WO1995001381A1 - Polymer blends comprising sulfonate group-containing surfactants - Google Patents

Polymer blends comprising sulfonate group-containing surfactants Download PDF

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WO1995001381A1
WO1995001381A1 PCT/US1994/006552 US9406552W WO9501381A1 WO 1995001381 A1 WO1995001381 A1 WO 1995001381A1 US 9406552 W US9406552 W US 9406552W WO 9501381 A1 WO9501381 A1 WO 9501381A1
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polymer blend
percent
surfactant
acrylate
acid
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PCT/US1994/006552
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French (fr)
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Chih-Herng James Su
Peter Webb Raynolds
Hieu Duy Phan
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Eastman Chemical Company
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/10Printing inks based on artificial resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/02Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/04Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K5/00Use of organic ingredients
    • C08K5/36Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41Compounds containing sulfur bound to oxygen
    • C08K5/42Sulfonic acids; Derivatives thereof

Abstract

Disclosed are polymer blends of polyesters or polyesteramides, a styrene polymer, and a sulfonate group-containing surfactant or a nonylphenol ethoxylated surfactant. The blends are preferably prepared by polymerizing a styrene monomer in the presence of the polyester or polyesteramide.

Description

POLYMER BLENDS COMPRISING SULFONATE GROUP-CONTAINING SURFACTANTS

Cross—Reference to Related to Application This application is related to U.S. Serial Number

08/085,221, entitled "Polymer Blends Giving High Gloss", by Peter . Reynolds, filed on even date herewith.

Field of the Invention The present invention concerns polymer blends of a polyester or polyestera ide, a styrene polymer, sulfonate group—containing surfactants or nonylphenol ethoxylated surfactants and mixtures thereof.

Description of the Related Art

There continues to be much interest in water- dispersed polymers for inks because of the problems associated with solvent emissions from solvent—based inks. Certain polyesters are water—dispersible as a result of sulfonate groups on the polyester backbone. These polyesters have been described in, for example, U. S. Patents 3,734,874; 3,546,008 and 3,779,993.

Water—dispersible polyesters have been used in textile sizes and have been used to develop aqueous inks. Inks containing a water—dissipatable polyester are well known in the art as disclosed in U. S. Patents 4,704,309 and 4,738,785. Water—dispersed polyester- polystyrene blends useful as coatings and adhesives have been generally disclosed in U. S. Patents 4,939,233 and 4,946,932. These inks have many desirable features, including excellent gloss and color development, good rewet characteristics, and low odor. However, because of the wide range of printing conditions and substrates used in the printing industry, a given ink formulation can have ideal properties for some applications and poor properties for other applications. High gloss and block resistance are properties that are highly desirable for many ink applications. It would be highly desirable to have a material that imparts good gloss, and/or block resistance to films prepared from aqueous polyester dispersions while maintaining the other advantages associated with the use of the water—dispersible polyester. A water—dispersed polyester—polystyrene blend having an additional small amount of "hydrophilic vinyl polymer" is disclosed in Japanese Kokai Patent Application No. Hei 3[1991]-146549. The use of a non- ionic unsaturated polyester as a surfactant in the polymerization of styrene to obtain a coarse dispersion is disclosed in European Patent Application EP 400,410. A phthalic anhydride—5—sodiosulfoisophthalic acid— tetraethyleneglycol condensation polymer was used as a surfactant and dispersing polymer for dyes (K. M. Chen and H. J. Liu, J. Appl. Poly. Sci. , 1987, No. 34, pp.

1879—1888) , and this surfactant was used in an emulsion polymerization with styrene (T. L. McCartney and I. Piir a, Polymer Bull., April 1990, No. 23, pp. 367—371) The need for low—odor, zero—VOC (volatile organic solvent content) emulsion polymers has been described in a review article of new developments in water—borne acrylics for the printing ink industry (H. J. Hartschuh, American Ink Maker, January 1991, pp. 34 ff.). This invention addresses all of these needs, and achieves the desired result with the use of a water—dispersible polyester as both a polymeric surfactant and coalescing aide and an additional sulfonate—containing surfactant.

A water dispersible polyester—polystyrene blend derived from polyester containing 4—8 mole % of an unsaturated dicarboxylic acid is described in U. S. t Patent 4,119,680.

Summary of the Invention One object of the present invention is to provide water—dispersed polyester—styrene blends, useful as coatings and inks that exhibit high gloss and excellent heat blocking characteristics.

Another object of the present invention is to provide water-dispersed polyester—styrene blends having low odor levels, and substantially no volatile organic solvent problems.

Yet another object of the present invention is to provide a method of producing the useful polyester— styrene blends of the present invention.

Accordingly, one form of the present invention relates to a polymer blend comprising (A) 2 weight percent to 50 weight percent of a water— dispersible sulfonate group—containing polyester or polyester amide comprising;

(a) aromatic and aliphatic and ionic dicarboxylic acids such that

(i) the mole percent of ionic diacid is 7 mole percent to 25 mole percent of the total diacids, and

(ii) the mole percent of aromatic diacids is equal to or greater than 50% of the total diacids,

(b) diols comprising no more than 50 mole percent, more preferably 50 mole percent, of the total diols being selected from the group consisting of 1,4—cyclohexanedimethanol, 1,3—cyclohexanedimethanol, and 1,2—cyclohexanedimethanol; (B) 45 to 97.5 weight percent of a styrene polymer comprising:

(a) 30 to 100 mole percent of repeating units from a styrene compound, and (C) 0.5 to 5 weight percent of a sulfonate group- containing surfactant of (A) wherein said surfactant is different than said polyester or polyesteramide of component (A) or a nonylphenol ethoxylated surfactant and mixtures thereof. Another form of the present invention relates to a polymer blend comprising

(A) 2 weight percent to 30 weight percent of a water— dispersible sulfonate group—containing polyester or polyester amide comprising; (a) aromatic and aliphatic and ionic dicarboxylic acids such that (i) the mole percent of ionic diacid is 7 mole percent to 25 mole percent, and (ii) the mole percent of aromatic diacids is equal to or greater than 50%,

(b) diols comprising no more than 50 mole percent of the total diols being selected from the group consisting of 1,4—cyclohexanedimethanol, 1,3—cyclohexanedimethanol, and 1,2—cyclohexanedimethanol;

(B) 65 to 97.5 mole percent of a styrene polymer comprising:

(a) 30 to 100 mole percent of repeating units from a styrene compound, and (C) 0.5 to 5 weight percent of a sulfonate group- containing surfactant wherein said surfactant is different than said polyester or polyesteramide of component (A) or a nonylphenol ethoxylated surfactant and mixtures thereof. Yet another form of the present invention relate., to a polymer blend comprising

(A) 2 weight percent to 50 weight percent of a water— dispersible sulfonate group—containing polyester or polyester amide comprising;

(a) aromatic and aliphatic and ionic dicarboxylic acids such that

(i) the mole percent of ionic diacid is 7 mole percent to 25 mole percent, and (ii) the mole percent of aromatic diacids is equal to or greater than 50 %,

(b) diols comprising no more than 50 mole percent of the total diols being selected from the group consisting of 1,4—cyclohexanedimethanol, 1,3—cyclohexanedimethanol, and

1,2—cyclohexanedimethanol;

(B) 45 to 97.5 mole percent of a styrene polymer comprising:

(a) greater than 50 mole percent of a styrene monomer, and

(b) the balance consisting of repeating units from at least one other ethylenically unsaturated monomer, and

(C) 0.5 to 5 weight percent of a sulfonate group— containing surfactant wherein said surfactant is different than said polyester or polyesteramide of component (A) or a nonylphenol ethoxylated surfactant and mixtures thereof. A further form of the invention relates to a method of preparing a water—dispersed polymer blend comprising the steps of

(A) preparing an aqueous polymerization mixture by contacting (1) a water—dispersible sulfonate group—containing polyester or polyesteramide. (2) one or more monomers, wherein said monomers: comprise:

(a) 50 to 100 mole percent of a styrene monomer, (3) a polymerization initiator, and (4) water,

(B) polymerizing said monomers to provide said water— dispersible polymer blend, and

(C) during step (B) , adding from 0.5 to 5 weight percent of a sulfonate group—containing surfactant wherein said surfactant is different than said polyester or polyesteramide of step (A) (1) or a nonylphenol ethoxylated surfactant and mixtures thereof. Preferred forms of the invention, as well as other embodiments, objects, features and advantages of this invention, will be apparent from the following detailed description of the present invention.

Description of the Preferred Embodiments of the Invention

Polystyrene is inexpensive. It produces coatings and inks with many desirable characteristics. The residual monomer does not have an offensive odor (in contrast to many acrylates) , and glossy films are produced when the latex is applied to a surface. One serious deficiency of pure polystyrene latexes is that they do not form films which are physically robust and resistant to rubbing and abrasion. This deficiency occurs because, during drying, the individual particles of polystyrene in the latex do not fuse together to form a strong, continuous film in the absence of special additives called coalescing aides.

