FI63592C - PIGMENT INNATURE OF LATEX DISPERSION-MAOLFAERGKOMPOSITION - Google Patents

Description

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Patents and Registered Publications of United States of America Publication 31.03.83 (32) (33) (31) Pyr * «tty · * υ © ΙΙ (· υ * —e * jtrd prlorlut (71) SCM Corporation, 299 Park Avenue, New York, New York, USA (US) (72) Alexander Ramig, Jr., Brunswick, Ohio, USA (US) (7U) Oy Kolster Ab (5U) Pigment-containing aqueous latex dispersion-paint combination -Pigment innehällande vattenhaltig latexdispersion-milfärgkomposition

The invention relates to an aqueous latex dispersion paint combination which is combined with a cured paint film having a solids content of 30 to 70% by weight and which, based on the volume of dry matter, contains: 25 to 70% of a film-forming latex binder of polymer particles by weight the major part is in the range of 0.1 to 1.0 μιη and has a glass transition temperature of at least about 5 ° C below the coalescence temperature, the latex binder being a polymer or copolymer of ethylenically unsaturated monomers? 10 to 60% of solid, non-porous, non-film-forming polymer particles having a weight average diameter of about 0.1 to 1 .mu.m and having a glass transition temperature at least 30 ° C higher than the glass transition temperature of the binder, these non-film-forming polymeric particles being unsaturated monomers; \ 2 63592.

5 to 25% of an opaque pigment having a refractive index of at least 1.8; 0 to 60% opaque pigment.

The invention relates to opaque, opaque latex paints.

Conventional latex paints are prepared by sufficiently dispersing a dimming pigment, such as titanium dioxide, in the transparent polymeric binders forming the film. These conventional latex paints give a matte paint film. Recently, opaque or decorative paint films have been introduced based on the presence of air cavities in the paint films provided by cellular or porous particles (see, e.g., GB Patent 1,178,162, CA Patent 856,863, and GB Patent 1,192,212). Opacity has also been achieved by sealing air from the cavity formed in the film to the paint film, and these coatings are commonly referred to as "bubble coatings." opaque paint films are conventional latex paints mixed with titanium dioxide and Pigment fillers such as calcium carbonate.

U.S. Patent Nos. 4,124,548 and 3,839,253 disclose latex paints which, in addition to pigments and conventional additives, contain plastic particles which, however, are much larger than the polymer particles used in the paint compositions of this invention.

DE-A-2 412 066 discloses a latex coating which also contains plastic particles. With these known paint compositions, the bulk content (PVC) of the pigment is less than or equal to the critical PVC, while in the paint combinations according to the invention the PVC is higher than the critical PVC.

GB patent 1,229,503 also discloses a latex coating which contains e.g. plastic particles. However, this coating is intended for coating paper and is intended to cause the ink to be absorbed onto the surface, while the paint surface obtained with the paint according to the invention tends to prevent dirt and ink from adhering to it.

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A common parameter for describing atex paints is the volume content of the pigment (PVC), which is the percentage of the volume of pigment present in the dried paint film relative to the total volume of the dried paint film. At a given PVC value, the volume of pigments in the paint film suddenly causes quite a bit of air cavities in the dry paint film due to the lack of binder. The PVC value obtained at this level of pigment content is called the critical PVC value, in which there is a deficiency of binder so that there is insufficient binder present in the paint film to encapsulate the pigment particles and fill any remaining cavities in the film. In the case of such a porosity impulse, the physical strength properties of the dried paint film suddenly deteriorate at higher PVC values due to the absence of the binder of the paint film, whereby the physical properties of conventional paint films deteriorate substantially or by leaps and bounds due to increased pigment loading. In conventional known latex paints, the opacity and porosity have approximately the same sensitivity to the impact of air voids in the paint film, where opacity usually increases with film porosity, but most of the With a PVC value that has become known as a critical PVC value from prior art paints. The glazing resistance of conventional prior art paints deteriorates sharply as the opacity or opacity properties of the paint film increase, with the result that the critical PVC of conventional latex paints is a narrow PVC area (Figure 1) where critical PVC is usually ^ level) and the best physical properties of the paint film.

It has now been found that latex paints containing a non-solid film plastic pigment and opaque pigments give hard, dried paint films with substantially increased opacity as well as substantially improved physical properties. Improved opacity is obtained over a wide area of PVC before excessive porosity develops in the paint film, thereby causing the earth, * ^ 4 63592

The advantageous usable PVC range combines both maximum opacity and maximum glazing resistance as well as other optimized physical properties. The novel latex paints of this invention having PVC above critical PVC provide good opaque paint films with the desired paint film integrity properties.

The aqueous latex dispersion-paint combination according to the invention is characterized in that the pigment volume content (PVC) of the latex paint is 30-75%, whereby the PVC is higher than the critical PVC measured on the basis of opacity.

Figure 1 is a scale graph showing the physical properties of paint films provided by a typical known latex paint as a function of pigment volume content (PVC).

Figure 2 is a scale graph showing the physical properties of the paint films provided by the paint of the present invention as a function of pigment volume content (PVC).

Figure 3 is a graphical representation of a scale comparing the opacity of different paint films as a function of paint film porosity.

Figure 4 is a graphical representation similar to that of Figure 2, showing opacity as a function of PVC with different amounts of TiCl 2.

Figure 5 is a graphical representation similar to that of Figure 2 showing the retention of the integrity properties of the paint film provided by the latex paint of the present invention at high PVC values above the critical surface porosity (CSP) PVC.

Figure 6 shows gloss (60 °) and gloss (85 °) as a function of PVC compared to the paint films of the present invention compared to known paint films.

Fig. 7 is a scale graph showing opacity as a function of TiCl 2 content at a constant PVC value relative to known paints.

The different PVC values shown in the figure have been obtained by changing the relative volume of the binder, either by increasing or decreasing the given pigment component, but at the same time keeping the volume% of the other pigment components unchanged. The paint films shown in the figures are shown in more detail in the examples.

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Figure 1 shows a typical prior art paint film as a function of PVC containing 23% v / v titanium dioxide and varying amounts of calcium carbonate pigment as a filler pigment to give varying values for pigment volume (PVC). Opacity and glazing resistance are presented as a function of PVC. The critical PVC is found to be on the PVC axis of the narrow region, with just enough binder present in the paint film to encapsulate each pigment particle and fill the cavities between the pigments. Critical PVC is defined in Figure 1 by the refraction of the opacity curve and the refraction of the glazing resistance curve as the point where the refractions in both curves are in substantially the same PVC. As can be seen from Figure 1, the glazing resistance decreases sharply as the opacity increases, so that the glazing resistance and the opacity cannot be at the same time. The opacity and glazing resistance are both sensitive to the settling of air cavities in the dry paint film, this is also evident near the critical PVC and the PVC values above it. Many other conventional physical properties of paint films, such as abrasion resistance, tensile strength, and the like, decrease quite drastically when critical PVC is achieved.

