JPH07286137A - Latex paint containing no organic solvent and based on multistage polymer - Google Patents

Abstract

PURPOSE: To provide the subject paint not containing an org. solvent and containing a multistage polymer containing a specific hydrophobic polymer domain and a hydrophobic polymer domain more hydrophilic than this domain and excellent in environmental preservability, freeze-defreezing stability, the abrasion resistance of a coating film, wet adhesion or the like.

CONSTITUTION: The objective paint contains no org. solvent and contains a multistage polymer containing (A) a hydrophobic polymer domain and (B) a hydrophobic polymer domain more hydrophilic than the component (A) and is characterized in that one of the components A and B has a glass transition temp. of -5--55°C and the other one of them has a glass transition temp. of 0-50°C and the component B is polymerized in the presence of the component A.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

The present invention is a latex paint coating which is free of organic solvents and contains a multiphase emulsion polymer synthesized from acrylic and vinyl monomers.

The desired properties of paints, namely that they can be used at temperatures low enough for application over a long seasonal range, can withstand repeated cycles of freezing and thawing, and avoid sticking or blocking and dust pickup in the intended application. The ability to form sufficiently hard films is enhanced in latex-based paints by the addition of coalescing solvents and antifreeze agents. The flocculating solvent (eg butyl carbitol acetate) and the antifreezing agent (eg propylene glycol, ethylene glycol) are volatile organic compounds, present up to 360 g per liter of paint and free of water. It is widely known that volatile organic compounds are harmful to the environment,
There is a need for latex-based paints that do not contain coalescing solvents or antifreeze agents.

Cohesive solvents are required because the polymers used in latex paints have the lowest minimum film forming temperature (MFFT) and the highest glass transition temperature (T).
because it should have g). The minimum film formation temperature is the lowest temperature at which polymer particles agglomerate with each other when the solvent-based water evaporates to form a continuous film. Polymers with low MFFT extend the temperature range over which paint can be applied. The Tg is the temperature at which a polymer changes from an amorphous, soft and viscous state to a glassy, hard and rigid state. Polymers with a high Tg form paint coatings that are hard, abrasion resistant, and blocking resistant. The coalescing solvent lowers the Tg of the polymer to give the desired low MFFT on application, and spreads the paint evenly and evaporates to give a high Tg film. Antifreeze agents are added to paints to provide freeze-thaw stability.

Many factors contribute to the polymer properties, as measured by Tg and MFFT index, such as polymer chemical composition, molecular structure, and particle morphology. Therefore, it is known that the manipulation of these factors is important to obtain an effective latex paint. In fact, a common solution in paint coatings to the problem of having a high Tg and the lowest MFFT, in addition to coatings containing coalescing solvents and antifreezes, is to formulate multi-stage polymers. This polymer is typically a hard (high Tg) core (which forms a hard film on drying) and a soft (low T).
g) Having a shell, which contributes to the low MFFT and the ability to form films at low temperatures. Although the use of multi-stage polymers for this purpose has been described in the literature, it is believed that the coatings described in the literature include flocculating solvents and antifreeze agents.

US Pat. No. 4,455,402 describes the synthesis of two-step polymers in the presence of coagulation aids to give coatings with low MFFT values. US Patent No.
5,021,469 discloses the synthesis of multiphase latex particles for gloss paints formulated in the presence of a flocculant. U.S. Pat. No. 4,654,397 describes a two-stage latex particle, i.e. a soft first stage / hard second stage synthesis, to provide a coating binder incorporated into a dissolved paint that provides good block resistance. U.S. Pat. No. 4,263,193 discloses styrene acrylic (first stage) and ethylene vinyl acetate (second stage) with excellent film forming properties, which gives good block resistance when used in paint coatings containing hexylene glycol. Describes a method for synthesizing the resin.

US Pat. No. 4,150,005 describes an essentially plasticized polymer having a water-swellable or water-soluble hydrophilic first polymer stage and a less hydrophilic second polymer stage. It has been described. US Patent No.
4,569,964 describes interpenetrating polymer networks prepared by incorporating monovinyl monomers into an already existing crosslinked hydrophilic polymer network (Polymer I).

Due to increasing environmental limits on volatile organic emissions, it has a low MFFT but good blocking resistance, abrasion resistance, and freeze-thaw stability, and There is a need for latex paint coatings that can be formulated without the need for coalescing solvents or antifreeze agents.

The present invention comprises a multi-stage polymer that is organic solvent free and has a first hydrophobic polymer domain and a second hydrophobic polymer domain that is more hydrophilic than the first polymer domain. Is a waterborne base paint made from acrylic or vinyl containing monomers.

The latex polymer particles of the present invention are characterized by a multi-stage polymer having soft (low Tg) polymer domains and hard (high Tg) polymer domains, which is characterized by subsequent stage polymerizations in the first and second stages. It is produced by a multi-step emulsion polymerization which takes place in the presence of polymer domains. Usually, this polymerization is a two-step polymerization, where either step forms a soft or rigid polymer domain. The soft polymer domains have a Tg range of -5 to -55 ° C and the hard polymer domains have a Tg range of 0 to + 50 ° C as measured by a standard differential operating calorimeter. Preferably, there is a Tg difference of 10-50 ° C. between the two stages.

