulated according to this invention often exhibit a separation force of less than 1.75 N/cm 2 after being pressed together at ambient temperature and humidity for 4 days.
- Scrub resistance is conveniently measured according to ASTM 2486 or DIN 53778, after 7 or 28 days aging time. Resistances according to this test commonly exceed 640 strokes, preferably 700 strokes, more preferably 1000 strokes, with a weight loss of no greater than 0.506, preferably no greater than 0.45 grams. Scrubbing resistance is determined as the average of two samples, whose individual values do not vary by more than 25 percent. Weight loss is determined according to DIN 53778.
- the paint formulation may contain organic cosolvents and coalescents, it is preferred that these be minimized and most preferred that they be eliminated.
- the preferred paint formulation will contain less than 8 percent by weight, more preferably less than 3 percent by weight, and most preferably essentially none of an organic cosolvent and less than 8 percent by weight, more preferably less than 3 percent by weight and most preferably essentially none of a coalescent.
- An emulsion polymer (Latex Example 1 ) was prepared as follows:
- a fourth stream of 29.45 parts styrene and 1 part of acrylic acid was added over a period of 100 minutes, an aqueous stream containing 0.2 part sodium persulfate was added over the course of an hour and an aqueous stream containing 0.1 part ascorbic acid was added over a period of 20 minutes.
- the temperature of the reactor contents was thereafter increased to 90°C for 10 minutes.
- the latex was neutralized with potassium hydroxide.
- the product (Latex Example 1 ) had a particle size of approximately 140 nm and contained 48 percent solids.
- the T g of the resulting polymer is evaluated by DMTA using the method described before.
- the T g of the polymer prepared in the first stage (which includes the itaconic acid provided in the initial charge) is 15° to 25°C; that of the second stage polymer was 90°C.
- the latex was then blended in a 90:10 weight ratio (solids basis) with a second latex containing styrene/n-butyl acrylate copolymer particles which were prepared in a single-stage polymerization.
- the blended latex was designated Blended Latex Example 1.
- Latex Example 2 and Blended Latex Example 2 were prepared in the same manner, except the itaconic acid was increased to 1 part, and the acrylic acid was eliminated.
- the T g values of Latex Example 2 are similar to those of Latex Example 1.
- Latex Example 3 and Blended Latex Example 3 was prepared in the same manner as Latex Example 1 and Blended Latex Example 1 , except that only 0.5 part itaconic acid was used, 0.5 part of fumaric acid wasadded in the initial charge to the reactor, and the acrylic acid was eliminated.
- the T g values of Latex Example 3 are similar to those of Latex Example 1.
- Latex Example 4 and Blended Latex Example 4 is prepared in the same manner as Latex Example 1 and Blended Latex Example 1 , except the acrylic acid is reduced to 0.5 part.
- the T g values of Latex Example 4 are similar to those of Latex Example 1.
- Blended Latex Examples 1 to 4 were formulated into paints using a formulation as described in Table I.
- the paints were designated as Paint Samples 1 to 4, respectively. All have a PVC of 39 percent.
- Each paint was evaluated for minimum milm mormation temperature (MFFT) by casting a 150 ⁇ m film of the emulsion on a heating plate that had a temperature gradient. The film was dried and the minimum temperature at which a coherent film was formed was recorded as the MFFT. The Brookfield viscosity of the paints was measured after formulating and again after 28 days. Gloss was measured at 60° and 85° using a Byk color glossmeter on a 150 ⁇ m (wet thickness) film that was dried for one day at ambient conditions. The one-day room temperature blocking of this paint formulation was evaluated by drawing duplicate 150 ⁇ m (wet thickness) films on Leneta foil and drying the films for 1 day at room temperature.
- MFFT minimum milm mormation temperature
- the films were then placed face-to-face and either a 0.1 metric ton/square meter pressure or a 0.5 metric ton/square meter pressure was applied for 24 hours at room temperature.
- the films were then separated, with the force required to separate them being rated on a scale of 0 to 5, with 5 indicating no blocking (the films fall apart without added force) and 0 indicating that the films cannot be pulled apart without destroying them.
- the percentage of damage to the film was also observed and reported. Scrub resistance was evaluated according to ASTM 2486 after 7 days and again after 28 days; here, higher values indicated superior performance. This test was performed twice for each dried coating, and both results are reported. Weight loss upon scrubbing was measured according to DIN 53778, after 10,000 cycles.
- Latex Examples 1 to 4 were blended with a styrene/2-ethylhexyl acrylate copolymer latex which was modified with methacrylic acid and sodium styrene sulfonate.