Figure 2 shows graphically the glazing resistance and opacity of a paint film obtained with a latex paint according to the invention as a function of the bulk content (PVC) of the non-film-forming components or pigment. The paint films contain a binder, 23% by volume of opaque TiO 2, and varying amounts of non-film-forming solid plastic particles to obtain different PVC values. Critical PVC, measured on the basis of opacity, then critical PVC (opacity), appears as the refraction of the opacity curve and is determined graphically; the graphical specification is described in more detail by A. Ramig in Journal of Paint Technology, Vol. 47, (March 1975), pages 60-66, or in the Official Digest of the Federation of Societies for Paint Technology, (March 1965), from page 272 onwards. It is clear from Figure 2 that paints containing non-film-forming plastic particles and a given amount of opaque TiO2 surprisingly give paint films with maximum glazing resistance even at 6,63592 PVC values, which are much higher than conventional critical PVC. a value that substantially increases opacity. Thus, the main advantage of the present invention over the prior art is that squamous paint films with substantially higher impermeability are now obtained before excessive porosity develops in the paint film and in addition the good integrity properties of the film are maintained at high PVC values above critical surface porosity PVC. . The latex paints of this invention provide these substantially better paint films over a wide PVC range of 30-75% PVC. The lowest PVC level (30%) in the wide (30-75%) PVC range represents the lowest critical PVC for translucency, while the highest PVC level (75%) represents the maximum allowable PVC to maintain the integrity properties of the paint film. Preferred paints of the present invention provide paint films that substantially do not exhibit surface porosity and the PVC of such preferred paints is greater than critical PVC (translucency) but less than critical surface porosity PVC as measured by glazing resistance. The critical surface porosity-PVC, measured on the basis of glazing resistance, hereinafter critical surface PVC (glazing resistance), is at the inflection point of the PVC glazing resistance curve where the glazing resistance properties suddenly deteriorate and such a bending point in the The usable PVC range depends on the composition of the paint. The desired difference in PVC between critical PVC (opacity) and critical surface porosity PVC (glazing resistance) for preferred paints is at least about 5 PVC units. The preferred PVC range for low cost paints is between about 48% and 64% PVC. At least about 5% opaque pigment, such as TiCl 2, is required to achieve the minimum acceptable opacity for ordinary paint films up to about 0.2032 mm thick.

Figure 3 compares a plastic film provided by a known paint with the paint films of the present invention by showing the opacity as a function of the surface porosity of the paint films. Surface porosity was measured as Hg penetration porosity using an American Instrument Co <n Aminco Model 5-71213. The surface porosity is directly proportional to PVC, but primarily describes the increase in the surface porosity of the paint film when the critical surface porosity is reached and exceeded. Figure 3, as well as Figure 2, shows that the paint films of the present invention can achieve substantially better opacity prior to the appearance of excessive porosity in the paint film with JiVC values greater than the critical PVC of the paint film, thereby maintaining glazing resistance and other film integrity properties. substantially increasing non-compliance. It is believed that the increased opacity achieved in the area of curves A (Figure 3) is mainly due to the better dispersion of the opaque pigment in the paint film due to the efficient penetration of this pigment into the gaps between the plastic particles. The opacity achieved in area B of Figure 3 is primarily due to the formation of open cellular cavities in the paint film when sealing the plastic particles, increasing the number of microcavities, resulting in light scattering in the microcavity cells, resulting in increased opacity with minimally opaque paint film. Area C in Figure 3 is above the critical surface porosity PVC, where opacity increases slightly and glazing resistance properties deteriorate, but nevertheless surprisingly yields very useful porous paint films with good film density properties at high PVC values above the critical surface area. Useful PVC values according to the present invention are in the ranges A, B and C, provided that the surface porosity of the film is less than about 0.25 cm 2 / g, preferably 3 less than 0.15 cm 2 / g and very preferably less than 0, 10 cm 2 / g, measured by the penetration of mercury into pores with a diameter of less than 1.5 μm. The paint films of this invention fall widely in areas A, B and C, the preferred paint films in areas A and B and the most preferred paint films in area A in Figure 3. Non-film forming polymer particles substantially larger than 1.0 μm tend to form large microcavities which in turn, adversely increase excessive porosity in the paint film, and thus the size of the most preferred polymer particles is between about 0.1 and 0.6. Thus, the most preferred high quality 63592 and high opacity paints of the invention are generally made to correspond to area A, with the curves representative in Figure 3, and the preferred paints to correspond to areas B and C. All paints of this invention exceed the maximum opacity achieved with conventional paints made With PVC and the same amounts of dimming pigments.

Figure 4 shows graphically (as in Figure 2) the opacity of the paint films according to the invention as a function of the TiO 2 content. The paint film with a given TiCl 2 content + non-film-forming plastic particles is labeled with opacity (steepness ratio) as a function of the pigment volume percentage (PVC). The opacity, although not shown in Figure 4 at the 0% level of TiO 2, is essentially negligible below n.

In 60% PVC, while above 60% PVC, the opacity is measurable, but the result is below the acceptable opacity for conventional opaque paint films. Thus, it is required that at least 5% TiO 2 and preferably at least about 10%

TiO 2, calculated on the volume of dry solid, is present in the paint films of this invention.

Figure 5 illustrates a set of paint films according to the present invention with different PVC values. It is noted that better paint films can be obtained with latex paints with PVC values above critical surface porosity PVC, whereby the dried paint film has poor glazing resistance properties, but surprisingly retains film integrity properties such as abrasion resistance, abrasion resistance, gloss resistance, abrasion resistance, abrasion resistance, abrasion resistance, abrasion resistance. , soot resistance and abrasion resistance, as can be seen from the film integrity curve in Figure 5. Accordingly, the latex paint compositions of the invention can be blended with opaque extenders and filler pigments up to about 75% PVC.

Figure 6 shows the gloss of paint films as a function of PVC. Gloss is measured at 60 ° and gloss is measured at 85 ° according to ASTM D523-67. The gloss of conventional paints deteriorates sharply in the vicinity of about 30% PVC and the deterioration continues and the gloss asymptotically approaches 0-gloss at PVC values above the critical PVC.

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In contrast, both gloss and luster are restored in the paint films of this invention with PVC values above the critical PVC and continue to improve as the PVC grows.

Figure 7 shows the transparency (steepness ratio) of a set of paint films of the present invention as a function of increasing amounts of TiCl 4 and compares this to a prior art paint (dashed line) containing about 113 kg ΊΊΟ2 / 379 l of paint and having a solids volume of 33%. The paint film set shown in Figure 7 contains the indicated amounts of TiC> 2 + plastic particles to give unchanged PVC values.

The latex dispersion paint composition according to the invention contains a latex binder, solid non-film-forming polymer particles (plastic particles), an opaque pigment and optionally an opaque pigment. Various conventional additives can also be added to the paint, which affect the durability and application properties. Paint films are formed by combining a film-forming binder with a binder matrix at an application temperature to provide a hard, non-stick paint film.

Non-film forming particles are solid and non-porous while not forming a film under paint application conditions. Non-film-forming polymer particles can generally be identified by having a glass transition temperature of at least about 5 ° C, preferably about 15 ° C, and very preferably about 25 ° C higher than the ambient coalescence temperature at which the paint film coincides with the cured dry paint film. Thus, the paint films of the present invention applied and formed at about 25 ° C at room temperature contain non-film-forming polymer particles having a glass transition temperature of at least about 30 ° C, preferably above 40 ° C, and even more preferably at least 50 ° C. Similarly, paint films that have been acceleratively dried by heating processes contain non-film-forming polymer particles, preferably having a glass transition temperature at least about 25 ° C higher than the ambient binder fusion temperature. The term "glass transition temperature" is a well-known concept in the art and is generally defined as the onset of a broad molecular motion in which the polymer retains the outward appearance of the solid but becomes rubbery and then sticky as the temperature rises and undergoes plastic flow and elastic deformation. The polymer component having a glass transition temperature higher than room temperature is not a film former at room temperature. The glass transition temperature can be measured according to 41 Journal of Paint Technology, pages 167-178 (1969). The glass transition temperature (Tg) is best measured when such polymer particles are in a latex paint, taking into account the interactions of different paint components, such as coalescing agents. The Tg can be calculated based on the Fox equation or by evaluating the Vicat softening point by testing as described in ASTM-1525. Under accelerated drying conditions of the paint film, ambient coalescence temperatures are higher than room temperature, such as 49-53 ° C or even as high as .204 ° C. In high temperature maturation, the glass transition temperature of the non-film-forming polymer particle must be higher than the highest temperature of the film to be dried.