Many coalescing aides are slow-evaporating oxygenated organic compounds that act by softening the polymeric particles and allowing them to fuse togethe. into a continuous film. The coalescing aide then evaporates over a period of days or weeks, leaving a hard, abrasion resistant film. While commonly used to achieve strong films, these coalescing aides suffer from certain shortcomings. They contribute to the volatile organic content (VOC) of the coating; they occasionally have a noticeable odor; and they soften the ink or coating film until they evaporate over a period of days or week.

Water—dispersed polyesters may be used as coalescing aides. They are similar to the just- mentioned coalescing aides in that they are thought to facilitate fusing together of individual polystyrene particles. Polyesters differ from the coalescing aides just mentioned in that they are permanently incorporated into the polymer film. This can lead to other undesirable characteristics, one of which is decreased blocking temperature. At the "blocking temperature", two coated surfaces will stick together (an undesirable characteristic) under given conditions of temperature, time and humidity. It would be advantageous to design a water dispersible polyester that act as a coalescing aide but which would exhibit a high blocking temperature.

In U.S. Serial Number 08/085,221, entitled "Polymer Blends Giving High Gloss" by Peter W. Raynolds, filed concurrently herewith, it is disclosed that a good film forming aide for polystyrene is a brittle, ionic polyester polymer that is immiscible in polystyrene. The polyesters used in the present invention are not good solvents for polystyrene, yet they aid in film forming.

The water—dispersible polyesters useful in this invention show further utility in emulsion polymeriza- tion by their action as colloidal stabilizers. The polyesters allow for the partial or complete elimination of added surfactants during the emulsion polymerization. It has further been surprisingly found that the use of sulfonate group-containing surfactants which are different than the polyester or polyesteramide of the invention produce good films having high glass transition temperature 80 — 98°C and high gloss while maintaining excellent wet block properties as pigmented inks without additional coalescing aids.

The polyesters useful in this invention are water- dispersible as a result of sulfonate groups on the polyester backbone. Suitable compositions are those described in U. S. Patents 3,734,874; 3,546,008; 4,335,220 and 3,779,993, incorporated herein by reference. Basically, these polyesters and polyester¬ amides are described as having carbonyloxy inter¬ connecting groups in the linear molecular structure wherein up to 80 percent thereof may be carbonylamido linking groups, the polymer having an inherent viscosity of at least 0.1, and the polymer consisting essentially of the following components or ester forming or ester- amide forming derivatives thereof;

(a) at least one difunctional dicarboxylic acid which is aromatic aliphatic, and ionic or mixture thereof, such that;

(i) the mole percent of ionic diacid is 7 mole percent to 25 mole percent of the total diacids, and (ii) the mole percent of aromatic diacids is equal to or greater than 50%;

(b) from 2 to 25 mole percent, based on a total of all acid, hydroxyl and amino equivalents being equal to 200 mole percent, of at least one difunctional sulfomonomer containing at least one metal sulfonate group attached to an aromatic nucleus wherein the functional groups are hydroxy, carboxyl or amino; and (c) at least one glycol or a mixture of a glycol and a diamine having two —NRH groups, the glycol containing two —OH groups.

Dispersibility is related to the mole percent of sulfomonomer.

The polymer may contain at least one difunctional reactant selected from a hydroxycarboxylic acid having one -OH, and aminocarboxylic acid having one —NRH group, an amino alcohol having one —CR2—OH group and one —NRH or mixtures thereof, wherein each R is an H atom or an alkyl group of 1 to 4 carbon atoms. The dicarboxylic acid component of the polyester or polyesteramide comprises aliphatic dicarboxylic acids, ionic dicarboxylic acids, aromatic dicarboxylic acids, or mixtures of two or more of these acids. Examples of such dicarboxylic acids include succinic; glutaric; adipic; azelaic; sebacic; itaconic; 1,4—cyclohexane¬ dicarboxylic; phthalic; terephthalic and isophthalic.

It is preferred for the blends of the invention that the aromatic dicarboxylic acids are selected from the group consisting of terephthalic acid, isophthalic acid, phthalic acid and mixtures thereof.

It is preferred that the aliphatic dicarboxylic acids useful in the blends of the invention are selected from the group consisting of 1,4—cyclohexanedicarboxylic acid, 1,3—cyclohexanedicarboxylic acid, 1,2—cyclohexane— dicarboxylic acid, HOOC —(CH2)n —COOH, where n = 2—10, and mixtures thereof.

It is also preferred that the ionic dicarboxylic acids useful in the blends of the invention are selected from the group consisting of 5—sulfoisophthalic acid, 4—sulfophthalic acid and mixtures thereof. The mole percent of ionic diacid is preferably 7. mole percent to 25 mole percent of the total diacids and the mole percent of aromatic diacids is equal to or greater than 50 % of the total diacids. It should be understood that use of the corresponding acid anhydrides, esters, and acid chlorides of these acids is included in the term "dicarboxylic acid". Other suitable acids are disclosed in U. S. Patent 3,779,993. The difunctional sulfo—monomer component of the polyester or polyesteramide may advantageously be a dicarboxylic acid or an ester thereof containing a metal sulfonate group or a glycol containing a metal sulfonate group or a hydroxy acid containing a metal sulfonate group. The metal ion of the sulfonate salt may be Na+, Li+, K+ and the like. When a monovalent alkali metal ion is used, the resulting polyesters or polyesteramides are less readily dissipated by cold water and more readily dissipated by hot water. -Amines (NH4Θ, ΘR-L R2 R3 R4) where R=H, alkyl, benzyl, aromatic. The sulfo— monomer may also be the salt of these amines. When a divalent or a trivalent metal ion is used, the resulting polyesters or polyesteramides are not ordinarily easily dissipated by cold water but are more readily dissipated in hot water. It is possible to prepare the polyester or polyesteramide using, for example, as sodium sulfonate salt and later by ion—exchange replace this ion with a different ion, and thus alter the characteristics of the polymer. The difunctional monomer component may also be referred to as a difunctional sulfomonomer and is further described hereinbelow.

Advantageous difunctional sulfo—monomer components are those wherein the sulfonate salt group is attached to an aromatic acid nucleus such as benzene. naphthalene, diphenyl, oxydiphenyl, sulfonyldiphenyl ,-.r methylenediphenyl nucleus. Preferred results are obtained through the use of sodiosulfophthalic acid, sodiosulfoterephthalic acid, sodiosulfoisophthalic acid, 4—εulfonaphthalene—2,7—dicarboxylic acid, and their esters; metallosulfoaryl sulfonate as described in U. S. Patent 3,779,993.

Particularly superior results are achieved when the difunctional sulfo-monomer component is 5-sodiosulfo- isophthalic acid or its esters and the glycol is a mixture of ethylene glycol or 1,4—cyclohexanedimethanol with diethylene glycol.

When the sulfonate—containing difunctional monomer is an acid or its ester, the polyester or polyesteramide should contain at least 8 mole percent of said monomer based on total acid content, with more than 10 mole percent giving particularly advantageous results. Total acid content is calculated as the sum of (1) moles of component (a) namely dicarboxylic acids, (2) one—half of the moles of carboxyl—containing compounds of component (d) , (3) moles of component (c) which are dicarboxylic acids, and (4) one—half of the moles of component (c) which are monocarboxy—containing compounds.

Useful glycols for preparing copolyesters may consist of aliphatic, alicyclic, and aralkyl glycols. Examples of these glycols include ethylene glycol; propylene glycol; 1,3—propanediol; 2,4—dimethyl—2— ethylhexane—1,3—diol; 2,2—dimethyl—1,3—propanediol; 2—ethyl—2—butyl—1 ,3—propanediol; 2—ethyi—2—isobutyl—1,3— propanediol; 1,3—butanediol, 1,4—butanediol; 1,5— pentanediol; 1,6—hexanediol; 2,2,4—trimethyl—1,6— hexanediol; thiodiethanol; 1,2—cyclohexanedimethanol; 1,3—cyclohexanedimethanol; 1,4—cyclohexanedimethanol; 2,2,4,4—tetramethyl—1,3—cyclobutanediol; p—xylylenediol, 2-methyl-l,3-propanediol, and 2,2—dimethyl—3- hydroxypropyl—2,2—dimethyl—3—hydroxypropionate.