In a preferred embodiment, it is desirable to form the core polymer domain around which the shell polymer domain is formed. Preferably, the core polymer domain has a glass transition temperature of about -5 ° C to -55 ° C and the shell polymer domain has a glass transition temperature of about 0-50 ° C.

The core polymer domain is hydrophobic to the extent that the polymer is substantially water insoluble and non-water swellable. To maintain the hydrophobicity of the core polymer domain, the presence of hydrophilic monomers, such as those containing chemical moieties that render the polymer water sensitive, such as amide, hydroxyl or carboxyl moieties, is minimized. Preferably, the core polymer domain comprises less than 4% by weight hydrophilic monomers, more preferably less than 2% by weight, most preferably 0.5% by weight based on the total weight of monomers.
~ 1% by weight. The shell polymer domain is more hydrophilic than the core polymer domain, but is hydrophobic to the extent that the polymer is water insoluble or non-water swellable. Therefore, the shell polymer domain, like the core polymer domain, has a minimal presence of hydrophilic monomers. Inclusion of excess hydrophilic monomer increases water sensitivity, which reduces wet adhesion and wear resistance.

The polymer particles may vary in size, but for optimum coating properties the particles should be 35
It is preferred to have an average diameter of less than 0 nm. Generally, with the polymers of the present invention, a smaller average particle size results in a more water resistant polymer.

The soft polymer domain is 90-90% of the total polymer.
It is 10% by weight, preferably 80 to 10% by weight. The rigid polymer domain is 10-90% by weight of the total polymer, preferably 20
~ 90% by weight.

Both the soft and hard polymer domains are prepared as homopolymers or copolymers from vinyl or acrylic containing monomers or combinations of vinyl and acrylic monomers. The particular choice of monomer for either domain will depend on the desired Tg range of the domain. The Tg of the polymer stage is the Fox equation 1 / Tg (polymer) = W _(a) / Tg _(a) + W _(b) / T
g _(b) + ... (In the above formula, W _(a) and W _(b) are comonomer (a) and (b)
Is the weight fraction of Tg _(a) and Tg _(b) are the glass transition temperatures of homopolymers (a) and (b)). The glass transition temperatures of various homopolymers are reported in J. Brandup and E.H.Immergut, Polymer Handbook,
2nd edition, John Wiley & Sons, New York, p.139-192 (197)
It is shown in many documents including 5).

Suitable monomers are C ₁ -C ₁₂ alkyl esters of acrylic and methacrylic acid, preferably C ₁ -C ₄ alkyl esters of acrylic and methacrylic acid, 1
Vinyl esters of linear and branched carboxylic acids having -25, preferably 2-20 carbon atoms, such as vinyl acetate, vinyl propionate, vinyl butyrate,
Vinyl valeate, vinyl 2-ethylhexyl acrylate, vinyl isononananate, vinyl laurate, vinyl versatate, and styrene and styrene-induced resistance, for example α-methylstyrene, 2-chlorostyrene, 4-chlorostyrene, 2,5- Includes dichlorostyrene and 4-methoxystyrene. Preferred monomers are methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl acetate,
Vinyl versatate, ethylene, vinyl chloride, styrene and substituted styrenes.

To optimize the wet adhesion of the final paint coating, one or both of the soft and hard polymeric domains contain a wet adhesion monomer or combination of wet adhesion monomers. This monomer is known in the art and includes aminoethyl acrylate and methacrylate, dimethylaminopropyl acrylate and methacrylate, 3-dimethylamino-2,2-dimethylpropyl-1-.
Acrylate and methacrylate, 2-N-morpholinoethyl acrylate and methacrylate, 2-N-piperidinoethyl acrylate and methacrylate, N- (3-dimethylaminopropyl) acrylamide and methacrylamide, N- (3-dimethylamino-2, 2-Dimethylpropyl) acrylamide and methacrylamide, N-dimethylaminomethylacrylamide and methacrylamide, N- (4-morpholinomethyl) acrylamide and methacrylamide, vinylimidazole, vinylpyrrolidone, N- (2-methacryloyloxyethyl) ethyleneurea , N- (2-methacryloxyacetamidoethyl) -N, N'-ethyleneurea, allylalkylethyleneurea, N-methacrylamidomethylurea, N-methacryloylurea, N- [3- (1,
3-diazacyclohexane) -2-onepropyl] methacrylamide, 2- (1-imidazolyl) ethyl methacrylate,
2- (1-imidazolidin-2-one) ethylmethacrylate, N- (methacrylamido) ethylethyleneurea (DV
2422, Rhone Poulenc) as well as allylureido wet adhesive monomers (Sipomer WAM, Rhone Poulenc). The wet-adhesive monomer is preferably present in the soft and hard polymer domains in an amount of 0.2 to 2.0% by weight of the total polymer.