The glass transition temperature (Tg) of the non-film-forming solid polymer particles is measured from an aqueous latex emulsion paint mixture containing such polymer particles, taking into account the interactions of the various components of the paint, such as co-adjuvants. The weight average diameter of the non-film-forming polymer particles is between about 0.1 and 1.0. Preferably, the solid polymer particles are between about 0.1 and 0.8 and very preferably between about 0.1 and 0.6. Mean particle diameters can be measured according to known electron microscopic methods, as described by S. H. Maro in the Journal of Applied Physics, Vol. 23, page 900 (August 1952) or by centrifugal collision in Polymers Engineering and Science, Vol. 14, pp. 332-337 (May 1974). The non-film-forming particles have a refractive index in the range of about 1.3 to 1.7, as measured by the ASTM D-542 method, while their density or specific gravity is in the range of about 0.9 to 1.5. The non-film-forming polymer particles are solid and non-porous and are preferably substantially spherical in geometric shape. The matt paint preferably contains 10 to 60% and particularly preferably 15 to 50% by volume of dry solids of non-film-forming polymer particles. Preferably, the latex paint contains at least n, 10% non-film forming particles or contains such particles in a volume ratio greater than the volume ratio of the opacifying pigment. The non-membrane particles are ► ‘ί r *%> \. * 63592 11 preferably polystyrene, but may be polymers and copolymers of other ethylenically unsaturated monomers, as disclosed in U.S. Patent 3,423,351, provided that the Tg of the particles is sufficiently high and the particles remain discrete and do not coalesce at ambient application and maturation temperatures. The non-film-forming polymer particles may be copolymerized ethylenically unsaturated monomers which can be further polymerized via an ethylene double bond. Examples of such ethylenically unsaturated monomers are styrene, substituted styrenes, vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, some acrylic and methacrylic acid esters and tert-butyl acrylates having polymers having tert-butyl acrylates. Preferred polymer particles are polystyrene, polyvinyl chloride and polymethyl methacrylate, as further illustrated in the Examples.

The opaque pigments used in conjunction with the polymer particles of the film-forming towers are generally pigments with a refractive index of at least about 1.8. Typical white opacifying pigments include rutile and anatase-titanium dioxide, lithophone, zinc sulfides, lead titanate, antimony oxide, zirconia, titanium calcium, lead white, titanium barium, zinc oxide, lead zinc white, and their zinc white mixtures. The preferred white inorganic opacifying pigment is rutile titanium dioxide having an average particle size of from about 0.2 to 0.4. Titanium yellow and similar pigments with a high refractive index can be used both as dimming pigments and to impart color tones to the paint. Although most dimming pigments are white, all dimming pigments having a refractive index greater than about 1.8 should be considered suitable dimming pigments for the present invention, despite their color film coloring effect. The amount of opacifying dimming pigments in the paint combination according to the invention is 5 to 25%, based on the volume of dry solids of the latex paint, and preferably 10 to 25%, based on the volume of dry solids.

A film-forming binder is used to adhere the film to the paint surface at the paint application and paint film drying temperature i * λ ;. l

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12,63592 to form a binding matrix for dimming pigments, non-film-forming polymer particles (plastic particles) and other non-film-forming additives such as extender and filler pigment. The main part of the film-forming latex binder is polymer particles, preferably between 0.1 and 1.0. A film-forming binder having a major particle size by weight of not less than about 0.1 μm is preferred to obtain the desired opacity, which appears to be due to the inability of the binder particles to penetrate the micropore structure formed in the film as a result of non-film-forming particles. The weight average diameter of the film-forming latex polymer particles should be 0.1 to 1.0, preferably 0.3 to 0.8, in order to achieve the desired rheological properties.

Aqueous doped film-forming binder latexes can be very broadly classified emulsions or dispersions of synthetic resins suitable for mixing with latex paints. Suitable latexes, or when mixed with plasticizers, solvents, and the like, contain polymeric particles having a glass transition temperature suitable for film fusion and coalescence under application conditions. Thus, for air-drying latex paints at the usual temperature, e.g. 25 ° C, the film-forming binder latex has polymer particles having a glass transition temperature of less than 20 ° C and at least about 5 ° C and preferably at least 15 ° C below ambient coalescence temperature and therefore form a film or binding matrix at the coalescence temperature in such an environment. When the film has to be dried by acceleration, e.g. by heating in an oven, the glass transition temperature of the film-forming binder polymer particles may be substantially higher, but still preferably at least 15 ° C lower than the drying contact temperature, so that this binder forms a binding matrix film in accelerated drying. The glass transition temperature of the film-forming binder must be at least about 10 ° C lower than the glass transition temperature of the non-film-forming polymer particles, the glass transition temperature of the non-film-forming polymer particles must be higher than the extreme maximum temperature of the film to be dried. Preferably, the difference between the glass transition temperatures of the film-forming and non-film-forming polymer particles is about 30 ° C.

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The glass transition temperatures can be measured when the film-forming polymer particles are present in the latex paint composition, taking into account the interactions of the various components of the paint, such as co-adjuvants.

Typical polymeric film-forming binders suitable for the latex dispersion paints of this invention, which are applied at about room temperature, include ethylenically unsaturated monomers, such as polymers containing vinyl acetate, acrylate, methacrylate, isoprene, styrene, butadiene, butadiene, - and / or dibutyl maleate polymers and copolymers and are often mixed with stabilizers and additives and are disclosed, for example, in the following U.S. patents: 2 H9 8,712; 2,676,930; 2,700,026; 2,702,284; 2,728,737; 2,731,434; 2,731,435; 2,739,136; 2,773,849; 2,807,597; 2,803,950; 2,833,747; 2,837,444; 2,852,475; 2,852,476; 2,868,752; 2,875,166; 2,881,143; 2,883,355} 2,884,397; 2,886,546; 2,887,460; 2,880,421; 2,888,422; 2,888,505; 2,889,236; 2,889,314; 2,892,802; 2,894,927; 2,895,930; 2 B97 100; 2,897,165; 2,899,397; 2,905,649; 2,907,720; 2,902,721; 2,904,523; 2,912,399; 2,913,429; 2,914,497; 2,917,476; 2,921,046; 2,922,781; 2,933,467; 2,933,469; 2,934,529; 2,936,295 and 2,937,156.

Other film-forming binders that are useful when working at higher temperatures are polymers that often contain vinyl chloride units. Various film-forming acrylic binders are useful in the paint combination of this invention, and include polymers of methacrylic acid, acrylic acid and mixtures thereof, copolymers of acrylic acid and / or methacrylic acid esters / acrylate esters and terpolymers with styrene and / or vinyl acetate and / or vinyl terpolymers with acrylonitrile as well as emulsion copolymers such as polymerized oils and phenolic monomers, as disclosed in U.S. Patent No. 2,972,151. Suitable film-forming

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Latex binders include: those which are polymers of vinyl and vinylidene and contain vinyl acetate, vinyl chloride, vinylidene chloride and the like in units; those which are hydrocarbon polymers and copolymers and contain ethylene or propylene units and either butadiene, oxidized butadiene, iso-propylene, oxidized isoprene, butadiene-styrene, butadiene-vinyltoluene, isoprene or halo-derived styrene and their styrene containing acrylic and containing units of acrylic acid, methacrylic acid, their esters and acrylonitrile; copolymers containing hydrocarbon monomers with unsaturated substances, such as the reaction product of maleic acid with styrene; and, more broadly, various other resinous and rubbery elastomeric latex products which are polymers and copolymers of ethylenically unsaturated monomers and which are polymers available in a stable latex form and which are capable of adhering to a pigmented film-forming binder when applied to a surface cure at room temperature or elevated temperature. Coagulation aids such as diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol monophenyl ether or 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate in the formulation

The dimming pigment interacts effectively with the plastic pigment and spreads evenly throughout the paint film with the plastic pigment. The increased opacity achieved before the settling of abundant surface porosity is thought to be mainly due to the increased dispersion and increased range of motion of the opacifying pigment caused by the extensive mobility of the plastic particles and the formation of a substantially closed cellular micropore structure in the paint film. Ordinary paint films are generally about 0.0254 to 0.0762 mm thick when applied with a brush or roller, and these thick films of the opaque paint of the invention must contain 5 to 25% opaque pigment, such as rutile TiO 2, based on dry the volume of solids.