It is preferable that said glycols are diols comprising no more than 75 mole percent, more preferably 50 mole percent, of the total diols being selected from the group consisting of 1,4—cyclohexanedimethanol, 1,3— cyclohexanedimethanol, and 1,2—cyclohexanedimethanol. It is also preferable that the remainder of the mole percentage of the total diols is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol,

1,5—pentanediol, 1,4—butanediol, 1,3—propanediol,

1,3—cyclobutanediol, 2,2—dimethyl—3—hydroxypropy1—2,2- dimethyl—3—hydroxypropionate, butylethylpropanediol and mixtures thereof. If ethylene glycol is one component of the glycol mixture, superior results are achieved if at least 30% by weight of one other glycol is used. Useful polyesters include those wherein the sulfomonomer is a dicarboxylic acid and constitutes 7 to 35 mole percent, preferably 10 to 25 mole percent based on the sum of (1) the moles of the total dicarboxylic acid content of components (a) and (b) , and (2) one—half of the moles of any hydroxycarboxylic acid. Other useful polyesters include those wherein the sulfomonomer is a glycol and constitutes 7 mole percent to 35 mole percent based on the sum of the total glycol content measured in moles of (b) and (c) , and one—half of the moles of any hydroxycarboxylic acid. Thus, a preferred polyester or polyesteramide useful herein comprises a polymer blend wherein said water—dispersible polyester or polyesteramide comprises a polymer having carbonyloxy linking groups in the linear molecular structure wherein up to 80 percent of the linking groups are carbonyla ido linking groups, the polymer having an inherent viscosity of from 0.1 to 1.0 measured in a 60/40 parts by weight solution of

Figure imgf000015_0001
at 25°C and at a concentration of 0.5 gram of polymer in 100 mL of the solvent, the polymer containing substantially equimolar proportions of acid equivalents (100 mole percent) to hydroxy and amino equivalents (100 mole percent) , the polymer comprising the reaction products of reactants selected from (a) , (b) , (c) , and (d) , or the ester forming or esteramide forming derivatives thereof, as follows, wherein all stated mole percentages are based on the total of all acid, hydroxyl, and amino equivalents being equal to 200 mole percent:

(a) at least one difunctional dicarboxylic acid; (b) from 7 to 25 mole percent of at least one difunctional sulfomonomer containing at least one metallic sulfonate group or nitrogen—containing nonmetallic sulfonate group attached to an aromatic or aliphatic nucleus wherein the functional groups are hydroxy, carboxyl, or amino;

(c) at least one difunctional reactant selected from a glycol or a mixture of a glycol and diamine having two —NRH groups, the glycol containing two —OH groups; and (d) from 0 to 40 mole percent of difunctional reactant selected from hydroxycarboxylic acids having one — C(R)2—OH group, aminocarboxylie acids having one — NRH group, amino—alcohols having one —C(R)2—OR group and one —NRH group, or mixtures of said difunctional reactants; wherein each R in the (c) and (d) reactants is a hydrogen atom or an alkyl group of 1 to 4 carbons. More preferably the polyester has an inherent viscosity of from 0.20 to 0.38, an acid moiety of from 75 to 92 mole percent isophthalic acid and/or terephthalic acid and, conversely, from 25 to 8 mole percent 5—sodiosulfoisophthalic acid, and a glycol moiety of from 50 to 100 mole percent diethylene glycol, 2,2-dimethyl-l,3-propanediol, ethylene glycol and, conversely, from 50 to 0 mole percent 1,4—cyclohexanedimethanol, 1,3—cyclohexanedimethanol, 1,2—cyclohexanedimethanol, or mixtures thereof.

Even more preferably, the polyester comprises an acid moiety comprising from 80 to 83 mole percent isophthalic acid and conversely from 20 to 17 mole percent 5—sodiosulfoisophthalic acid, and said glycol moiety comprises form 52—56 mole percent diethylene glycol and conversely from 48—44 mole percent 1,4—cyclohexanedimethanol.

It is preferable that the polymer blends of the invention contain 45 to 97.5 percent of a styrene polymer comprising 30 to 100 weight percent of repeating units from a styrene compound.

The styrene monomer useful herein is preferably of the structure

Figure imgf000016_0001

wherein R1 is H or methyl, R2 is a lower alkyl group of 1 to 6 carbon atoms, and m is an integer of 0 to 2. Preferably m is 0 or 1, and R2 is methyl, and R1 is H. The most preferable styrene monomers are styrene, — ethyl styrene, 4—methyl styrene, 3—methyl styrene, t—butyl styrene, and mixtures thereof.

The meth(aerylate) monomer useful herein preferably is of the structure

COOR3

CH2:

R

wherein R3 is H or an alkyl group of 1 to 10 carbon atoms, optionally substituted with one or two substituents selected from the group consisting of C^—C6 alkoxy, hydroxy, epoxy, acetoacetoxy and halogen, and R1 has the same meaning as previously defined.

Most preferably, the (meth)acrylate monomer is selected from the group consisting of butyl acrylate, ethyl acrylate, propyl acrylate, 2—ethylhexyl acrylate, 2—hydroxyethyl acrylate, methyl methacrylate, hydroxyethyl methacrylate, glycidyl (meth)acrylate, acetoacetoxyethyl methacrylate, and mixtures thereof.

It is also preferred that component (B) , the styrene polymer comprises up to 70 weight percent of repeating units from a compound selected from the group consisting of (meth)acrylate compounds, sodium 2— aerylamido—2—methyl—1—propanesulfonate, ammonium 2— acrylamido—2— ethyl—1—propane—sulfonate, potassium 2—aerylamido—2—methyl—1—propanesulfonate, lithium 2—acrylamido—2— ethyl—1—propanesulfonate, sodium

2—acrylamido—2—methyl—1—propane a ine, and mixtures thereof. It is also preferred that component (B) further '. comprises repeating units from acrylic acid, methacrylie acid, acrylonitrile, methacrylonitrile, aerylamide, methacrylamide, N—methylolacrylonitrile, N—methylol— aerylamide, N-methylacrylamide, methyl acrylate, methyl ethacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n—butyl acrylate, n—butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2—ethylhexyl acrylate, 2—ethylhexyl methacrylate, stearyl acrylate, stearyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-ethoxyethyl acrylate, 2—ethoxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acetoacetoxy— ethyl acrylate, acetoacetoxyethyl methacrylate, a diol acrylate, a diol methacrylate, and mixtures thereof.

The polymer blends of the invention also comprise 0.5 to 5 weight percent of a sulfonate group—containing surfactant where the surfactant is different than the water— ispersible sulfonate group—containing polyester or polyesteramide of component (A) or a nonylphenol ethoxylated surfactant and mixtures thereof.

The preferred sulfonate group—containing surfactant of component (C) of the invention is selected from the group consisting of

Figure imgf000018_0001

0=«^ ^.-OR

and further wherein R is C13H27 or 2—ethylhexyl,

Figure imgf000019_0001

Figure imgf000019_0002
wherein n — 2—50, preferably 2—24, and wherein m = 10-100, preferably 2-50, and dodecylbenzene sulfonate.

It is also preferred that the sulfonated group- containing surfactant and the nonylphenol ethoxylated surfactant is

Figure imgf000019_0003
wherein n = 10—120 and R = C9H19 or C8H17.

The polymer blends may comprise additives other than coalescing aids, as previously mentioned. These additives may be surfactants, chain transfer agents, alcohols, antifoams, and combinations thereof.

The surfactants useful in the invention, in addition to component (C) of the invention, include nonionie surfactants. The additional nonionie surfactants include one or more block copolymers of propylene oxide and ethylene oxide.

In the process of the present invention the monomers are polymerized in the presence of the sulfonate—group containing polymer (i.e., the polyester or polyesteramide) .

Nonionie surfactants useful in component (C) of the invention include nonylphenol ethoxylated surfactants. Preferred nonylphenol ethoxylated surfactants are nonylphenol ethoxylate, nonylphenoxy poly(ethyleneoxy. ethanol.

More preferred nonylphenol ethoxylated surfactants are

Figure imgf000020_0001
wherein n = 10-120 and R — CgH19 or C8H17 , and

Figure imgf000020_0002
wherein n = 10—120 and R = cgHi9 or C 8 H 17* It is more preferred that both

Figure imgf000020_0003
wherein n = 10—120 and R — CgH19 or C8H17 and

Figure imgf000020_0004
wherein n = 10—120 and R ■= C9H19 or C8H17.

In the method of the present invention, the polymer blends of the present invention are prepared in aqueous dispersions. The monomers are generally added to an aqueous dispersion of the water—dispersible polyester and polymerized by free radical initiation in conventional emulsion or suspension polymerization processes. The preferred ratio of polyester to monomer will vary widely and depends on the intended application for the blend.

The polymerization can be initiated by a water- soluble free radical initiator known in the art such as sodium or potassium persulfate or, less preferably, by an oil—soluble initiator such as AIBN or benzoyl peroxide. Other useful initiators include redox initiators such as sodium persulfate/sodium . metabisulfite and sodium formaldehyde sulfoxylate/ Fe/hydrogen peroxide.