To prevent intermixing between the two polymer domains and to improve the block resistance of the paint coating,
Either or both domains are polyfunctional crosslinkable monomers having two or more polymerizable carbon-carbon double bonds per molecule, such as vinyl or allyl acrylates or methacrylates, diol polyfunctional acrylates and methacrylates, and methylene. Contains low levels of bisacrylamide. The polyfunctional monomer is present in an amount of 0.01-5% by weight of total polymer.

Carboxylic acid monomers are known to impart mechanical and colloidal stability to latex particles. Usually, the paint is approximately 5 to 10% by weight and contains a sufficient amount of antifreezing agent (ethylene glycol, propylene glycol). Copolymerization of low levels of carboxylic acid monomers in the polymer backbone does not require freeze-thaw additives. For example, as an unsaturated carboxyl component, about 0.2-
The use of 4, preferably about 0.5-2.0% by weight carboxylic acid gives a latex that can withstand 5 or more freeze-thaw cycles. High levels of acid monomer increase the water sensitivity of the coating and are therefore undesirable. Examples of suitable carboxylic acid monomers, C ₃ -C ₆ monocarboxylic acids, such as methacrylic acid, acrylic acid, monomethyl maleate, and monoethyl maleate and C ₄ -C _6,
Dicarboxylic acids such as fumaric acid, maleic acid, and itaconic acid.

In a typical two-step process, the monomers for either the hard or soft polymer domains are 50-150 n.
In situ emulsion polymerized to an average particle size of m 2, then monomers for the other polymer domains are added to the polymerization medium and polymerized in the presence of the first domain polymer particles to a desired average particle size of less than 350 nm.

The polymerization of the first polymer domain is carried out by known polymerization methods in aqueous emulsion. If desired
Conventional seeding methods are used to help control the polymerization to achieve the desired average particle size and particle size distribution for the first polymer domain. The polymeric species are typically used in an amount corresponding to 0.1-4% by weight of the total polymer and are about 20-60% the size of the diameter of the first polymer domains formed. The seed latex may comprise prefabricated latex or polymer powder or may be formed in situ.
The monomer composition of the seed latex can vary, but is preferably substantially the same as the composition of the first polymer domain particles.

The monomers or comonomers used in the preparation of the first domain polymer particles and the desired species are dispersed in water by sufficient stirring to emulsify the mixture. The aqueous medium may also contain free-radical polymerization catalysts, emulsifiers (ie surfactants), or other ingredients known and commonly used as emulsion polymerization aids.

Suitable free radical polymerization catalysts are those known to accelerate emulsion polymerization and include water soluble oxidizing agents such as organic peroxides (eg t-butyl hydroperoxide,
Cumene hydroperoxide, etc.), inorganic oxidants (eg hydrogen peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, etc.) and catalysts that are activated in the aqueous phase by water-soluble reducing agents. Such catalysts are used in catalytic amounts sufficient to cause polymerization. Generally, the catalytic amount is about 0.01 to 5% by weight, based on the total monomers polymerized. Alternatively, heating or catalyst compounds that activate the polymerization, other means of forming organic groups, such as exposure to activating radiation, may be used.

Suitable emulsifiers include the anionic, cationic, and nonionic emulsifiers commonly used in emulsion polymerization. Generally, at least one anionic emulsifier is used, and one or more nonionic emulsifiers may also be used. Examples of anionic emulsifiers are alkylaryl sulfonates, alkali metal alkyl sulphates, sulphonated alkyl esters and fatty acid soaps. Specific examples include sodium dodecyl benzene sulfonate, sodium butyl naphthalene sulfonate, sodium lauryl sulfate, disodium dodecyl diphenyl ether disulfonate, N-octadecyl disodium sulfosuccinate and dioctyl sodium sulfosuccinate. The emulsifier is used in an amount to achieve a suitable emulsification and give the desired particle size and size distribution.

Other components known to be effective for various purposes in emulsion polymerization, such as acids, salts, chain transfer agents, and chelating agents may also be used in the preparation of the polymer. For example, when the polymerizable component contains a monoethylenically unsaturated carboxylic acid comonomer, acidic conditions (pH 2 to 7,
Polymerization in 2-5) is preferable. In such instances, the aqueous medium may contain known weak acids and salts thereof, which are commonly used to provide a buffer system in the desired pH range. Without the monoethylenically unsaturated carboxylic acid monomer, the pH of the aqueous medium is about 2 to about 10.

The method of mixing the polymerization components may be carried out by known monomer feeding methods such as continuous monomer addition, intermittent monomer addition, or addition of all of the monomers at once. The total amount of the aqueous medium containing the polymerization additive may be present in the polymerization vessel prior to adding the monomers, or the aqueous medium or a portion thereof may be added during the polymerization.

The polymerization to form the first polymer domain is usually about 50-110 with stirring of the emulsified mixture.
It is started by heating to a temperature of ℃, preferably 60 to 100 ℃. Polymerization is continued by maintaining the emulsified mixture at a selected temperature until the monomer is converted to polymer.