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In general, it can be said that the thinner the film, the higher the concentration of opaque pigment must be. In order to obtain the best coverage in such films, pigment-rutile-TiCl 2, preferably 10 to 25%, based on the volume of dry solids, is used.

The paint of this invention may further contain opaque filler or extender pigments, often referred to as inert in the art, and are clays such as kaolinitic clays, silica, talc, mica, wolastonite, heavy slag, shale meal, calcium carbonate, and the like. All filler or extender pigments have fairly low refractive indices and can generally be described as pigments other than the opaque pigment. The effective diameter of the filler and extender pigments should generally not exceed 44 μm for painting purposes and generally their particle size will not be substantially greater than 25 μm for the best finishes. The proportion of filler and extender pigments may be from 0 to 60% of the latex paint, based on the volume of dry solids, and is preferably from about 5 to 50% at higher pigment loads. Preferred filler and extender pigments include calcined clay, amorphous silica, crystalline silica, and diatomaceous silica, which have not been found to significantly reduce the highly desirable and preferred film-forming particles and opaque pigments dispersed in dried paint films. In contrast, conventional latex paints containing filler and filler pigments invariably show a significant deterioration in the integrity properties of the film at PVC values above the critical PVC.

The latex paint of the present invention may contain coloring pigments, which are pigments that impart a characteristic color tone to the available latex emulsion paint. Coloring pigments are generally, for example, ferrite yellow oxide, ferric oxide, "brown" iron oxide (which is a mixture of red, yellow and brown iron oxide), iron skin brown oxide (which is a mixture similar to the previous one), crude mushroom and burnt Sienna, crude and burnt Umbra, green chromium oxide, phthalocyanine green (chlorinated copper-phthalic nitrile), nitroso-beta-naphthol green iron salt, copper, phthalic V V. *.

16 63592 nitrile blue, ultramarine blue, kimrime, soot, toluidine red, parachlor red, para tint (red, alkali resistant red, BON red and maroon), cadmium red and yellow sulphides, Watchung red, crap lacquer , Duratone red, carmine red, chromium (lead chromate), chromium orange, hansa yellow dyes (which are azo combinations of methanitroparatoluidine and acetoacetanilide), and gold nickel azo complexes such as those disclosed in U.S. Patent No. 2,396,327. such as pearlescent graphite, pearlescent glass melt, etc., and fluorescent, pearlescent, and opalescent agents can be broadly classified as coloring pigments because such pigment additives impart specific optical effects such as pearlescent and pearlescent effects. The proportion of coloring pigments is 0 to 20% and preferably 0 to 10%, based on the volume of dry solids of the latex paints of this invention, and such coloring pigments are generally, but not always, opaque; this depends on their refractive index.

An interesting and valuable feature of the latex emulsion paint of the present invention is that higher gloss and gloss can be achieved with high PVC values, which are achieved in particular with non-film-forming monodispersed polymer particles of approximately the same size. Useful monodispersed polymer particles can be prepared by careful seeding and emulsion polymerization, as disclosed in U.S. Patent 3,423,351. contains anionic and nonionic surfactants under emulsion polymerization conditions, the proportion of surfactants being carefully controlled together with the temperature and solubility of the polymerizable liquid in the reaction mixture. The particle diameter of the suspension or emulsion can be easily determined by electron microscopic methods. When determining the uniformity of the particle diameter, the weighted average diameter (D) is divided by the numerical mean diameter (D) to give the D / D ratio w n.

de, i.e. the polydispersion coefficient, which determines whether the suspension of polymer particles is monodispersed or polydispersed. With a ratio of DM / D

w n • · ** 4.

o · 'It, · 63592 17 is 1.00, the particles are completely monodispersed and in the latex paint of the present invention all polymer particles are considered to be monodispersed when the Dw / Dn ratio is between 1.0 and about 1.1 and preferably between 1.00 and 1.05.

A surprising additional advantage can be achieved with paint combinations f having a very high content of non-film-forming components and high PVC values above critical surface porosity PVC (glazing resistance), whereby the dried paint films produced have low glazing resistance but unexpectedly retain essential glazing properties. soil resistance, soot resistance, scratch resistance, stain resistance, abrasion resistance and abrasion resistance, and similar film non-perishability properties. The high pigment / binder ratio is above the PVC level, with sufficient film-forming binder available to completely encapsulate the non-film-forming solid components. In contrast, conventional latex paints without plastic polymer particles lack cohesiveness and film integrity at high PVC values above critical PVC due to the discontinuous paint phase. In this case, the latex paint according to the invention preferably has a film-forming binder containing at least about 40% by weight of copolymerized acrylic unsaturated monomers, such as, for example, acrylic and methacrylic acid, methyl acrylate and methacrylate, ethyl acrylate and methacrylate and methacrylate, , propyl acrylate and methacrylate, 2-ethylhexyl acrylate and methacrylate, and various reaction products such as butyl, phenyl and cresyl glycidyl ethers reacted with acrylic and methacrylic acids, hydroxyacrylate acrylates and methacrylates, and methacrylates, as well as aminoacrylates and methacrylates. Other useful binders for paints blended with PVC values above the critical surface porosity PVC include acrylic copolymers containing up to 60% styrene, styrene-butadiene copolymers containing n # 35- 65% copolymerized styrene or styrene derivatives, as well as acrylonitrile copolymers, vinyl chloride and vinylidene chloride, often mixed with plasticized monomers such as dibutyl maleate, butadiene or alkyl acrylates.

The film-forming binders used for bonding at the paint application temperature cause the paint film to dry and form a binding matrix for dimming pigments, film-forming polymer (plastic part), non-dimming pigment extensions and fillers, and other non-film-forming additives. Coupling agents such as diethylene glycol monoethyl ether acetate, 2,2,4-trimethyl-1,3-pentadiol monoisobutyrate or dibutyl phthalate are useful binders in the latex paints of this invention.

The PVC of the latex paint combination of the present invention is 30 to 75%, wherein the PVC of the paint combination is greater than the critical PVC as measured by opacity. Latex paints have a PVC content of up to 75% and can provide paint films with excellent film integrity properties such as abrasion resistance, gloss resistance, scratch resistance, stain resistance, abrasion resistance, abrasion resistance, abrasion resistance and abrasion resistance. in accordance with test No 2486, modified so that the spacer has not been used. The abrasion test is performed with a 10% aqueous slurry of Crest soap used as a abrasive abrasive medium and expressed as the number of abrasions to remove 50% of the paint film thickness. The indestructibility properties of the film can be suitably measured by abrasion resistance, with the minimum film indestructibility properties of paint films made in accordance with this invention lasting at least about 100 abrasions, preferably more than 450 abrasions for good paint films and preferably at least about 600 abrasions for high quality paints. The most preferred paints have PVC greater than critical PVC (opacity) and less than critical surface porosity PVC (glazing resistance), indicating that the most preferred paint films have very low film surface porosity. With paint films provided in accordance with the present invention with PVC values greater than critical.