A typical temperature range for the polymerization reaction is 20°C to 90°C with 60°C to 85°C being preferred.

The sulfonate—group containing polymers which are used in the present invention typically become very viscous at concentrations above 34 percent total solids. Thus, the reaction typically is begun with a polyester or polyesteramide dispersion that is 30 percent total solids or less. However, the dispersions are prepared at final total solids levels up to from 20 percent to 60 percent. A total solids content of 35 percent to 50 percent is preferred. The increase in solids level is achieved during polymerization by controlling the amount of water, if any, which is added along with the monomer. Thus, the method of the present invention for preparing water dispersed polymer blends can be described as comprising the steps of:

(A) adding to a container a first portion of a water—dispersible sulfonate group—containing polyester or polyesteramide, sulfonate group- containing surfactant and water wherein (1) the amount of said polyester or polyesteramide is present in an amount of 0 to 60% by weight of the total said polyester or polyesteramide in the final product, and (2) the amount of said surfactant in step (A) is less than 40% of the total said surfactant in said final product,

(B) preparing an aqueous polymerization mixture by contacting (1) a water—dispersible sulfonate group— \ containing polyester or polyesteramide,

(2) one or more monomers, wherein said monomers comprise: (a) 50 to 100 wt. percent of a styrene monomer,

(3) a polymerization initiator

(4) water

(C) polymerizing said monomers of component (A) (2) to provide said water—dispersible polymer blend, and

(D) during step (C) , adding from 0.5 to 5 wt. percent of said surfactant wherein said surfactant is different than the polyester or polyesteramide of (A) (1) .

In the polymerization method it is preferred that component (A) is present in an amount of 2—10 weight percent, and component (B) is present in an amount of 80—98 weight percent.

It is also preferred that the polymerization mixture contain up to 20 weight percent of a C-^ to C alcohol, especially propanol. Lesser amounts of the alcohol (e.g., up to 5, 10 or 15 percent) can be employed. In the polymerization method of the invention, more preferred is wherein component (A) is present in an amount of 2—10 weight percent, component (B) is present in an amount of 80-98 weight percent, and the alcohol is present in an amount of up to 10 weight percent. It is even more preferred that component (A) is present in an amount of 3—6 weight percent, component (B) is present in an amount of 90-95 weight percent, and the alcohol is present in an amount of up to 5 weight percent. The method of the present invention produces polymer blends which are significantly different than mere physical mixing of two preformed polymers. For example, the blends produced by the invention method have monodisperse or monomodal particle size distributions. The particle size distribution of the blends produced by the method of the invention preferably has an average particle size diameter of 40 to 300 nanometers (nm) . Additionally, since the polyester acts as all or part of the surfactant needed to produce stable polystyrene latex, additional surfactants would have to be added to a polystyrene latex if it were prepared separately. These added surfactants could lead to increased cost and inferior performance.

In a preferred embodiment, the sulfonate group- containing polymer is prepared, generally by melt polymerization, and an aqueous dispersion containing from 10 percent to 30 percent total solids is prepared from the polyester or polyesteramide directly. A mixture of one or more monomers and the polymerization initiators may then be added to the aqueous dispersion of the polyester or polyesteramide and polymerization initiated to produce an aqueous dispersion. The aqueous dispersion so produced can be prepared with total solids contents from 20 percent to 60 percent. Preferably, the pH is, or is adjusted to be, within the range of 4—8 in order to minimize hydrolysis of the polyester.

The preferred embodiments of the polymer blends of the invention are applicable to the method of the present invention.

The polymer blends of the invention may also be useful in ink compositions. The invention can be further illustrated by the _. following examples of preferred embodiments thereof, although it will be understood that these examples are included merely for the purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated. All percentages are by weight, unless otherwise specified.

As used herein, the term "I.V." is inherent viscosity measured in a 60/40 parts by weight solution of phenol/tetrachloroethane at 25°C and at a concentration of 0.5 gram of polymer in 100 mL of the solvent. "Acid number" is defined as the milligrams of potassium hydroxide required to neutralize one gram of polymer to the phenolphthalein end—point.

EXAMPLES

For the purposes of these examples, Polyester A is a water—dispersible, sulfonate—group containing polyester which contains 82 mole % isophthalic acid, 18 mole % 5—sodiosulfoisphthalic acid, 54 mole % diethylene glycol, 46 mole % 1,4—cyclohexanedimethanol, with an I.V. of 0.3 and an acid number of 3. Polyester B is a water—dispersible—sulfonate—group containing polyester having an acid content of 89 mole % isophthalic acid, 11 mole % 5-sodiosulfoisophthalic acid (SIP) ; a glycol content of 72.3 mole % diethylene glycol and 27.7 mole % ethylene glycol.

EXAMPLE 1 — Preparation of a latex containing 5 weight % Polyester A. 85 weight % styrene and 10 weight percent EHA (2—ethylhexylacrylate) latex

(a) An initiator solution is prepared by adding ammonium persulfate (0.6g) into deionized water (90g) .

(b) Polyester A, an aqueous dispersion (67.9g) (33.4% solids), deionized water (431.7g) , sodium carbonate (0.3g), styrene (382.5g), 2-EHA (2-ethylhexylacrylatc) (45g) , IGEPAL (Trademark) 970 [CAS 9016-45-9, nonylphenoxypoly(ethyleneoxy)ethanol] (0.6g), and ALIPAL (Trademark) C0436 (CAS 9051—574, an ammonium salt of sulfatedpolyethoxy nonylphenol) (10.5g) were mixed using a mixer.

(c) Deionized water (107.9g), ALIPAL C0436 (l.lg), and SURFYNOL (Trademark) 104PA, 2, 4, 7, 9-tetramethyl-5- decyn—4,7—diol (0.8g), were added into three neck 1 liter flask which was equipped with a water condenser and nitrogen blanket.

Reaction: The temperature controller was set at 75°C. (a) was charged to the reactor over 3 hours to through a metering pump to the reactor, (b) was charged to the reactor starting 10 minutes after the start of charge (a) .

When the latex is drawn down as a thin film over 55 pound (24.95 kg) clay coated paper printed with a red ink, the gloss, without additives was 60 percent at a 60° angle using a reflectometer. It also possesses heat block test results of 180°F/5sec/40psi (82.2 °C/5sec/275.8kPa) .

EXAMPLE 2 — Preparation of a latex containing 5 weight % of Polyester A and 95 weight % of styrene (a) An initiator solution is prepared by dispersing ammonium persulfate (0.4g) into deionized water (60g) . (b) Polyester A aqueous dispersion (45.3g) (33.4% solids), deionized water (287.8g), sodium carbonate (0.2g), styrene (285g) , IGEPAL 970 (0.4g), and ALIPAL C0436 (7.0g) were mixed using a mixer, (c) Deionized water (71.9g), ALIPAL C0436 (0.7g), and SURFYNOL 104PA (0.5g) were added into three neck 1 liter flask which was equipped with a water condenser and . nitrogen blanket.

Reaction: The temperature controller was set at 75°C. (a) was charged over 3 hours. (b) was charged to the reactor starting 10 minutes after the start of charge (a) .

When the latex is drawn down as a thin film over 55 pound (24.95 kg) clay coated paper printed with a red ink, the gloss, without additives was 62 percent at a 60° angle using a reflectometer. It also possesses heat block test results of 210°F/5sec/40psi(98.9°C/5sec/275.8kPa) .

EXAMPLE 3 — Preparation of a latex containing 5 weight % of Polyester B and 95 weight % of styrene (a) An initiator solution is prepared by adding ammonium persulfate (0.4g) into deionized water (60g) . (b) Polyester B — aqueous dispersion (50.8g), deionized water (287.8g), sodium carbonate (O.lg), styrene (285g) , IGEPAL CO970 (0.4g), and ALIPAL C0436 (7.0g) were mixed using the a mixer, (c) Deionized water (70.8g), ALIPAL C0436 (0.7g), and SURFYNOL 104PA (0.5g) were added into three neck 1L flask which was equipped with a water condenser and nitrogen blanket.

Reaction: The temperature controller was set at 75°C. (a) was charged over 3 hours. (b) was charged to the reactor starting 10 minutes after the start of charge (a) .

When the latex is drawn down as a thin film over 55 pound (24.95 kg) clay coated paper printed with a red ink, the gloss, without additives was 61 percent at a 60° angle using a reflectometer. It also possesses heat block test results of

210°F/5sec/40psi(98.9°C/5sec/275.8kPa) .