After polymerization to form the first polymer domain particles, the latex is filtered to remove the precoagulum and then storage stabilized by the addition of small amounts of known stabilizer surfactants (first Until subsequent use as dispersed first domain particles in a two-step polymerization). Preferably, the filtration and intermediate stabilization steps of the first polymer latex are eliminated by directly polymerizing the monomer for the second polymer domain. The monomer for the second polymer domain is dispersed in the aqueous medium containing the first polymer domain particles by stirring and is added in a similar manner and in the same desired polymerization aid in the preparation of the first polymer domain particles. It may be used and polymerized with stirring. In forming the second polymer domain, a conventional chain transfer agent such as bromoform, carbon tetrachloride, long chain mercaptans (such as lauryl mercaptan, dodecyl mercaptan, etc.), or other known chain transfer agents, based on total monomer, is used. about
It is preferably used in an amount of 0.1 to 3.0% by weight.

After polymerization, the solids content of the resulting aqueous heterogeneous polymer latex is adjusted to the desired level by adding water or removing water by distillation. Generally, the desired level of polymer solids content is about 20-65% by weight, preferably about 45-60% by weight, based on total weight.

The preferred particle size is achieved directly by polymerization. However, the resulting latex may be screened to remove particles outside the desired size range and narrow the particle size distribution.

For various applications, small amounts of additives such as surfactants, bactericides (eg formaldehyde), pH
It is sometimes desirable to have modifiers and defoamers in the latex, which is done by conventional methods and may be done at any point during the manufacture of the latex.

Examples The following examples are for making a two-step latex for use in paint coatings free of volatile organic compounds, paint coatings containing this latex, comparative latex and paint coatings containing comparative latex, low temperature film forming properties, A method of testing paint coatings for block resistance and washability, as well as a comparison of test results between the inventive examples and comparative examples is described.

The cast test method blocking film (6 mil (150 [mu] m)) to Leneta 3-B opacity chart on, constant temperature and humidity (22 ° C., 40 to 60% relative humidity) at 1, 2, 3 And dried for 7 days. Two
Sheets of coated charts are placed face-to-face, 0.070 kg / cm for one day at a temperature of 22 ° C and 40-60% relative humidity.
A pressure of ² (1 psi) was applied. 35 ° C for the other two charts
The pressure of 0.070 kg / cm ² was applied in the oven for 30 minutes. The blocking resistance was visually measured when the panel was peeled off by hand, and classified as follows.

Blocking resistance Grade Separation type 10 No tackiness 9 Minor tackiness 8 Very slight tackiness 7 Very slight to slight tackiness 6 Minor tackiness 5 Medium tackiness 4 Stickiness 3 Peeling off 5 to 25% of the film was torn when peeled 2 25 to 50% of the film was torn when peeled 1 50 to 75% of the film was torn when peeled 0 0 to 75 when peeled 100% film torn

The low temperature film-forming paint was conditioned in a refrigerator at 2-5 ° C. for 1 hour and a 3 mil (150 μm) film of this paint was applied to 19BR leneta.
It was applied on the chart. The film was dried overnight at 2-5 ° C and observed for cracks. It is believed that the paint forms an acceptable film when there is no difference between the film applied at 5 ° C and the film applied at room temperature (22 ° C).

Abrasion Resistance ( Washability ) A test wash panel was prepared by casting a 3 mil film of paint on a leneta chart and drying the paint for 48 hours. The dried chart was fixed to a glass panel and placed in a washing machine equipped with a bath for holding the test panel and a washing brush. The brush was prepared by soaking in water for 15 minutes and then in a wash solution of 20% wash soap (Lava) for 0.5 hour. Start the washer and moisten the panel with the wash solution. The number of strokes was recorded when a 0.5 inch (1.27 cm) black chart was shown from the test panel.

Wet Adhesion A wash panel was prepared by casting a semi-gloss alkyd base (selected as the most difficult test of wet adhesion ) on a leneta chart to 3 mil film. The chart was aged at room temperature for at least 1 week. The test latex was then cast on an aged alkyd surface to a 3 mil film and dried for 48 hours.
The dried chart was fixed to a glass panel and placed in a washing machine equipped with a bath for holding the test panel and a washing brush. The brushes were conditioned by soaking in warm water for 30 minutes and then placed in a machine holder. The test panel was placed in the bath under the brush and 200g of warm water (50 ° C) was added to the bath. The washer was started and operated for 400 stalks. If the coating is intact, use 8 g of dry abrasive (Aja
x) was placed under the brush and the machine was run for another 100 stalks. This last step was repeated until the coating was stripped, ie the test paint was stripped from the alkyd base. The number of stalks before peeling was recorded.

Composition of Paint Screening Paints It should be noted that the pigments and fillers in the paint paint impart hardness to the paint film to which it is attached. The relationship between film hardness and the amount of pigment is expressed by the pigment volume concentration, which is the partial volume of pigment in a unit volume of resin. Thus, a low PVC coating composition contains a relatively low level of pigment and a high PVC coating composition contains a high level of pigment. In low PVC paints, coating hardness is primarily determined by the Tg of the latex. In high PVC paints, extender pigments primarily determine the coating hardness. Latex in low PVC paint develops high PV because it develops film formation and final hardness.
It requires more cohesive aid than C paint. In this system, film properties and paint durability are dramatically reduced when the amount of film forming aid is low.