I! 63592 19 surface porosity PVC, has poorer vitrification properties than preferred films made so that critical surface porosity PVC is not exceeded. Surprisingly, such higher PVC films of the present invention retain their excellent film integrity properties. This is thought to be achieved by tightly sealing solid, non-porous plastic particles.

The solid, non-film-forming particles appear to be effectively resistant to abrasion even when such particles wear out of motion, they have the advantage of showing your exposed solid polymer rather than openings such as would result in hollow or hollow cell particles. Thus, the paint of the present invention could be expected to represent a more resistant surface against soiling and sooting even when worn to some extent, and less dry mineral pigment per unit area would be exposed than the corresponding conventional paint film, with the dry pigment often being quite susceptible to absorbable surface markings. Thus, although the paint film of the invention in these upper PVC regions clearly suffers from a "binder deficiency", it can have good film integrity properties up to 75% PVC. Such unexpectedly good performance may be due to some interaction between the stiffness, the plastic particles of the non-film forming towers, and the latex binder, the former possibly acting as a binder extender or excipient in some way.

The latex emulsion paint of the invention can be prepared in a dispersing mill such as a Cowles disperser. Preferably, the conventional components of the pigment dispersion, with the exception of the non-film-forming particles and the film-forming binder, are first mixed together in a disintegrating mill, or alternatively in a sand mill, rock grinder, roller mill or ball mill. The non-film-forming polymer particles and the film-forming binder, as well as the conventional softened ingredients, are then added to the resulting mixture and mixed suitably with a conventional tank mixer. The resulting paint is thoroughly dispersed, dispersion.

The following examples illustrate the advantages of the present invention and provide methods for practicing the invention,. J »'. * * 4 1,‘ 20 63592

Example 1

A pigmented latex emulsion paint was prepared as follows:

Pigment-grinding mixture kg 1

Water 7.94 7.949

Bactericidal agent; 1- (3-chloroallyl) -3,5,7-triazol-1-atsonioadamataanikloridi,

(S

(Dcwicil 100, manufactured by Dow Chemical Co) 0.45 0.454

thickener; a 2.5% aqueous solution of hydroxyethyl cellulose having a solution viscosity of 15,000 cps. ("Collosize QR 1500") 45.36 45.874

anti-foaming agent; mineral oil and silica derivatives ("Drew L-475") 0.91 0.984

Pigment dispersant; sodium salt of polyacrylic acid (Tamol 731, manufactured by

Rohm & Haas, Co.) 3.54 2.990 (S)

a wetting agent; (Triton CF-32, manufactured by Rohm & Haas Co.) 0.113 0.114

Rutile-TiO2 79.38 19.796

Dilution

Water 53.57 53.633

Aggregating agent; 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate 1.09 1.136

Aggregating agent; diethylene glycol butyl ether acetate 4.45 4.542

Film-forming binder latex; vinyl acetate dibutyl maleate copolymer 94.21 86.714

Latex of non-film forming particles; polystyrene 0.2325 fin 115.44 111.279

Defoamer ("Dow L-475") 0.91 0.984

thickener; As a 2.5% aqueous solution of hydroxyethylcellulose 41.91 42.392

A total of 442,273 378,841

The pigment volume content (PVC) obtained was 65%, the solids content by volume was 33% and the solids content by weight was 45.3%.

63592 21

The paint films were dried at room temperature (22.2 ° C) for at least 15 hours before subsequent measurements. The opacity was measured with a 0.0762 mm wet film applied to a "Lenata Form 38" opaque washer and dried at 22.2 ° C for 16 hours, the reflectance ratio being measured against the black and white portions on the opaque washer using "Color Eye "spectrophotometer to give a slope ratio expressed as the reflection of black against white. Surface porosity was measured by glazing resistance, whereby 0.0762 mm of wet test dye was applied with a "Bird" applicator to a "Lenata Form 38" opaque washer and dried at 22.2 ° C for at least 16 hours. A 0.0381 mm wet alkyd enamel film (white alkyd Y-5950 containing 17.3% TiO 2; 14.5% inert matter; 30.7% tall oil alkyd; 37.5% mineral spirit (produced by Clidden Durkee Division of SCM Corporation) for dried paint film and alkyd enamel was dried at room temperature for 24 hours. Surface porosity was also measured by the K&N ink resistance test, in which 0.0762 mm wet test paint was applied to a "2C Lenata" opaque washer with a 0.0762 mm "Bird" spreader and air dried for 16 hours. then pour from a rectangular 2C washer onto the white test paint surfaces and allow to dry for 2 minutes. s paper i wipes. The absorption of the ink into the test film is then determined by reading the percentage reflectance on an Y-scale of an "IDL Color Eye" colorimeter spectrophotometer (Instrument Development Labs, Kollmorgan Corporation) using a white vitrolite standard. Porosity is expressed as a percentage of the reflection ratio. Similar paint films, 0.0762 mm thick, wet and dried at 22.2 ° C for 16 hours, were subjected to abrasion resistance test (modified ASTM Test No. D-2486) and stain resistance test (Test No. D-2198). . The results obtained are shown in Table 1 below.

63592 22

Table 1 Property PVC 65% Volume of solids 33%

TiO2 content (kg / 379 1) 79.5 Opacity (slope ratio) 0.970

Surface porosity (glazing resistance) 80%

Surface porosity (K&N ink resistance) 80%

Abrasion resistance (abrasion resistance) excellent

Excellent resistance to staining

Excellent gloss resistance

Gloss (% reflectance at 85 ° C) 60%

Gloss (percentage of reflection at 60 ° C) 8%

Example 2

A paint similar to Example 1 was prepared by mixing with 56% PVC to contain non-film-forming polymer particles with a diameter of 0.520 μm. The paint films were tested according to Example 1 and the results are summarized in Table 2.

Example 3

The paint of Example 1 was prepared by mixing with a PVC value of 64% to contain non-film-forming polymer particles with a diameter of 0.231. The paint films were tested according to Example 1 and the results are summarized in Table 2.

Example 4

The paint of Example 1 was prepared with 70% PVC. The paint films obtained from these were tested according to Example 1 and the results are summarized in Table 2.

Example 5

A prior art paint was formed containing a film-forming latex binder which was a copolymer of 82% vinyl acetate and 18% dibutyl maleate, 115.8 kg of TiO 2 (23%) and inert substances. The paint contained 21% TiO 2 by volume; 5.3% CaCO 3; 7.7% silica and silicates; 16.2% latex binder; 2% additives; 2.8% glycol and glycol ethers; and 45% water, bringing the volume of solids to 33% and PVC to 42.6%. The paint according to the prior art was tested according to Example 1 and the results obtained are summarized in Table 2.