EXAMPLE 4 — Preparation of a latex containing 5 weight % of JONCRYL fTrademark. 67 and 95 weight % of styrene (a) An initiator solution is prepared by adding ammonium persulfate (0.4g) into deionized water (60g) . (b) JONCRYL 67 (52.6g) (28.5% aqueous solution), deionized water (271.4g), styrene (285g) , IGEPAL CO970 (0.4g), and ALIPAL C0436 (7.0g) were mixed using a mixer. JONCRYL 67 is an acrylic polymer emulsion sold by S.C. Johnson and Sons, Inc., Racine, Wis. 43403, U.S.A. It is an emulsion sold having a molecular weight of 10,000, an acid number of 190 and a Tg (glass transition temperature) of 70.

(c) Deionized water (71.9g), ALIPAL C0436 (0.7g), and SURFYNOL 104PA (0.5g) were added into three neck 1 liter flask which was equipped with a water condenser and nitrogen blanket.

Reaction: The temperature controller was set at 75°C. (a) was charged over 3 hours. (b) was charged to the reactor starting 10 minutes after the start of charge (a) .

When the latex is drawn down as a thin film over 55 pound (24.95 kg) clay coated paper printed with a red ink, the gloss, without additives was 12 percent at a 60° angle using a reflectometer.

EXAMPLE 5 — Preparation of a latex containing 5 weight % Polyester A and 95 weight % of styrene containing anionic surfactant only (a) An initiator solution is prepared by adding ammonium persulfate (0.4g) into deionized water (60g) .

(b) Polyester A aqueous dispersion (46.2g) (33.4% solids), deionized water (273.5g), sodium carbonate (O.llg), styrene (285g) , and ALIPAL C0436 (9.3g) were mixed using the a mixer.

(c) Deionized water (75g) and ALIPAL C0436 (0.7g) were added into three neck 1 liter flask which was equipped with a water condenser and nitrogen blanket.

Reaction: The temperature controller was set at 75°C. (a) was charged over 3 hours. (b) was charged to the reactor starting 10 minutes after the start of charge (a) .

When the latex is drawn down as a thin film over 55 pound (24.95 kg) clay coated paper printed with a red ink, the gloss, without additives was 57 percent at a 60° angle using a reflectometer.

EXAMPLE 6 — Preparation of a latex containing 5 weight % Polyester A and 95 weight % of styrene containing nonionie surfactant only

(a) An initiator solution is prepared by adding ammonium persulfate (0.4g) into deionized water (60g) .

(b) Polyester A aqueous dispersion (46.2g) (33.4% solids), deionized water (274.5g), sodium carbonate (O.llg), styrene (285g) , and Triton N-101 [nonylphenoxypoly(ethyleneoxy) ethanol] (8.3g) were mixed using the a mixer.

(c) Deionized water (75g) and Triton N—101 (0.7g) were added into three neck 1 liter flask which was equipped with a water condenser and nitrogen blanket. Reaction: The temperature controller is set at 75°C. (a) is charged over 3 hours to the reactor. (b) was charged to the reactor starting 10 minutes after the start of charge (a) .

When the latex is drawn down as a thin film over 55 pound (24.95 kg) clay coated paper printed with a red ink, the gloss, without additives was 56 percent at a 60° angle using a reflectometer.

EXAMPLE 7 — Preparation of a latex containing 30 weight % Polyester A and 70 weight % of styrene containing nonionie surfactant only

(a) An initiator solution is prepared by adding ammonium persulfate (0.4g) into deionized water (60g) .

(b) Polyester A (276.9g) (33.4% aqueous solution), deionized water (227.2g) , sodium carbonate (0.2g), styrene (210g) , IGEPAL CO970 (0.4g) , and ALIPAL C0436 (7.0g) were mixed using a mixer. (c) Deionized water (71.9g), ALIPAL C0436 (0.7g), and

SURFYNOL 104PA (0.5g) were added into three neck 1 liter flask which was equipped with a water condenser and nitrogen blanket.

The temperature was set at 75°C. (a) was charged over 3 hours to the reactor. (b) was charged to the reactor starting 10 minutes after the charge of (a) .

When the latex is drawn down as a thin film over 55 pound (24.95 kg) clay coated paper printed with a red ink, the gloss, without additives was 42 percent at a 60° angle using a reflectometer. EXAMPLE 8 — Preparation of a latex containing Polyester A and styrene

(a) An initiator solution is prepared by adding ammonium persulfate (0.56g) into deionized water (60g) . (b) deionized water (88.9g), 12.Og of the initiator solution of (a), and IGEPAL 970 [CAS 9016-45-9, nonylphenoxypoly(ethyleneoxy)ethanol] were mixed using a mixer.

(c) Deionized water (266.8g), IGEPAL 970 (1.98g), 0.26g sodium carbonate, 45.5g of Polyester A, and styrene (285.Og) .

Reaction: The temperature controller was set at 75°C. (a) was charged over 3 hours to the reactor. (c) was charged to the reactor over 2.5 hours, beginning 10 minutes after starting charge (a) . After approximately 60 minutes, a lot of deposits were noted in the reactor.

EXAMPLE 9 — Preparation of a latex containing 5 weight % of Polyester A and 95 weight % of styrene

(a) An initiator solution is prepared by dispersing ammonium persulfate (0.5g) into deionized water (50g) .

(b) deionized water (75.0), ALIPAL C0436 (0.70g), SURFYNOL 465 (0.40g), component (c) , (75.Og)

(c) deionized water (284.72), sodium carbonate (0.13g), Polyester A (45.45), styrene (285g) , ALIPAL C0436

(5.0g), and SURFYNOL 465 (3.0g) were mixed using a mixer.

Reaction: The temperature controller was set at 75°C. (a) is charged through the metering pump to the reactor when temperature reaches 75°C. (c) was then charged to the reactor over 2.5 hours, beginning 10 minutes afte.v the start of charge (A) .

EXAMPLE 10 — Preparation of a latex containing 5 weight % of Polyester A. 55 weight % of MMA

(methylmethacrylate) and 40 weight % BA fbutylacrylate)

(a) An initiator solution is prepared by adding ammonium persulfate (0.5g) into deionized water (50g)

(b) ionized water (75.Og), ALIPAL C0436 (0.7g), SURFYNOL 465 (0.40g), component (c) (75.Og),

(c) deionized water (284.72g), sodium carbonate (0.13g), Polyester A (45.45g), MMA (165.Og), BA (120.Og), SURFYNOL 465 (3.0g) and ALIPAL C0436 (5.0g) were mixed using the a mixer.

Reaction: The temperature controller was set at 75°C. (a) was charged through a metering pump to the reactor. When the temperature reached 75°C, 10 in. (c) was charged to the reactor over 2.5 hours, beginning 10 minutes after the start of charge (a) .

The invention has been described in detail with particular reference to the preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. Moreover, all patents, patent applications (published or unpublished, foreign or domestic) , literature references or other publications noted above are incorporated herein by reference for any disclosure pertinent to the practice of this invention.