The paints used in the multi-stage latex test are shown below.

[Table 1]

1. BYK 156 dispersant is a trademark mixture. 2. BYK 034 defoamer is a trademark mixture. 3. Natrosol 250 HR is hydroxyethyl cellulose. 4. Titanox 2020 or Tioxide RTC-90 is rutile titanium dioxide. 5. Verwhite is a calcium carbonate pigment. 6. Rexol 25.9 is an ethoxylated nonylphenol surfactant containing 9-10 moles ethylene oxide. Rexol
45/407 is an ethoxylated octylphenol surfactant containing 40 mol ethylene oxide. 7. Acrysol RM-2020 is a water-based solventless polyurethane flow improver. 8. Kathon LX contains up to 14% 5-chloro-2 as the active ingredient
-Methyl-4-isothiazolin-3-one and 2-methyl-4-
It is a fungicide having isothiazolin-3-one. 9. Drew L-475 is a defoamer made from a blend of a silica derivative containing 100% active material and an inorganic oil. 10. ASP-170 is an aluminum silicate pigment. 11. Hegman is a unit of crushed material used in industry.

The following examples illustrate the preparation, composition and properties of various two-stage latices. Latex particle size is BI-9
0 Measured by a particle size analyzer (manufactured by Brookhaven Instruments).

Example I: Two-step all acrylic latex (soft first step / hard second step) Anionic surfactant, Alipal EP-110 (Rhone Poulenc)
Non-ionic surfactant, Igepal CA-897 (Rhone Po
ulenc) and a series of 2 containing standard wet adhesion monomer DV 2422 (Rhone Poulenc) by the following method.
A staged all-acrylic (methyl methacrylate / butyl acrylate / methacrylic acid) latex was prepared. The ingredients for one of the latexes produced are as follows. Concentrations are given in parts per 100 parts of monomer.

[0042]

[Table 2]

In a 3 liter reaction vessel equipped with a reflux condenser, addition funnel and stirrer, water, anionic surfactant and defoamer were gently stirred and heated to 78 ° C. Then 5
2.0 g of the first stage monomer mixture and 7.0 g of catalyst solution were added to the reaction vessel and the reaction mixture was kept at the same temperature for 20 minutes.
The rest of the first stage monomer mixture was added to the reaction over 2 hours. At the end of the first stage addition, the reaction was again held at 78 ° C. for 20 minutes, then the addition of the second stage monomer mixture was started,
It was added over 1 hour and 40 minutes. At the end of the second stage addition, the reaction was kept at 78 ° C for 20 minutes and then cooled to room temperature. After the reaction mixture had cooled, 0.5 g hydrogen peroxide and 0.2 g isoascorbic acid were added, bringing the temperature to 65 ° C. The pH of the obtained emulsion was adjusted to 8.0 by adding a 26.6% ammonium hydroxide aqueous solution.

The latex obtained was called 1C and had the following physical properties: A series of polymer emulsions designated 51.5% solids, 150 nm particle size, 222 mPas (cps) viscosity, and pH 8.0 1A, 1B, 1D and 1E were prepared by the above method. Examples 1A to 1E above
Each of them was cast into a 3 mil film on glass,
Dry overnight at ° C. They were then tested for tack and visually inspected for cracks. The latex properties and composition are shown in Table 3.

[0045]

[Table 3] ^a Calculated by Fox equation ^b MMA is methyl methacrylate and BA is butyl acrylate

Example II: Homogeneous All-Acrylic Latex A one-step all-acrylic latex of the same monomer composition as Latex 1C was prepared by homogenous emulsion polymerization rather than two-step polymerization. The latex obtained is called 1F and has the following physical properties: 51.5% solids, 145 nm particle size, and pH.
Had 8.0.

Example III: All-acrylic latex for coatings with coating aids 52 parts methyl methacrylate (MMA) and 48 parts butyl acrylate (BA) monomer composition, by the method of Example I and the surfactant system. A one-step all-acrylic latex was produced by a semi-continuous polymerization method. The latex obtained is called 1G and has the following physical properties: 51.1% solids, 23
0mPas (cps) viscosity, 160 ° C Tg, 158nm particle size, and pH
Had 8.0.

Example IV: Test Results for All Acrylic Latex in Paint Paints Latexes 1A-1E were blended into paint paints containing no volatile organic compounds and tested for Latex 1F, Latex 1G for low temperature film forming and blocking resistance properties. And a composition containing a flocculant and a commercial paint. The results are shown in Table 4. The result is that the block resistance of the two-stage latex 1C is superior to that of the homogeneous latex 1F, and the agglomerated all acrylic 1G and the commercial semi-gloss paint 1H are used.
It is shown to be comparable to.

Two Stage All Acrylic Latex 1 of Example I
The paint properties of C were compared to the aggregated all acrylic latex 1G of Example III. The results are shown in Table 5. The results show that the two-stage latex is comparable in film forming and freeze-thaw stability to paints containing coagulation aids and is superior in abrasion resistance and wet adhesion.