- Latex Examples 1 to 4 can be formulated into a similar paint composition without being blended with a second latex. Such paint compositions will have excellent blocking and scrub resistance, but may be slightly more prone to cracking when applied to porous substrates at low temperature.
- a suitable reactor To a suitable reactor is added an initial charge of 68.066 parts water, 0.806 part of a polystyrene latex, 0.75 part of itaconic acid and 0.01 part of a 40 percent solution of VERSENOL * 120 brand chelating agent in water.
- the reactor contents were heated to 80°C.
- the third stream contained 48.25 parts butyl acrylate and 20 parts styrene, and is added over 200 minutes. The temperature of the reactor contents was maintained at 80°C throughout the addition of these streams.
- a fourth stream of 29 parts styrene and 0.5 part acrylic acid is added over a period of 100 minutes.
- the T g of the resulting polymer was evaluated by DMTA using the method described before.
- the T g of the polymer prepared in the first stage (which includes the itaconic acid provided in the initial charge) was -2°C; that of the second stage polymer was 85°C.
- a fourth stream of 28.5 parts styrene and 1 part acrylic acid was added over a period of 100 minutes.
- An aqueous stream containing 0.2 part sodium persulfate was added over the course of an hour.
- An aqueous stream containing 3 parts water and 0.1 part ascorbic acid was added over a period of 20 minutes.
- the temperature of the reactor contents was then increased to 90°C for 10 minutes.
- the latex was neutralized with potassium hydroxide.
- the product had a particle size of approximately 140 nm and contained 50 percent solids.
- the T g of the resulting polymer was evaluated by DMTA using the method described before.
- the T g of the polymer prepared in the first stage (which includes the itaconic acid provided in the initial charge) was -1 °C; that of the second stage polymer is 65°C.
- the latex was then blended in a 90:10 weight ratio (solids basis) with a second latex containing styrene/n-butyl acrylate copolymer particles which were prepared in a single-stage polymerization.
- the resulting blended latex was then formulated into an 80 percent PVC coating having the following ingredients:
- Blended Latex (50% solids) 100.0 Acrylsol TT-935 9 (30%) 2.0
- Titanium dioxide from SCM Chemicals
- the initial viscosity as measured on a Kreb Stormer viscometer at 25°C, was below 140 Krebs units.
- the MFFT is less than 0°C.
- the scrub resistance as measured by DIN 53778 after 7 days drying, was 1300 strokes on each of two evaluations, with weight losses in the two evaluations being 2.428 g and 2.22 g, respectively.
- the resistance of the paint to cracking is evaluated by applying a 600 ⁇ m thick film of the coating on the non-printed side of plasterboard at 5°C, and drying. Only minimal cracking is seen.
- a commercially available latex is also evaluated for scrub resistance in the same coating formulation.
- the scrub resistance is 700 and 1 100 strokes when tested twice, with weight losses of 1.93 g and 2.436 g, respectively. These stroke values are far lower than those of the coating of this invention, indicating a much poorer scrub resistance.
- the commercially available latex performs similarly to that of the coating made from the blended latex of this example. Opacity, yellowness and whiteness are also similar for both coatings.
- a fourth stream of 29 parts styrene and 1 part acrylic acid was added over a period of 100 minutes.
- the temperature of the reactor contents was then increased to 90°C for 10 minutes.
- the latex was neutralized with potassium hydroxide.
- the product had a particle size of approximately 140 nm and contained 50.5 percent solids.
- the T g of the resulting polymer was evaluated by DMTA using the method described before.