Claims

CLAIMS WHAT IS CLAIMED IS: 1. A polymer blend comprising:
(A) 2 wt. percent to 50 wt. percent of a water— dispersible sulfonate group—containing polyester or polyesteramide comprising; (a) aromatic and aliphatic and ionic dicarboxylic acids such that (i) the mole percent of ionic diacid is 7 mole percent to 25 mole percent of the total diacids, and (ii) the mole percent of aromatic diacids is equal to or greater than 50% of the total diacids, (b) diols comprising no more than 50 mole percent of the total diols being selected from the group consisting of 1,4—cyclohexanedimethanol, 1,3—cyclo¬ hexanedimethanol, and 1,2—cyclohexane— dimethanol;
(B) 45 to 97.5 wt. percent of a styrene polymer comprising:
(a) 30 to 100 wt. percent of repeating units from a styrene compound, and (C) 0.5 to 5 wt. percent of either a sulfonate group—containing surfactant wherein said surfactant is different than said polyester or polyesteramide of component (A) or a nonylphenol ethoxylated surfactant and mixtures thereof.
2. The polymer blend of Claim 1 wherein said sulfonate group—containing surfactant is
Figure imgf000033_0001
and further wherein R is C13H27 or 2—ethylhexyl.
3. The polymer blend of Claim 1 wherein sulfonate- group containing surfactant is
Figure imgf000033_0002
4. The polymer blend of Claim 1 wherein said sulfonate—group containing surfactant is
Figure imgf000033_0003
wherein n = 2—50 and m = 2—50.
5. The polymer blend of Claim 1 wherein said sulfonated group—containing surfactant and said nonylphenol ethoxylated surfactant is
Figure imgf000033_0004
wherein n = 10—120 and R = C9H19 or C8H17.
6. The polymer blend of Claim 1 wherein said surfactant is dodecylbenzene sulfonate.
7. The polymer blend of Claim 1 wherein the styrene compound in component (B) is selected from the group consisting of styrene, α—methyl styrene, \ 3—methyl styrene, 4— ethyl styrene, t—butyl styrene, and mixtures thereof.
8. The polymer blend of Claim 1 wherein component (B) comprises:
(a) 30 to 100 wt. percent of repeating units from a styrene compound, and
(b) up to 70 wt. percent of repeating units from a compound selected from the group consisting of
(meth)acrylate compounds, sodium 2-acrylamidc— 2—methyl—1—propanesulfonate, ammonium 2- acrylamido—2—methyl—1—propanesulfonate, potassium 2—acrylamido—2—methyl—1— propanesulfonate, lithium 2—acrylamido—2— methyl—1—propanesulfonate, sodium 2—acryl¬ amido—2—methyl—1—propanesulfonate, and mixtures thereof.
9. The polymer blend of Claim 8 wherein component (a) is selected from the group consisting of styrene, α—methyl styrene, 3—methyl styrene, 4— ethyl styrene, t—butyl styrene, and mixtures thereof, and component (b) is selected from the group consisting of acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, aerylamide, methacryla ide, N-methylolacrylonitrile, N—methylolacrylamide, N-methylacrylamide, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n—propyl acrylate, n—propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n—butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, stearyl acrylate, stearyl meth— acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, 2—ethoxyethyl acrylate, 2—ethoxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acetoacetoxyethyl acrylate, acetoacetoxyethyl methacrylate, a diol acrylate, a diol methacrylate, and mixtures thereof.
10. The polymer blend of Claim 1 wherein said polymer blend further comprises additives.
11. The polymer blend of Claim 10 wherein said additives are selected from the group consisting of surfactants, chain transfer agents, alcohols, anti- foams, coalescing aides, and combinations thereof.
12. The polymer blend of Claim 1 further comprising an additional nonionie surfactant which is different than a nonylphenol ethoxylated surfactant.
13. The polymer blend of Claim 1 wherein said nonylphenol ethoxylated surfactant is nonylphenol ethoxylate.
14. The polymer blend of Claim 1 wherein said nonylphenol ethoxylated surfactant is
Figure imgf000035_0001
wherein n •= 10—120 and R = C9H19 or C8H17 .
15. The polymer blend of Claim 1 wherein said nonylphenol ethoxylated surfactant is
Figure imgf000035_0002
wherein n = 10—120 and R = C9H19 or C8H17.
16. The polymer blend of Claim 1 wherein said nonylphenol ethoxylated surfactant is nonylphenoxypoly(ethyleneoxy) ethanol.
17. The polymer blend of Claim 12 wherein said nonionie surfactant is one or more block copolymers of propylene oxide and ethylene oxide.
18. The polymer blend of Claim 1 wherein said (A) water—dispersible polyester or polyesteramide comprises a polymer having carbonyloxy linking groups in the linear molecular structure wherein up to 80 percent of the linking groups are carbonyl— amido linking groups, the polymer having an inherent viscosity of from 0.1 to 1.0 dL/g measured in a 60/40 parts by weight solution of phenol tetrachloroethane at 25°C and at a concen¬ tration of 0.5 gram of polymer in 100 mL of the solvent, the polymer containing substantially equimolar proportions of acid equivalents (100 mole %) to hydroxy and amino equivalents (100 mole %) , the polymer comprising the reaction products of reactants selected from (a) , (b) , (c) , and (d) , or the ester forming or esteramide forming derivatives thereof, as follows, wherein all stated mole percentages are based on the total of all acid, hydroxyl, and amino equivalents being equal to 200 mole percent:
(a) at least one difunctional dicarboxylic acid;
(b) from 7 to 25 mole percent of at least one difunctional sulfomonomer containing at least one metallic sulfonate group or nitrogen-containing nonmetallic sulfonate group attached to an aromatic or aliphatic nucleus wherein the functional groups are hydroxy, carboxyl, or amino;
(c) at least one difunctional reactant selected from a glycol or a mixture of a glycol and diamine having two —NRH groups, the glycol containing to —OH groups; and
(d) from 0 to 40 mole percent of difunctional reactant selected from hydroxycarboxylic acids having one —C(R)2—OH group, aminocarboxylic acids having one —NRH group, amino—alcohols having one —C(R)2— OH group and one —NRH group, or mixtures of said difunctional reactants; wherein each R in the (c) and (d) reactants is a hydrogen atom or an alkyl group of 1 to 4 carbons;
(B) said styrene compound is of the structure
Figure imgf000037_0001
wherein R1 is H or methyl, R2 is a lower alkyl group of l to 6 carbon atoms, and m is an integer of 0 to 2.
19. The polymer blend of Claim 1 wherein
(a) the aromatic dicarboxylic acids are selected from the group consisting of terephthalic acid, isophthalic acid, phthalic acid and mixtures thereof;
(b) the aliphatic dicarboxylic acids are selected from the group consisting of 1,4—cyclohexane¬ dicarboxylic acid, 1,3—cyclohexanedicarboxylic acid, 1,2—cyclohexanedicarboxylic acid, and HOOC-(CH2)n —COOH where n is an integer of 2—
10, and mixtures thereof,
(c) the ionic dicarboxylic acids are selected from the group consisting of 5—sulfoisophthalic acid, 4—sulfophthalic acid and mixtures thereof,
(d) no more than 50 mole % of the diols being selected from the group consisting of
1,4—cyclohexanedimethanol, 1,3-cyclohexane— dimethanol, and 1,2—cyclohexanedimethanol, and (e) the remainder of the diols being selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 2— ethyl—1,3-propanediol, 1,5-pentanediol,
1,4-butanediol, 1,3—propanediol, 1,3—cyclo— butanediol, 2,2—dimethyl—3—hydroxypropy1—2,2— dimethyl—3—hydroxypropionate, butylethyl— propanediol and mixtures thereof.
20. A polymer blend comprising:
(A) 2 wt. percent to 30 wt. percent of a water— dispersible sulfonate group—containing polyester or polyester amide comprising; (a) aromatic and aliphatic and ionic dicarboxylic acids such that
(i) the mole percent of ionic diacid is 7 mole percent to 25 mole percent, and
(ii) the mole percent of aromatic diacids is equal to or greater than 50%,
(b) diols comprising no more than 50 mole percent of the total diols being selected from the group consisting of
1,4—cyclohexanedimethanol, 1,3—cyclo¬ hexanedimethanol, and 1,2—cyclohexane¬ dimethanol;
(B) 65 to 97.5 wt. percent of a styrene polymer comprising:
(a) 30 to 100 wt. percent of repeating units from a styrene compound, and
(C) 0.5 to 5 wt. percent of either a sulfonate group—containing surfactant wherein said surfactant is different than said polyester or polyesteramide of (A) or a nonylphenol ethoxylated surfactant and mixtures thereof.
21. The polymer blend of Claim 20 wherein said sulfonate—containing group surfactant is
Figure imgf000039_0001
o= X-oR o o* and further wherein R is C13H27 or 2-ethylhexyl,
22 The polymer blend of Claim 20 wherein said sulfonated group-containing surfactant and said nonylphenol ethoxylated surfactant is
Figure imgf000040_0001
wherein n — 10—120 and R = C9H19 or C8H17 .
23. The polymer blend of Claim 20 wherein said anionic surfactant is
Figure imgf000040_0002
24. The polymer blend of Claim 20 wherein said anionic surfactant is
Figure imgf000040_0003
wherein n = 2—50 and m = 2-50.
25. The polymer blend of Claim 20 wherein said anionic surfactant is dodecylbenzene sulfonate.