[0050]

[Table 4] ^a homogeneous composition of 2-stage latex 1C 42.5 MMA / 57.5 BA ^b homogeneous all acrylic latex 1G: 52 MMA / 48 BA
No coagulation aid ^c Homogeneous all acrylic latex 1G: 52 MMA / 48 BA agglomerated with 6% Texanol, a product of Eastman Kodak ^d Commercial semi-gloss paint with coagulation aid

[0051]

[Table 5]

Example V: Two-stage all acrylic latex (hard first stage / soft second stage) First stage monomer composition is 33.8 MMA / 31.2 BA / 0.65 MAA and second stage composition is 11.2 MMA / 23.8 BA / A two-stage all-acrylic (methyl methacrylate, butyl acrylate, and methacrylic acid) latex was prepared using the method and surfactant system described in Example I, except at 0.35 MAA. This latex was designated 2A and had the following physical properties: 52.8% solids, pH 8.0, 163 nm particle size.

Example VI: Homogeneous Copolymer A one-step all acrylic latex of the same monomer composition as Latex 2A was prepared by homogenous emulsion polymerization using the same surfactant system as the two-step polymerization of Example I. The latex obtained was designated 2B and had the following physical properties: 51.2% solids, pH 8.0, and 140 nm particle size.

Example VII: Test Results of Hard First Stage / Soft Second Stage All Acrylic Latex in Paint Coatings Latex 2A and 2B were incorporated into Paint Screening Coating I and tested for block and low temperature film forming properties. The results are shown in Table 6, which shows that the two-stage latex has better properties than the homogeneous latex,
It is shown to be comparable to paints containing a coalescing solvent.

[0055]

[Table 6] ^a two-domain composition ^b homogeneous composition of latex 2A: 45 MMA / 55 BA / 1 MMA ^c all-acrylic latex 1G without coagulation aid ^d all-acrylic latex with 6% coagulation aid 1G ^{e with} coagulation aid Commercial semi-gloss paint

Example VIII: Two-Step Styrene-Acrylic Latex A series of two-step styrene / methyl methacrylate / butyl acrylate latices were prepared using the polymerization method of Example I and the surfactant system. This latex is referred to as 3A, 3B and 3C. The latex composition and properties are shown in Table 7.

Example IX: Homogeneous Styrene-Acrylic Latex A homogeneous styrene / methyl methacrylate / butyl acrylate terpolymer latex was synthesized using the method of Example I and the surfactant system, except that a first stage pre-emulsion feed was used. This monomer composition is latex 3
Same as B. The obtained latex is called 3D,
It has the following physical properties: 53.0% solids, 219nm particle size, pH
It had 8.0, 0.006% grit (200M). The physical properties are shown in Table 7.

Example X: Styrene-acrylic latex compounded with flocculation aid A styrene / acrylic latex was synthesized using a one-step pre-emulsion feed. The latex obtained has a monomer composition of styrene 54.4 / butyl acrylate 45.6 and is referred to as 3E. It had the following physical properties: 53% solids, pH 8.0, 175 nm particle size, 0.0032% grid (200M) and Tg 20.4 ° C.

[0059]

[Table 7] ^a 3B homogeneous composition ^b Calculated by Fox Kishi

Example XI: Styrene / Acrylic Latex Test Results in Paint Paints Latex 3A-3E was Paint Screening Paint I
And II and tested for block resistance and low temperature film forming properties. The results are shown in Table 8. This is 2
It is shown that staged styrene / acrylic latex 3B exhibits film forming properties and excellent block resistance comparable to agglomerated Sample 3E.

Two-stage styrene / acrylic latex 3B
Paint properties of styrene / acrylic polymer 3E were compared. The results are shown in Table 9. This shows that the two-stage latex is comparable to the styrene / acrylic latex compounded with the flocculating solvent.

[0062]

[Table 8] ^a homogeneous composition of latex 3B ^b styrene-acrylic latex containing 6% Texanol

[0063]

[Table 9]

Example XII: Two-Step Vinyl Ester Terpolymer Latex A series of two-step vinyl ester copolymers, designated 4A-4C, were prepared using the method of Example I and the surfactant system. The latex properties and composition are shown in Table 10.

Example XIII: Homogeneous Vinyl Ester Latex A homogenous one stage vinyl ester latex was prepared using the monomer composition of Latex 4B and the surfactant system. The latex obtained was called 4D and had the following physical properties: 56.0% solids, 234 nm particle size and pH 8.0.

[0066]

[Table 10] ^a Calculated according to Fox equation ^b Monomer: VA is vinyl acetate, BA is syrup, VV-10 is vinyl ester of unsaturated monocarboxylic acid containing 10 carbon atoms, V2E -H is vinyl 2-ethylhexanoate

Example XIV: Test Results of Vinyl Ester Latex in Paint Paint Latex 4A-4B and Nacan Products Ltd, Canada
Commercially available 6% Texanol agglomerated commercial vinyl acrylic resin was incorporated into Paint Screening Paint I and tested for block resistance and low temperature film forming properties. The results are shown in Table 11 and show that the two-stage latices 4A and 4B are superior in block resistance to commercial paints containing flocculants and paint coatings containing homogeneous polymer 4D.