- the T g of the polymer prepared in the first stage (which includes the itaconic acid provided in the initial charge) was 3°C; that of the second stage polymer was 95°C.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU62682/98A AU6268298A (en) | 1997-02-04 | 1998-02-04 | Emulsion polymers which provide scrub resistance and blocking resistance in high and low PVC paint formulations |
CA002279495A CA2279495A1 (en) | 1997-02-04 | 1998-02-04 | Emulsion polymers which provide scrub resistance and blocking resistance in high and low pvc paint formulations |
BR9807302-8A BR9807302A (en) | 1997-02-04 | 1998-02-04 | Emulsion polymers that provide cleaning resistance and blocking resistance in upper and lower pvc paint formulations |
EP98904929A EP0963387A1 (en) | 1997-02-04 | 1998-02-04 | Emulsion polymers which provide scrub resistance and blocking resistance in high and low pvc paint formulations |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9702241.2 | 1997-02-04 | ||
GBGB9702241.2A GB9702241D0 (en) | 1997-02-04 | 1997-02-04 | Emulsion polymers which provide scrub resistance and blocking resistance in high and low pvc paint formulations |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998033831A1 true WO1998033831A1 (en) | 1998-08-06 |
Family
ID=10807054
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1998/002188 WO1998033831A1 (en) | 1997-02-04 | 1998-02-04 | Emulsion polymers which provide scrub resistance and blocking resistance in high and low pvc paint formulations |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0963387A1 (en) |
KR (1) | KR20000070782A (en) |
AR (1) | AR011630A1 (en) |
AU (1) | AU6268298A (en) |
BR (1) | BR9807302A (en) |
CA (1) | CA2279495A1 (en) |
GB (1) | GB9702241D0 (en) |
WO (1) | WO1998033831A1 (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SG79293A1 (en) * | 1998-12-08 | 2001-03-20 | Rohm & Haas | Dirt pickup resistant coating binder and coatings |
WO2001064765A1 (en) * | 2000-03-03 | 2001-09-07 | Basf Coatings Ag | Aqueous (meth)acrylate copolymer dispersions, method for producing the same, and the use thereof |
EP1193273A1 (en) * | 2000-09-25 | 2002-04-03 | Rohm And Haas Company | Aqueous acrylic emulsion polymer composition |
EP1199332A2 (en) * | 2000-10-18 | 2002-04-24 | Röhm GmbH & Co. KG | Aqueous Monomer-Polymer System |
US6673854B2 (en) | 2001-10-05 | 2004-01-06 | National Starch And Chemical Investment Holding Corporation | Vinyl acetate/ethylene emulsion stabilized with a phosphate surfactant |
US6794436B2 (en) | 2001-05-31 | 2004-09-21 | Basf Aktiengesellschaft | Solvent-free pigmented formulation |
US7241834B2 (en) | 2000-09-25 | 2007-07-10 | Rohm And Haas Company | Aqueous acrylic emulsion polymer composition |
US7964057B2 (en) | 2006-01-10 | 2011-06-21 | Rohm And Haas Company | Cold seal adhesive |
CN108368188A (en) * | 2015-12-21 | 2018-08-03 | 陶氏环球技术有限责任公司 | Multistage aqueous emulsion polymer and the water-based paint compositions formed by it |
WO2022051168A1 (en) * | 2020-09-03 | 2022-03-10 | Arkema Inc. | Coating composition with improved block and humidity resistance, direct to metal adherence and low voc content |
Citations (8)
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US4351875A (en) * | 1978-09-25 | 1982-09-28 | Rohm And Haas Company | Heteropolymer acrylic latices and textiles treated therewith |
US4916171A (en) * | 1984-07-25 | 1990-04-10 | Rohm And Haas Company | Polymers comprising alkali-insoluble core/alkali-soluble shell and copositions thereof |
US4939212A (en) * | 1989-03-31 | 1990-07-03 | The B. F. Goodrich Company | Elasticized vinyl dispersion resins having outstanding stability |
EP0450511A2 (en) * | 1990-04-06 | 1991-10-09 | BASF Aktiengesellschaft | Particulate graft polymers and thermoplastic moulding compositions with improved toughness prepared therefrom |
EP0532234A1 (en) * | 1991-09-09 | 1993-03-17 | Rohm And Haas Company | Poly (vinyl chloride) blends and additives therefor |
US5280075A (en) * | 1989-10-23 | 1994-01-18 | Takeda Chemical Industries, Ltd. | Core-shell polymer and its use |
EP0583926A2 (en) * | 1992-08-18 | 1994-02-23 | Rohm And Haas Company | Acrylic thermoplastic elastomer |
US5308890A (en) * | 1993-02-26 | 1994-05-03 | Rohm And Haas Company | Emulsion polymer blend of a multi-stage latex and a non-film forming latex |
-
1997
- 1997-02-04 GB GBGB9702241.2A patent/GB9702241D0/en active Pending
-
1998
- 1998-02-04 BR BR9807302-8A patent/BR9807302A/en unknown