26. The polymer blend of Claim 20 wherein the styrene compound in component (B) is selected from the group consisting of styrene, α-methyl styrene, 3-methyl styrene, 4—methyl styrene, t—butyl styrene, and mixtures thereof.
27. The polymer blend of Claim 20 wherein component (B) comprises:
(a) 30 to 100 wt. percent of repeating units from a styrene compound, and (b) up to 70 wt. percent of repeating units frc*,. a compound selected from the group consisting of (meth)acrylate compounds, sodium 2—acrylamido— 2—methyl—1—propanesulfonate, ammonium 2— aerylamido—2—methyl—1—propanesulfonate, potassium 2—acrylamido—2—methyl—1— propanesulfonate, lithium 2—acrylamido—2— methyl—1—propanesulfonate, sodium 2—acryl¬ amido—2— ethyl—1—propane sulfonate, and mixtures thereof.
28. The polymer blend of Claim 27 wherein said (A) water—dispersible polyester or polyesteramide comprises a polymer having carbonyloxy linking groups in the linear molecular structure wherein up to 80 percent of the linking groups are carbonyl- a ido linking groups, the polymer having an inherent viscosity of from 0.1 to 1.0 measured in a 60/40 parts by weight solution of
Figure imgf000041_0001
at 25°C and at a concen¬ tration of 0.5 gram of polymer in 100 mL of the solvent, the polymer containing substantially equimolar proportions of acid equivalents (100 mole %) to hydroxy and amino equivalents (100 mole %) , the polymer comprising the reaction products of reactants selected from (a) , (b) , (c) , and (d) , or the ester forming or esteramide forming derivatives thereof, as follows, wherein all stated mole percentages are based on the total of all acid, hydroxyl, and amino equivalents being equal to 200 mole percent:
(a) at least one difunctional dicarboxylic acid;
(b) from 7 to 25 mole percent of at least one difunctional sulfomonomer containing at least one metallic sulfonate group or nitrogen- containing nonmetallic sulfonate group attached to an aromatic or cycloaliphatic nucleus wherein the functional groups are hydroxy, carboxyl, or amino;
(c) at least one difunctional reactant selected from a glycol or a mixture of a glycol and diamine having two —NRH groups, the glycol containing two —OH groups; and
(d) from 0 to 40 mole percent of difunctional reactant selected from hydroxycarboxylic acids having one —C(R)2—OH group, aminocarboxylic acids having one —NRH group, amino—alcohols having one —C(R)2—OH group and one —NRH group, or mixtures of said difunctional reactants; wherein each R in the (c) and (d) reactants is a hydrogen atom or an alkyl group of 1 to 4 carbons; (B) said styrene compound is of the structure
Figure imgf000042_0001
wherein R1 is H or methyl, R2 is a lower alkyl group of 1 to 6 carbon atoms, and is an integer of 0 to 2; and (C) said (meth)acrylic compound is of the structure
COOR3
CH-
wherein R3 is H or an alkyl group of 1 to 10 carbon atoms, optionally substituted with one or two substituents selected from the group consisting of hydroxy, acetoacetoxy, C-^—C6 alkoxy, epoxy and halogen, and R1 is H or methyl.
29. The polymer blend of Claim 20 wherein component (B) comprises:
(a) 30 to 100 wt. percent of repeating units from a styrene compound selected from the group consisting of styrene, α—methyl styrene, 3— methyl styrene, 4—methyl styrene, t—butyl styrene, and mixtures thereof, and
(b) up to 70 wt. percent of repeating units from a compound selected from the group consisting of (meth)acrylate compounds, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, aerylamide, methacrylamide, N-methylolacrylonitrile, N-methylolacrylamide, N-methylacrylamide, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl metha¬ crylate, n—propyl acrylate, n—propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n—butyl acrylate, n—butyl methacrylate, isobutyl acrylate, isobutyl • methacrylate, 2—ethylhexyl acrylate, 2—ethylhexyl methacrylate, stearyl acrylate, stearyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, 2—ethoxyethyl acrylate, 2—ethoxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, aceto¬ acetoxyethyl acrylate, acetoacetoxyethyl methacrylate, a diol acrylate, a diol methacrylate sodium 2-acrylamido—2-methyl-1- propanesulfonate, ammonium 2—acrylamido—2— methyl—1—propanesulfonate, potassium 2—acrylamido—2—methyl—1—propanesulfonate, lithium 2—acrylamido—2—methyl—1—propane— sulfonate, sodium 2—acrylamido—2—methyl—1— propane amine, and mixtures thereof.
30. The polymer blend of Claim 20 wherein said polymer blend also contains additives.
31. The polymer blend of Claim 30 wherein said additives are selected from the group consisting of surfactants, chain transfer agents, alcohols, anti- foams, coalescing aids, and combinations thereof.
32. The polymer blend of Claim 20 wherein
(a) the aromatic dicarboxylic acids are selected from the group consisting of terephthalic acid, isophthalic acid, phthalic acid and mixtures thereof;
(b) the aliphatic dicarboxylic acids are selected from the group consisting of 1,4—cyclohexane¬ dicarboxylic acid, 1,3—cyclohexanedicarboxylic acid, 1,2—cyclohexanedicarboxylic acid, and mixtures thereof, and HOOC—(CH )n—COOH wherr n is an integer of 2—10,
(c) the ionic dicarboxylic acids are selected from the group consisting of 5—sulfoisophthalic acid, 4—sulfophthalic acid and mixtures thereof,
(d) no more than 50 mole % of the diols being selected from the group consisting of
1,4-cyclohexanedimethanol, 1,3-cyclohexane- dimethanol, and 1,2-cyclohexanedimethanol, and
(e) the remainder being selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,5—pentanediol, 1,4—butane¬ diol, 1,3—propanediol, 1,3—cyclobutanediol, 2,2-dimethyl—3—hydroxypropyl—2,2—dimethyl—3— hydroxypropionate, butylethylpropanediol and mixtures thereof.
33. The polymer blend of Claim 20 further comprising surfactant is an additional nonionie surfactant which is different than a nonylphenol ethoxylated surfactant.
34. The polymer blend of Claim 20 wherein said nonylphenol ethoxylated surfactant is a nonylphenol ethoxylate.
35. The polymer blend of Claim 20 wherein said nonylphenol ethoxylated surfactant is
Figure imgf000045_0001
wherein n = 10—120 and R = C9H19 or C8H17.
36. The polymer blend of Claim 20 wherein said nonylphenol ethoxylated surfactant is
Figure imgf000046_0001
wherein n = 10—120 and R = C9H19 or C8H17.
37. The polymer blend of Claim 20 wherein said 5 nonylphenol ethoxylated surfactant is nonylphenoxypoly(ethyleneoxy) ethanol.
38. The polymer blend of Claim 33 wherein said nonionie surfactant is one or more block copolymers of 0 propylene oxide and ethylene oxide.
39. A polymer blend comprising:
(A) 2 wt. percent to 50 wt. percent of a water- dispersible sulfonate group—containing 5 polyester or polyesteramide comprising;
(a) aromatic and aliphatic and ionic dicarboxylic acids such that
(i) the mole percent of ionic diacid is 7 mole percent to 25 mole percent, 0 and
(ii) the mole percent of aromatic diacids is equal to or greater than 50% of the total diacids.
(b) diols comprising no more than 50 mole 5 percent of the total diols being selected from the group consisting of 1,4—cyclohexanedimethanol, 1,3—cyclo¬ hexanedimethanol, and 1,2—cyclohexane¬ dimethanol; 0 (B) 45 to 97.5 wt. percent of a styrene polymer comprising: (a) greater than 50 wt. percent of a styre.»e monomer, and
(b) the balance consisting of repeating units from at least one other ethylenically unsaturated monomer, and
(C) 0.5 to 5 wt. percent of a sulfonate group- containing surfactant wherein said surfactant is different than said polyester or polyesteramide of (A) .
40. The polymer blend of Claim 39 wherein said surfactant is
Figure imgf000047_0001
D=A >-OR
and further wherein R is C13H27 or 2—ethylhexyl.
41. The polymer blend of Claim 39 wherein said surfactant is
Figure imgf000047_0002
42. The polymer blend of Claim 39 wherein said surfactant is
Figure imgf000047_0003
wherein n = 2—50 and m = 2-50.
43. The polymer blend of Claim 39 wherein said surfactant is dodecylbenzene sulfonate.
44. The polymer blend of Claim 39 wherein component-. (B) (a) is selected from the group consisting of styrene, α—methyl styrene, 3—methyl styrene,
4—methyl styrene, t—butyl styrene, and mixtures thereof, and component (B) (b) is selected from the group consisting of acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, aerylamide, methacrylamide, N—methylolacrylonitrile, N-methylolacrylamide, N-methylacrylamide, methyl acrylate methyl methacrylate, ethyl acrylate, ethyl methacrylate, n—propyl acrylate, n—propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n—butyl acrylate, n—butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2—ethylhexyl acrylate, 2—ethylhexyl methacrylate, stearyl acrylate, stearyl meth¬ acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, 2—ethoxyethyl acrylate, 2—ethoxyethyl methacrylate, glycidyl acrylate, glycidyl meth- acrylate, acetoacetoxyethyl acrylate,. aceto¬ acetoxyethyl methacrylate, a diol acrylate, a diol methacrylate, vinyl acetate, vinylidene chloride, butadiene, 1—methylbutadiene, 2— ethylbutadiene, 2—chloro—butadiene, diisobutylene, cyclopentadiene, divinylbenzene, diallylphthalate, and mixtures thereof.