[0068]

[Table 11] ^a Homogeneous polymerization of latex 4B ^b Nocan's commercial vinyl acrylic resin agglomerated with 6% Texanol

Example XV: All Acrylic with Wet Adhesive /
Vinyl-Acrylic Terpolymer A soft all acrylic / hard vinyl-acrylic two-stage terpolymer was prepared using the surfactant system and method of Example I. Wet adhesive monomer (DV 2422) in an amount of 0.5% by weight of total polymer was polymerized to the first stage polymer domain. This latex is referred to as 5A and 5B. The latex properties and composition are shown in Table 12.

[0070]

[Table 12] ^a Calculated by Fox equation

Example XVI: Test Results of All-Acrylic / Vinyl-Acrylic Latex in Paint Paints Commercial paints in which latexes 5A and 5B were incorporated into paint screening paints I and II and contained anti-blocking and low temperature film forming properties with each other and a flocculant. Compared to 4E. The results are shown in Table 13, which is Latex 5B.
Is an excellent paint and shows that Latex 5A is comparable to commercial products containing a flocculant.

Latex 5A and 5B were blended into Paint Screening Paints I and III and compared to a commercial paint containing a flocculant (Nacan's vinyl acrylic) and All Acrylic Latex 1G blended with a flocculating solvent. The results are shown in Table 14. This shows that the two-stage polymer is excellent for use in paints.

[0073]

[Table 13] ^a Nocan's vinyl acrylic latex agglomerated with 6% Texanol

[0074]

[Table 14] ^a Nocan's vinyl acrylic latex agglomerated with 6% Texanol ^b All acrylic latex agglomerated with 6% Texanol

The above examples represent preferred embodiments of the invention, but not all embodiments.

 ─────────────────────────────────────────────────── —————————————————————————————————————— Inventor Lean Fan Canada, Ontario K 4 Z 3 P 4, Mississauga, Bristol Road East # 155 99 (72) Inventor William Carly, Canada N 3B2 -3, Elmira, Bowman Street 7 (72) Inventor Judy Martinamisan, Ontario, Canada El 6wai 2K 4, Brampton, Steels Avenue West No. 1210 220

Claims (18)