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Example 6

The following pigmented latex emulsion paint was prepared: A. The following ingredients were dispersed in a "Cowles" solvent for about 55 minutes: 255 parts of rutile pigment TiO 2, 50 parts of calcined clay, 60 parts of calcium carbonate, 3 parts of a nonionic surfactant which is a mixture of isooctylphenoxyethanol containing 9-10 ethylene oxide units per mole of phenol ("Triton X-100'Ί, 8 parts of a 15% aqueous solution of the sodium salt of the polymeric carboxylic acid TTamol 731"), 1 part of an antifoam, with a mineral oils and silica derivatives ("Drew 913SX"), 12 parts ethylene glycol, 2.4 parts water-soluble cellulose thickener, which is hydroxypropylmethylcellulose containing about 19-24% methoxyl and about 4-12% hydroxypropoxyl, 1 part antimicrobial substance, 1- (3-chloroallyl) -3,5,7-triazo-1-azonioadamantane chloride, 150 parts of water B. The following substances were added to Part A: 2.3 parts of cellulose thickener, hydroxypropylmethylcellulose, 16 part of diethylene glycol monoethyl ether, 4 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 4 parts of a nonionic surfactant which is the ammonium salt of octylphenoxypolyoxyethylene ethanol sulphate ester (Alipal CO-435 ®, manufacturer G AF Co.) 4 parts of a dispersant which is the sodium salt of polymethacrylic acid in 30% aqueous solution ("Tamol 850"), 4 parts of an antifoam which is a mixture of mineral oils and silica derivative ("Drew 913 SX").

C. A series of latex coals were prepared by mixing Part B (containing Part A) with an aqueous dispersion of polystyrene particles and a film-forming latex. The weight average particle size of the polystyrene particles was 0.2450 μτα, the Dw / ° n was 1.1, the weight content of the substances was 51.4%, the density was 1.029 kg / l and the glass transition temperature was about 100 ° C. The film-forming latex binder was an aqueous dispersion of a film-forming latex binder with 82% vinyl acetate copolymerized with 18% dibutyl maleate, having a dry matter content of 54.5% by weight and a weight average particle size of about 0.60000 .mu.m. glass transition temperature (Tg) 15 ° C. Water was added to each paint dispersion to give a dry matter volume of 33.1% for each indicated preparation. The pigment volume (PVC) content of the dry film obtained for each preparation is shown in Table 3. The percentages obtained for the aqueous dispersion of polystyrene and the aqueous dispersion of the film-forming latex binder were calculated on the basis of the solid dry volume. The sample marked as "reference" was a conventional latex paint consisting of a 57.5% copolymer of 82% vinyl acetate and 18% dibutyl maleate, based on the volume of dry solids, based on 23% of rutile-TiO2 by volume of dry solids. 19.5% inert substances as described in Example 5.

Table 3

Monodispersed Film-forming Pigment by volume Sample No. Polystyrene particles Latex binder (PV2) A-61 3.4% 57.5% 42.5% B-65 12.4% 48.5% 51.5% C-69 23 .5% 37.4% 62.6% D-70 33.5% 27.4% 72.6%

Comparison 0 57.5% 42.5%

The paint films of the above samples were air dried at room temperature (22.2 ° C) for at least 16 hours. The film-forming latex fused to the matrix, dispersing the particles remaining in the polystyrene. Other dried paint films were also tested for scattering and opacity; the results obtained are shown in Table 4.

26 _. ,, ι 63592

Table 4 Χ (0.98) **, dry film thickness NSyte nto S *, scattering (nm 1) for steepness ratio 0.98 (nm) _ A-61 216.5 0.0483 B-65 232.3 0.0470 C-69 212.6 0.0508 D-70 315.0 0.0356

Comparison 181.1 0.0610 * S = Kubelka-Munk scattering coefficient, ** X (0.98) = X is the thickness of the dry film which gives a slope ratio of 0.98 on the "Lenata Porin 3B" translucent mat. Transparency is determined with Kubelka-Munk solution for multiple light scattering (see Reflectance Spectroscopy, Springs-Verlog, New York (1969), starting on page 106).

Similar dried model films were tested for their glazing resistance and abrasion resistance as described below, and the results obtained are shown in Table 5.

Table 5

Relative abrasion resistance Sample No. Glazing resistance Abrasion resistance in% compared to comparison_ A-61 88.4% 947 abrasions 105% B-65 83.7% 1347 abrasions 150% C-69 89.0% 1800 abrasions 200% D-70 3 .8% 700 rubs 78%

Comparison 84.9% 900 rubs 100%

Glazing resistance was tested by applying a 0.0762 mm wet film with a "Bird" applicator to an "Lenata Form 3B" opaque substrate and drying at 22.2 ° C for at least 16 hours. A 0.0381 mm wet alkyd film (Glidden, white semi-gloss Y-5950) is then applied to a dry latex paint film and dried at room temperature for 24 hours. Alkyd has very poor durability properties. The gloss of the alkyd on the latex paint surface is compared to the gloss of the same alkyd applied to a surface-sealed substrate. The glazing resistance is expressed as a ratio or as a percentage of the gloss applied to the latex paint compared to the gloss li 63592 27 obtained on the surface-sealed substrate. Abrasion resistance was measured by applying a latex paint in a 0/1524 mm layer to a "Lenata Form P-121-ION" substrate with a "Bird" spreader and air drying at 22.2 ° C for at least 16 hours. The dried films are tested in a "Gardner" scrubber using a 10% aqueous solution of "105 Crest" soap. The abrasion resistance is expressed as the number of abrasions leading to soiling (i.e., 50% of the paint film is abraded).

Better paint film properties can be achieved over a substantially wider range of PVC, resulting in excellent films with higher PVC values. Conventional paints have a narrow critical PVC area where the opacity of the paint and the glazing resistance properties are a kind of compromise. Conventional latex paints generally have a glazing resistance of about 85% and an abrasion resistance of less than 1000 abrasions to wettability.

Example 7

The paint samples shown in Table 6 below were prepared in the same manner as in Example 6. The pigmenting rutile TiO 2 content was gradually reduced. The opacity was maintained by increasing the content of plastic polymer particles while decreasing the content of titanium dioxide. The volume of the polystyrene polymer particles was adjusted to maintain the pigment volume content (PVC) of the dry film at about 62.6%. The volume fractions of the ingredients shown in Table 6 are volume fractions in dry film as volumes of solid solids based on dry matter volume.

Table 6

TiO2- Polystyrene- Inert volume- Film-forming Sample No. volume fraction volume fraction fraction_ latex volume fraction E-69 23.0% 23.5% 16.1% 37.4% F-76 21.7% 24.8% 16, 1% 37.4% G ~ 75 19.0% 27.5% 16.1% 37.4% H-74 16.2% 30.3% 16.1% 37.4% 1-73 13.5 % 33.0% 16.1% 37.4%

Comparison 23.0% 0.0% 18.5% 57.5% 28,63592

The paint films obtained from the above were tested as described in Examples 1 and 6, and the results are shown in Table 7 below.

Table 7

Film, thickness Sample No. Decompose S, (ran 1) for steepness ratio Abrasion resistance Glazing resistance 0.98 (nm) E-69 216.5 0.0508 1800 abrasion- 89.0% times F-76 204.7 0.0559 1200 abrasion- 86.6¾ times G-75 212.6 0.0508 1850 abrasion- 84.3% times H-74 220.5 0.0508 2000 abrasion- 88.4% times 1-73 212.6 0.0508 1400 abrasion- 78.6% times

Comparison of 181.1 0.0610 900 rubs-84.9% times

Example 8

Paint samples were prepared in the same manner as in Example 6. As shown in Table 8 below, the concentration of rutile titanium dioxide pigment was kept unchanged and the concentration of polystyrene particles was varied. An inert material, as shown in the table, was added to keep the dry film pigment volume (PVC) content at about 63.0%. The volume fraction of pigments and film-forming latex is also shown in the table.

63592 29

Table 8

Monode of Sperged Inert Film Forming

Volume latex of TiO 2 - polystyrene Sample No. volume fraction volume fraction_ fraction_ volume fraction_ J-9D 13.5% 8.4% 41.1% 37.0% K-9C 13.5% 16.8% 32.7% 37 .0% L-9B 13.5% 25.1% 24.4% 37.0% M-9A 13.5% 33.5% 16.0% 37.0% N-7B 13.5% 37, 5% 12.0% 37.0% 0-7C 13.5% 41.5% 8.0% 37.0% P-7D 13.5% 45.5% 4.0% 37.0% Q- 7E 13.5% 49.5% 0 37.0%

Comparison 13.5% 0 49.5% 37.0%

The paint films obtained from the previous combinations were tested in the same manner as in Example 6. The results are summarized in the following Table 9. The gloss was measured at 85 ° C by the method of ASTM D-523-67.