45. The polymer blend of Claim 39 wherein said (A) water—dispersible polyester or polyesteramide comprises a polymer having carbonyloxy linking groups in the linear molecular structure wherein up to 80 percent of the linking groups are carbonyl- a ido linking groups, the polymer having an inherent viscosity of from 0.1 to 1.0 measured in a 60/40 parts by weight solution of phenol. tetrachloroethane at 25°C and at a conceπ - tration of 0.5 gram of polymer in 100 mL of the solvent, the polymer containing substantially equimolar proportions of acid equivalents (100 mole %) to hydroxy and amino equivalents (100 mole %) , the polymer comprising the reaction products of reactants selected from (a) , (b) , (c) , and (d) , or the ester forming or esteramide forming derivatives thereof, as follows, wherein all stated mole percentages are based on the total of all acid, hydroxyl, and amino equivalents being equal to 200 mole percent:
(a) at least one difunctional dicarboxylic acid; (b) from 7 to 25 mole percent of at least one difunctional sulfomonomer containing at least one metallic sulfonate group or nitrogen—containing nonmetallic sulfonate group attached to an aromatic or cycloaliphatic nucleus wherein the functional groups are hydroxy, carboxyl, or amino;
(c) at least one difunctional reactant selected from a glycol or a mixture of a glycol and diamine having two —NRH groups, the glycol containing two —OH groups; and
(d) from 0 to 40 mole percent of difunctional reactant selected from hydroxycarboxylic acids having one —C(R)2—OH group, aminocarboxylic acids having one —NRH group, amino—alcohols having one —C(R)2— OH group and one —NRH group, or mixtures of said difunctional reactants; wherein each R in the (c) and (d) reactants is a hydrogen atom or an alkyl group of 1 to 4 carbons; (B) said styrene compound is of the structure
Figure imgf000050_0001
wherein R1 is H or methyl, R2 is a lower alkyl group of 1 to 6 carbon atoms, and m is an integer of 0 to 2; and
(C) said (meth)acrylic compound is of the structure
COO 3
CH,
wherein R3 is H or an alkyl group of 1 to 10 carbon atoms, optionally substituted with one or two substituents selected from the group consisting of hydroxy, acetoacetoxy, C-^—C6 alkoxy, epoxy and halogen, and R1 is H or methyl.
46. The polymer blend of Claim 1 wherein (a) the aromatic dicarboxylic acids are selected from the group consisting of terephthalic acid, isophthalic acid, phthalic acid and - mixtures thereof;
(b) the aliphatic dicarboxylic acids are selected from the group consisting of 1,4—cyclohexane— dicarboxylic acid, 1,3—cyclohexanedicarboxylic acid, 1,2—cyclohexanedicarboxylic acid, and mixtures thereof, and HOOC-(CH2)n —COOH where n is an integer of 2—10,
(c) the ionic dicarboxylic acids are selected from the group consisting of 5-sulfoisophthalic acid, 4—sulfophthalic acid and mixtures thereof,
(d) no more than 50 mole % of the diols being selected from the group consisting of 1,4—cyclohexanedimethanol, 1,3—cyclohexane¬ dimethanol, and 1,2—cyclohexanedimethanol, and
(e) the remainder being selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,5—pentanediol, 1,4—butane¬ diol, 1,3—propanediol , 1,3—cyclobutanediol , 2,2—dimethyl—3—hydroxypropy1—2,2—dimethyl—3— hydroxypropionate, butylethylpropanediol and mixtures thereof.
47. The polymer blend of Claim 39 wherein said polymer blend also contains additives.
48. The polymer blend of Claim 47 wherein said additives are selected from the group consisting of surfactants, chain transfer agents, alcohols, anti- foams, coalescing aides, and combinations thereof.
49. The polymer blend of Claim 39 wherein said water— dispersible polyester has an inherent viscosity of from 0.20 to 0.38, and acid moiety of from 75 to 92 mole percent isophthalic acid and/or terephthalic acid and conversely from 25 to 8 mole percent
5-sodiosulfoisophthalic acid, and a glycol moiety of from 50 to 100 mole percent diethylene glycol and conversely from 50 to 0 mole percent 1,4— cyclohexanedimethanol, 2,2—dimethyl—1,3— propanediol, ethylene glycol, or mixtures thereof.
50. The polymer blend of Claim 49 wherein said acid moiety comprises from 80 to 83 mole percent isophthalic acid and conversely from 20 to 17 mole percent 5—sodiosulfoisophthalic acid, and said glycol moiety comprises from 52 to 56 mole percent diethylene glycol and conversely from 48 to 44 mole percent 1,4—cyclohexanedimethanol.
51. The polymer blend of Claim 39 further comprising surfactant is an additional nonionie surfactant which is different than a nonylphenol ethoxylated surfactant.
52. The polymer blend of Claim 39 wherein said nonylphenol ethoxylated surfactant is a nonylphenol ethoxylate.
53. The polymer blend of Claim 39 wherein said nonylphenol ethoxylated surfactant is
Figure imgf000052_0001
wherein n = 10-120 and R = C9H19 or C8H17 ,
54. The polymer blend of Claim 39 wherein said nonylphenol ethoxylated surfactant is
Figure imgf000053_0001
wherein n = 10—120 and R = C9H19 or C8H17.
55. The polymer blend of Claim 39 wherein said nonylphenol ethoxylated surfactant is nonylphenoxypoly(ethyleneoxy) ethanol.
56. The polymer blend of Claim 51 wherein said nonionie surfactant is one or more block copolymers of propylene oxide and ethylene oxide.
57. The polymer blend of Claim 1 prepared by polymerizing monomers to form compound (B) in the presence of said polyester or polyesteramide.
58. An aqueous dispersion comprising water and the polymer blend of Claim 1.
59. The aqueous dispersion of Claim 58 wherein the polymer blend is the polymer blend of Claim 20.
60. The aqueous dispersion of Claim 58 wherein the polymer blend is the polymer blend of Claim 39.
61. The aqueous dispersion of Claim 59 comprising 20 to 60 weight percent solids.
62. The aqueous dispersion of Claim 59 comprising 35 to 50 weight percent solids.
63. The aqueous dispersion of Claim 60 comprising 28 to 60 weight percent solids.
64. The aqueous dispersion of Claim 59 comprising 35 to 50 weight percent solids.
65. The aqueous dispersion of Claim 59 containing up to 15 weight percent of a Cl to C4 alcohol.
66. The aqueous dispersion of Claim 59 containing up to 10 weight percent of a Cl to C4 alcohol.
67. The aqueous dispersion of Claim 64 containing up to 15 weight percent of a Cl to C4 alcohol.
68. A method of preparing a water—dispersed polymer blend comprising the steps of:
(A) adding to a container a first portion of a water—dispersible sulfonate group—containing polyester or polyesteramide, sulfonate group- containing surfactant and water wherein
(1) the amount of said polyester or polyesteramide is present in an amount of 0 to 60% by weight of the total said polyester or polyesteramide in the final product, and
(2) the amount of said surfactant in step (A) is less than 40% of the total said surfactant in said final product, (B) preparing an aqueous polymerization mixture by contacting
(1) a water—dispersible sulfonate group- containing polyester or polyesteramide,
(2) one or more monomers, wherein said monomers comprise: (a) 50 to 100 wt. percent of a styrene monomer,
(3) a polymerization initator
(4) water (C) polymerizing said monomers of component (A) (2) to provide said water—dispersible polymer blend, and (D) during step (C) , adding from 0.5 to 5 wt. percent of said surfactant wherein said surfactant is different than the polyester or polyesteramide of (A) (1) .
69. The method of Claim 68 wherein said monomers of component (A) (2) comprise (a) 30 to 100 wt. percent of repeating units from a styrene compound, (b) up to 70 wt. percent of repeating units from a (meth)acrylate compound.
70. An ink composition comprising the polymer blend of Claim 1.
71. An ink composition comprising the polymer blend of Claim 20.
72. An ink composition comprising the polymer blend of Claim 39.
PCT/US1994/006552 1993-06-29 1994-06-13 Polymer blends comprising sulfonate group-containing surfactants WO1995001381A1 (en)

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WO1998000449A1 (en) * 1996-06-28 1998-01-08 Eastman Chemical Company Waterborne polymer composition having a small particle size
WO1998003567A1 (en) * 1996-07-23 1998-01-29 Basf Aktiengesellschaft Process for preparing water-dispersible polymer blends
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WO1997028198A1 (en) * 1996-01-31 1997-08-07 Eastman Chemical Company Small particle size polyester/acrylic hybrid latexes
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WO1998000449A1 (en) * 1996-06-28 1998-01-08 Eastman Chemical Company Waterborne polymer composition having a small particle size
WO1998003567A1 (en) * 1996-07-23 1998-01-29 Basf Aktiengesellschaft Process for preparing water-dispersible polymer blends
CN101992306A (en) * 2009-08-17 2011-03-30 株式会社O-M制作所 Automatic rotating-type turret device for work machinery
CN101992306B (en) * 2009-08-17 2015-05-20 株式会社O-M制作所 Automatic rotating-type turret device for work machinery

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