[Claims] 1. A first polymer comprising an organic solvent free multistage polymer comprising a first hydrophobic polymer domain and a second hydrophobic polymer domain which is more hydrophilic than the first polymer domain. One of the domain and the second polymer domain has a glass transition temperature of about −5 ° C. to −55 ° C., the other has a glass transition temperature of about 0 to 50 ° C., and the second polymer domain is the first Latex paint paints polymerized in the presence of the polymer domain of. 2. A multistage polymer comprising C ₁ -C ₁₂ alkyl esters of acrylic and methacrylic acid, vinyl esters of linear and branched C ₁ -C ₂₅ carboxylic acids, styrene, C.
The latex paint coating composition according to claim 1, comprising a reaction product of a monomer selected from the group consisting of _1- C ₄ alkyl-substituted styrene and halogenated styrene. 3. A monomer selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl acetate, ethylene, vinyl chloride, and styrene. Latex paint paint described. 4. The multistage polymer comprises 0.2 to 2.
The latex paint coating composition of claim 2 further comprising a wet adhesion monomer polymerized to the multi-stage polymer in an amount of 0% by weight. 5. The wet adhesive monomer is aminoethyl acrylate and methacrylate, dimethylaminopropyl acrylate and methacrylate, 3-dimethylamino-.
2,2-Dimethylpropyl-1-acrylate and methacrylate, 2-N-morpholinoethyl acrylate and methacrylate, 2-N-piperidinoethyl acrylate and methacrylate, N- (3-dimethylaminopropyl) acrylamide and methacrylamide, N -(3-Dimethylamino-
2,2-Dimethylpropyl) acrylamide and methacrylamide, N-dimethylaminomethylacrylamide and methacrylamide, N- (4-morpholinomethyl) acrylamide and methacrylamide, vinylimidazole, vinylpyrrolidone, N- (2-methacryloyloxyethyl)
Ethyleneurea, N- (2-methacryloxyacetamidoethyl) -N, N'-ethyleneurea, allylalkylethyleneurea, N-methacrylamidomethylurea, N-methacryloylurea, N- [3- (1,3-dia Thecyclohexane) -2-
Onpropyl] methacrylamide, 2- (1-imidazolyl) ethyl methacrylate, 2- (1-imidazolidine-2-
ON) Ethyl methacrylate, N- (methacrylamide)
The latex paint paint according to claim 4, which is selected from the group consisting of ethyl ethylene urea and allyl ureide. 6. The multistage polymer comprises 0.01 to 5 of all polymers.
The latex paint coating according to claim 2, further comprising a polyfunctional crosslinkable monomer having two or more polymerizable carbon-carbon double bonds per molecule polymerized to the multi-stage polymer in an amount of% by weight. . 7. The polyfunctional crosslinking monomer is vinyl acrylate, vinyl methacrylate, allyl acrylate,
The latex paint paint according to claim 6, which is selected from the group consisting of allyl methacrylate, diol multifunctional allyl acrylate and methacrylate, and methylene-bisacrylamide. 8. The multistage polymer comprises 0.2 to 4.
0% by weight of C ₃ polymerized into this multistage polymer
To C ₆ monocarboxylic acid and C _{4 to} C ₆ dicarboxylic acid, further comprising a carboxylic acid selected from the group consisting of:
Latex paint paint described. 9. A multi-layer comprising an organic solvent-free hydrophobic core polymer domain having a glass transition temperature of about −5 ° C. to −55 ° C. and a hydrophobic shell polymer domain having a glass transition temperature of about 0 to 50 ° C. A stepwise core / shell polymer, wherein the shell domain is more hydrophilic than the core domain, each of the core domain and the shell domain is a C ₁ -C ₁₂ alkyl ester of acrylic acid and methacrylic acid, linear and branched C ₁ -C ₂₅ vinyl esters of carboxylic acids, styrene, C ₁ -C ₄ alkyl-substituted styrenes,
And a latex paint containing a reaction product of a monomer selected from the group consisting of halogenated styrene. 10. A multi-stage polymer comprising a first hydrophobic polymer domain and a second hydrophobic polymer domain that is more hydrophilic than the first polymer domain, the first polymer domain and the second polymer. One of the domains has a glass transition temperature of about -5 ° C to -55 ° C, the other has a glass transition temperature of about 0 to 50 ° C, and the second polymer domain is in the presence of the first polymer domain. A multi-stage polymer polymerized in. 11. The polymer is a C ₁ -C ₁₂ alkyl ester of acrylic acid and methacrylic acid, linear and branched C ₁
~ C ₂₅ vinyl ester of carboxylic acid, styrene, C ₁ ~
The multi-stage polymer according to claim 10, comprising a reaction product of a monomer selected from the group consisting of C ₄ alkyl- and alkoxy-substituted styrenes, and halogenated styrenes. 12. The monomer according to claim 11, wherein the monomer is selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl acetate, ethylene, vinyl chloride, and styrene. The described multi-stage polymer. 13. The multi-stage polymer of claim 10, further comprising polymerized wet adhesive monomer in an amount of 0.2 to 2.0% by weight of total polymer. 14. The wet adhesive monomer is aminoethyl acrylate and methacrylate, dimethylaminopropyl acrylate and methacrylate, 3-dimethylamino.
-2,2-dimethylpropyl-1-acrylate and methacrylate, 2-N-morpholinoethyl acrylate and methacrylate, 2-N-piperidinoethyl acrylate and methacrylate, N- (3-dimethylaminopropyl) acrylamide and methacrylamide, N- (3-dimethylamino-
2,2-Dimethylpropyl) acrylamide and methacrylamide, N-dimethylaminomethylacrylamide and methacrylamide, N- (4-morpholinomethyl) acrylamide and methacrylamide, vinylimidazole, vinylpyrrolidone, N- (2-methacryloyloxyethyl)
Ethyleneurea, N- (2-methacryloxyacetamidoethyl) -N, N'-ethyleneurea, allylalkylethyleneurea, N-methacrylamidomethylurea, N-methacryloylurea, N- [3- (1,3-dia Thecyclohexane) -2-
Onpropyl] methacrylamide, 2- (1-imidazolyl) ethyl methacrylate, 2- (1-imidazolidine-2-
ON) Ethyl methacrylate, N- (methacrylamide)
The multi-stage polymer according to claim 13, which is selected from the group consisting of ethyl ethylene urea and allyl ureido. 15. An amount of 0.01 to 5% by weight of the total polymer,
11. The multi-stage polymer of claim 10, further comprising a polymerized polyfunctional crosslinkable monomer having two or more polymerizable carbon-carbon double bonds per molecule. 16. The polyfunctional crosslinkable monomer of claim 15, wherein the polyfunctional crosslinkable monomer is selected from the group consisting of vinyl acrylate, vinyl methacrylate, allyl acrylate, allyl methacrylate, diol polyfunctional allyl acrylate and methacrylate, and methylenebisacrylamide. Staged polymer. 17. Polymerized C ₃ -C ₆ monocarboxylic acid and C ₄ -C in an amount of 0.2-4.0% by weight of the total polymer.
The multi-stage polymer according to claim 10, further comprising a carboxylic acid selected from the group consisting of ₆ dicarboxylic acids. 18. A hydrophobic core polymer domain having a glass transition temperature of about -5 ° C to -55 ° C, and about 0-50 ° C.
A hydrophobic shell polymer domain having a glass transition temperature of, wherein the shell domain is more hydrophilic than the core domain, and each of the core polymer domain and the shell polymer domain is C ₁ -C ₁₂ alkyl of acrylic acid and methacrylic acid. Ester, linear and branched chains C ₁ -C
₂₅ carboxylic acid vinyl ester, styrene, C ₁ -C ₄
A multi-stage core / shell polymer comprising a reaction product of a monomer selected from the group consisting of alkyl- and alkoxy-substituted styrenes, and halogenated styrenes, wherein the shell polymer domain is polymerized in the presence of the core polymer domain.