- 1998-02-04 WO PCT/US1998/002188 patent/WO1998033831A1/en not_active Application Discontinuation
- 1998-02-04 AU AU62682/98A patent/AU6268298A/en not_active Abandoned
- 1998-02-04 AR ARP980100489A patent/AR011630A1/en not_active Application Discontinuation
- 1998-02-04 CA CA002279495A patent/CA2279495A1/en not_active Abandoned
- 1998-02-04 KR KR1019997007043A patent/KR20000070782A/en not_active Application Discontinuation
- 1998-02-04 EP EP98904929A patent/EP0963387A1/en not_active Withdrawn
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4351875A (en) * | 1978-09-25 | 1982-09-28 | Rohm And Haas Company | Heteropolymer acrylic latices and textiles treated therewith |
US4916171A (en) * | 1984-07-25 | 1990-04-10 | Rohm And Haas Company | Polymers comprising alkali-insoluble core/alkali-soluble shell and copositions thereof |
US4939212A (en) * | 1989-03-31 | 1990-07-03 | The B. F. Goodrich Company | Elasticized vinyl dispersion resins having outstanding stability |
US5280075A (en) * | 1989-10-23 | 1994-01-18 | Takeda Chemical Industries, Ltd. | Core-shell polymer and its use |
EP0450511A2 (en) * | 1990-04-06 | 1991-10-09 | BASF Aktiengesellschaft | Particulate graft polymers and thermoplastic moulding compositions with improved toughness prepared therefrom |
EP0532234A1 (en) * | 1991-09-09 | 1993-03-17 | Rohm And Haas Company | Poly (vinyl chloride) blends and additives therefor |
EP0583926A2 (en) * | 1992-08-18 | 1994-02-23 | Rohm And Haas Company | Acrylic thermoplastic elastomer |
US5308890A (en) * | 1993-02-26 | 1994-05-03 | Rohm And Haas Company | Emulsion polymer blend of a multi-stage latex and a non-film forming latex |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SG79293A1 (en) * | 1998-12-08 | 2001-03-20 | Rohm & Haas | Dirt pickup resistant coating binder and coatings |
US6953822B2 (en) | 2000-03-03 | 2005-10-11 | Basf Coatings Ag | Aqueous (meth)acrylate copolymer dispersions, method for producing the same, and the use thereof |
WO2001064765A1 (en) * | 2000-03-03 | 2001-09-07 | Basf Coatings Ag | Aqueous (meth)acrylate copolymer dispersions, method for producing the same, and the use thereof |
EP1193273A1 (en) * | 2000-09-25 | 2002-04-03 | Rohm And Haas Company | Aqueous acrylic emulsion polymer composition |
US7241834B2 (en) | 2000-09-25 | 2007-07-10 | Rohm And Haas Company | Aqueous acrylic emulsion polymer composition |
EP1199332A3 (en) * | 2000-10-18 | 2002-07-10 | Röhm GmbH & Co. KG | Aqueous Monomer-Polymer System |
US6620876B2 (en) | 2000-10-18 | 2003-09-16 | Roehm Gmbh & Co., Kg | Aqueous monomer/polymer composition |
EP1199332A2 (en) * | 2000-10-18 | 2002-04-24 | Röhm GmbH & Co. KG | Aqueous Monomer-Polymer System |
US6794436B2 (en) | 2001-05-31 | 2004-09-21 | Basf Aktiengesellschaft | Solvent-free pigmented formulation |
US6673854B2 (en) | 2001-10-05 | 2004-01-06 | National Starch And Chemical Investment Holding Corporation | Vinyl acetate/ethylene emulsion stabilized with a phosphate surfactant |
US7964057B2 (en) | 2006-01-10 | 2011-06-21 | Rohm And Haas Company | Cold seal adhesive |
CN108368188A (en) * | 2015-12-21 | 2018-08-03 | 陶氏环球技术有限责任公司 | Multistage aqueous emulsion polymer and the water-based paint compositions formed by it |
KR20180093976A (en) * | 2015-12-21 | 2018-08-22 | 다우 글로벌 테크놀로지스 엘엘씨 | A multistage aqueous emulsion polymer and an aqueous coating composition formed therefrom |
EP3394115A4 (en) * | 2015-12-21 | 2019-08-28 | Dow Global Technologies, LLC | Multistage aqueous emulsion polymer and aqueous coating composition formed therefrom |
CN108368188B (en) * | 2015-12-21 | 2021-04-06 | 陶氏环球技术有限责任公司 | Multistage aqueous emulsion polymer and aqueous coating composition formed therefrom |
US11136428B2 (en) | 2015-12-21 | 2021-10-05 | Dow Global Technologies Llc | Multistage aqueous emulsion polymer and aqueous coating composition formed therefrom |
KR102398077B1 (en) | 2015-12-21 | 2022-05-12 | 다우 글로벌 테크놀로지스 엘엘씨 | Multi-stage aqueous emulsion polymer and aqueous coating composition formed therefrom |
WO2022051168A1 (en) * | 2020-09-03 | 2022-03-10 | Arkema Inc. | Coating composition with improved block and humidity resistance, direct to metal adherence and low voc content |
Also Published As
Publication number | Publication date |
---|---|
AU6268298A (en) | 1998-08-25 |
AR011630A1 (en) | 2000-08-30 |
KR20000070782A (en) | 2000-11-25 |
GB9702241D0 (en) | 1997-03-26 |
CA2279495A1 (en) | 1998-08-06 |
EP0963387A1 (en) | 1999-12-15 |
BR9807302A (en) | 2000-04-18 |
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