Table 9

Scattering Film thickness Glazing to 60 ° gloss reading, Sample No. S, (irm ^) for steepness ratio resistance ASTM D-523-67 _ _ 0.98 (nm) _ __ _ J-9D 157.5 0.0660 84 % 3.2 K-9C 165.4 0.0635 90% 4.8 L-9B 173.2 0.0610 96% 7.8 M-9A 208.7 0.0533 94% 20.6 N-7B 216 .0 0.0508 95% 31.8 0-7C 220.5 0.0508 94% 47.0 P-7D 212.6 0.0508 94% 60.6 Q-7E 216.5 0.0508 98% 73

Comparison 149.6 0.0686 35% 2.8

The above demonstrates the advantages of the present invention, in which the paint compositions give films with high gloss, although the dried films contain 63% by volume of pigment, while ordinary latex paint films at 60% give "flat" films in terms of brilliance. Gloss is measured according to ASTM test number D-523-67. In addition, there are notable advantages of the present invention in that the opacity increases as the plastic polymer content increases from 5% to 37%, while the porosity decreases, which is not characteristic of conventional paint films having a pigment volume content of 63%. Example 9

Paint mixtures were prepared in the same manner as in Example 4. In the following Table 10, the various film-forming latex binders shown were used in the paint preparation to maintain the Pigment-ti volume content in the dry film at about 63%. The total volume of solids was kept at about 33%.

Table 10

Film-forming Weight% Particle- Glass transition stage Sample No. latex binder dry matter whole space Tg_ R-23 Copolymer with 82% vinyl acetate and 18% di-

butyl maleate 54.4% 0.600 um 21 ° C

S-2 4 Terpolyzate of methyl methacrylate, butyl acrylate and acrylic acid

meri 50.0% 0.4800 μm 5 ° C

T-25 Copolymer of vinyl chloride and butyl acrylate 55.0% 0.1100 pm unknown U-26 Methyl methacrylate and butyl acrylate

copolymer 46.5% 0.1000 μm 9 ° C

V-27 Copolymer of 83% vinyl acetate and 17% 2-ethyl acetate

hexyl acrylate 51.0% 0.30000 μm 10 ° C

W-28 Vinyl acetate, vinyl chloride and ethyl

terene polymer 52.0% 0.4800 pm 15 ° C

X-29 Terpolymer of methyl lymethacrylate, netacrylic acid and butyl acrylate ^ 0% 0.0850 pm 65.0% 70% 0.6000 pm OQc 31 63592

The film-forming latex binders described above were mixed with polystyrene particles, opacifying pigments and inert substances as in the previous examples. The film-forming latex binders shown in Table 10 were used in sufficient quantities to keep the pigment volume content in the dry film at about 63%. The film-forming binders in Table 10, based on the volume of solids, were used 37%, monodispersed polystyrene particles 33.0% and TiCl 2 13.5%. However, by maintaining the ratio of ingredients unchanged, the following paints shown in Table 11 may not be optimized in quality because the preferred usable PVC range depends on the average particle size of the plastic particles as well as the relative particle size of the binder. Paint films made from these were tested in the same manner as in Example 10, and the results are summarized in the following Table 11.

Table 11 Film-forming Sample No. Latex binder Steepness ratio Glazing resistance X 37% R-23 0.965 99.5% Y 37% S-24 0.967 87.6% Z 37% T-25 0.951 86.5% AA 37% U -26 0.949 95.1% AB 37% V-27 0.965 47.7% AC 37% W-28 0.961 86.5% AD 37% X-29 0.967 86.0%

The steepness ratio was measured by applying a 0.0762 mm wet film to an "Lenata Form 3B" opaque washer and dry drying at 22.2 ° C for at least 16 hours. Reflection measurements were made against both white and black substrates using a "Color Eye" spectrophotometer. The steepness ratio is expressed as the ratio of black reflection to white reflection.

32 63592

Table 12

Film-forming Steepness TiC ^ m by volume Sample No. latex-binder PVC ratio Durability fraction_ AE R-23 65 0.979 89.0% 13% AF S-24 52 0.973 88.0% 13% A3 U-26 62 0.969 88.5% 13% AH X-29 60 0.976 89.5% 13%

Comparison with the industry's previously blocked product R-23 42 0.970 87.0% 23%

Example 10

Paint mixtures were prepared in a sauna as in Example 1 using homopolymer methyl methacrylate latex as plastic particles. PVC was 44%, TiCl 2 was 13% by volume of the solid paint, 33% by volume of the solids in the paint, leaving plastic particles 31% by volume in the dried paint film. A suitable PVC was selected as described herein to be at the point of critical surface porosity. Table 13 summarizes the opacity and porosity measurement results.

Example 11

Paint mixtures were prepared in the same manner as in Example 1 using homopolymer-vinyl chloride as plastic particles. PVC was 52%, solids volume 33%; the paint film contained, based on volume, 13% TiCl 4 and 39% plastic particles. A suitable PVC was selected to the point of critical surface porosity as described herein. Table 13 summarizes the results of the opacity and porosity measurements.

Table 13

Plastic Particle- Particle- Polydisperse- Glazing- Steepness- Composition Size Tunic_ PVC Durability Ratio

Honcpolymer vinyl chloride 0.1790 μη 1.12 52 81% 0.970

Hydropolymer methyl methacrylate 0.2694 μη 1.06 44 80% 0.966 li 63592 33

Example 12

The paint sample, designated C-69 in Example 6, was modified by the addition of 1% by weight of a black dye, which was also a 5.1% dispersion in ethylene glycol base. A 0.0762 mm thick wet paint film was applied to an opaque "Lenata Form 3B" substrate with a "Bird" applicator and air dried at room temperature for at least 16 hours. The reflectance of the dried film was 78.7 as measured through the Y-filter of a "Color Eye" spectrophotometer. For comparison, the reflection of a conventional dry latex paint film modified in the same way with 1% black dye was 73.6%. Conventional paint films require about 50% more TiCl 2 to give a dyeing force equivalent to the latex emulsion of this invention as measured by reflection.

The following Examples 13 to 17 (Tables 14 to 17) illustrate latex paints containing non-film-forming polymer particles with high PVC values above critical surface porosity PVC as measured by glazing resistance.

Example 13

Figure 5 shows a series of paint combinations made as follows. Two pigmented latex emulsion paints were prepared by high speed dispersion in an impeller type dispersing device (e.g., "Cowles" solvent) to Hegman 8, followed by low speed addition of a binder latex and a film-forming plastic pigment as follows:

Pigment masterbatch (kq / 379 1) (kg / 379 1)

Water 13.6 4.5

Protective agent: 1- (3-chloroallyl-3,5,7-triazo-1-azycnoadamantane chloride (Dowicil 100®i 0.5 0.5

Hydroxyethylcellulose (2.5% aqueous solution of Cellulosize QP-15,000) 22.7 45.5

Ethylene glycol 11.4 11.4

Defoamer: mineral oil and silicic acid derivatives ("Draw-L-475") 0.9 0.9

Pigment dispersant: sodium polyacrylate 3.77 3.77

Wetting agent ("Triton CF-32") 0.118 0.118

Rutile-TiO 2 (Zopaque RCL-7 manufactured by SCM Corporation) 113.5 113.5 dilution

Water 45.5 61.3

Foam steroid 1.4 0.9

Binder latex: copolymer with 50% butyl acrylate and 50% methyl methacrylate, 0.5000, Tg = 0 ° C and dry matter content 50% by weight 168.0 56.0

Plastic pigment: polystyrene, Tg = 100 ° C and dry matter content 55.8% 41.2 136.2

Combining agent: 2,2,4-trimethyl-1,3-pentanediol isobutyrate 5.0 1.8

Thickener: hydroxy or cellulose (2.5% aqueous solution) 46.2 34.5 Concentrated aqueous NH 4 0.68 0.68

Volume of pigment (PVC) 40% 80% Volume of solids 33% 33% Weight of solids 46.5% 46.1%

II

63592 35

A series of paints were prepared by mixing 40 PVC and 80 PVC paints in appropriate proportions to obtain a series of paints with PVC in the PVC range of 40-80%. After equilibrating the finished paints for 24 hours, the films were applied to appropriate substrates with a "Bird" film spreader to give a 0.0762 mm wet film for further testing.

The opacity was tested on films applied to a "Lenata Form 3B" medium with a 0.0762 mm "Bird" spreader and dried for 24 hours, the reflectance readings against the black and white parts of the medium were obtained with a "Color Eye" spectrophotometer and the steepness ratio is determined for reflection against black divided by reflection against white. Higher ratios indicate higher opacity, i.e. opacity.

The surface porosity was measured on the basis of the glazing resistance, whereby the film obtained from the opacity test was subsequently coated with a glossy alkyd enamel using a 0.0381 mm "Bird" applicator. The gloss of the alkyd on top of the test paint divided by the alkyd gloss on the compacted substrate alone is defined as the percentage glazing resistance. Higher numbers indicate lower surface porosity. Gloss is measured with a "Hunter" gloss measuring device at an inlet and reading angle of 60 °.

Alternatively, surface porosity can be tested by applying K&N test ink to the film, as well as glazing resistance, for 2 minutes and then removing with paper towels. Penetration of the ink into the paint film causes a darkening of the color that is proportional to the porosity of the film and is measured by reading the Y-scale reflection on an "IDL Color Eye" spectrophotometer using a white vitrolite standard. Larger numbers indicate lower porosity.

Abrasion resistance is measured according to ASTM test D-2486, except that no spacer is used. A 10% slurry of "Crest" soap is used as the abrasive medium and the results are expressed as the number of abrasions at which 50% of the paint film is removed. The abrasion resistance is preferably expressed as a percentage of the abrasion resistance of an approved commercial standard latex paint tested simultaneously on the same test substrate. The standard used here is Spred Satin Y 3000® (manufactured by Glidden-Durkee Div., SCM) latex paint containing 21% TiCl 2; 5.3% CaCO 2; 7.7% silicas and silicates; 16.2% vinyl acetate copolymer; 2.8% glycol ethers and glycols; as well as 45% water. In this case, 100% abrasion resistance indicates resistance equivalent to the standard. Higher percentage or abrasion resistance values indicate better abrasion resistance.

Resistance to staining and stain removal are measured according to ASTM test D-2198 with results presented in the same manner as for abrasion resistance.

The results of such a test are suitably described in property in a scale plot as a function of PVC. A PVC value undergoes a sharp change in either property, which is defined as the critical PVC for that physical property.

Example 14

Several latex paint combinations with varying binder polymers were blended and tested comparatively for film integrity properties (abrasion) as well as glazing resistance and opacity (steepness ratio). The physical properties of the paint film are expressed as a ratio to the standard-high quality conventional latex paint Spred Satin® as in Example 13. The performance values in Table 14 are proportional to the 100% reading (standard). All paints in Table 14 were mixed with 60% PVC. The volume of solids was kept at 32%, of which 19.2% were non-film-forming components and 12.8% were film-forming binder. The Tg of the binder was calculated according to Fox's equation 1 / Tg =, where Tg is in ° K for the copolymer; is the weight fraction of each comonomer; and T 1 is the homopolymer T 6 for each monomer at ° K. the test paints were mixed with the following ingredients, varying the binder combination as shown:

Paint ingredients Volume of dry matter / 379 1

TiO2 16,957 1

Calcined clay ("Optiwhite") 20,666 1 (S)

Silica (Min-U-Sil 10, manufacturer

Pennsylvania Glass Ccnpany) 8,554 1

Dairy (Celite 499) 4,921 1

Folystyreeniä; non-film forming polymer particles, 0.2800 fan, Tg = 100 ° C 21.575 l

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Example 15

The latex paint compositions were blended as described in Example 14, except that the volumes of both the polymer particles of the non-film forming film and the film-forming binder were varied to give PVC levels between 50 and 75%. The binder consisted of 60% butyl acrylate and 40% methyl methacrylate (dry matter content 50% by weight, Tg = -10 ° C, size 0.2000 μm). The plastic pigment was 0.2800 polystyrene. The plastic pigment / binder latex ratio is expressed as 1/100 l of paint and the paint films were tested as in Example 14.

Table 15

Plastic Pigment Glazing- Abrasion- Opaque PVO Binder Latex Durability Duration _? ςο 50 80%> 400% 78% 16.00 4 10 55 -hl "80%> 400% 85% 14.40 5 70 60 75%> 400% 90% 12.80 7 30 65 TTT ^ 53% 325% 105% 70 "ti !? 15% 260% 115% 75 0% 170% 125%

Example 16

In the same manner as in Example 15, the binder formed 50% butyl acrylate + 25% methyl methacrylate + 25% isobutyl methacrylate with a dry matter content of 65% by weight (Tg = -4 ° C, size 0.4950 μm). The PVC was modified as shown in Table 16 and the tests were performed in a manner comparable to Example 15.

40 63592

Table 16

Plastic pigment Glazing- Abrasion- Opaque FUZ binder inelatex durability duration _ 5 »H 90 * 270% 86 4 55 85% 270% 95% 60 70% 215% 110% 65 ΪΤ ^ 35% 160% 120% 70 -14¾ 5% 120 % 130%

y f OU

75% 95% 140% The above illustrative examples of the present invention show that latex paint compositions can be made with non-film forming polymer particles together with a dimming pigment to give substantially better dull paint films with PVC values between 30 and 75%, with PVC being more critical. PVC value measured by opacity.

li

Claims (3)

41 Claims 6 3 5 9 2 An aqueous latex dispersion paint composition> which is combined with a cured paint film having a solids content of 30 to 70% by weight and comprising, based on the volume of dry matter: 25 to 70% of a film-forming latex binder having a predominant weight of polymer particles in the range of 0.1 to 1.0 and having a glass transition temperature of at least about 5 ° C below the coalescence temperature, the latex binder being a polymer or copolymer of ethylenically unsaturated monomers; 10 to 60% of solid, non-porous, non-film-forming polymer particles having a weight average diameter of about 0.1 to 1.0 microns and having a glass transition temperature at least 30 ° C higher than the glass transition temperature of the binder, these non-film-forming tower particles being unsaturated monomers; 5 to 25% of an opaque pigment having a refractive index of at least 1.8; 0 to 60% opaque pigment; characterized in that the pigment volume content (PVC) of the latex paint is 30 to 75%, whereby the PVC is higher than the critical PVC measured on the basis of opacity. Aqueous latex paint combination according to Claim 1, characterized in that the pigment volume content (PVC) is from 48 to 64%. Latex paint combination according to Claim 1 or 2, characterized in that the PVC of the latex paint is greater than critical PVC, measured on the basis of opacity, and lower than critical surface porosity PVC, measured on the basis of glazing resistance.