JPH0155292B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to a new class of nonionic polyurethanes useful in thickening a wide range of aqueous systems, and more particularly to relatively low molecular weight polyurethanes characterized by hydrolytic stability, versatility and efficiency. It relates to a wide variety of aqueous systems including viscosity agents and their thickeners. The thickeners of the present invention provide a combination of properties not found in any known type of thickener. For example, although they are nonionic and have relatively low molecular weights, they are often very efficient viscosity modifiers. They are stable to water and alcohol and are not sensitive to biodegradation. They are versatile in that they not only practically thicken the finished form of aqueous systems, but also impart a number of subordinate properties as described below. Therefore, as additives to fiber binder compositions, they actually soften rather than stiffen the fabric. In latex paints, in particular, they not only thicken, but also often have excellent flow and leveling properties, and provide excellent viscosity control under both low and high shear conditions. The thickeners of the present invention are urethane polymers having at least three low molecular weight hydrophobic groups, at least two of which are terminal (external) hydrophobic groups. Many of the polymers also contain one or more internal hydrophobic groups. The hydrophobic groups together contain at least 20 carbon atoms and are self-
each having a molecular weight of at least about 1500, preferably at least about 3000, so that the polymer readily dissolves in water through solubilization or interaction with known solubilizers such as water-miscible alcohols or surfactants. Attached through hydrophilic (water-soluble) groups containing polyether segments. The molecular weight of polyurethane is approximately 10,000 to 200,000. The polymer is made in a non-aqueous solvent and is the reaction product of at least (a) and (c) of the following reactants; (a) at least one water-soluble polyether polyol; (b) at least one a water-insoluble organic polyisocyanate, (c) at least one monofunctional hydrophobic organic compound selected from monofunctional active hydrogen compounds and organic monoisocyanates, and (d) at least one polyhydric alcohol or polyhydric alcohol ether. . The product formed includes: (1) a reactant (a) containing at least three hydroxyl groups;
(2) A reaction product of the reactant (a), a reactant (b) containing two isocyanate groups, and the active hydrogen-containing compound described above. Such compounds in which the ratio of equivalents of (a) to (b) is between 0.5:1 and 1:1 are believed to be novel per se; all are believed to be useful in certain systems. (3) a reaction product of reactant (a), a reactant (b) containing at least three isocyanate groups, and an active hydrogen-containing compound; (4) a reaction product of reactant (a) and reactant (b); ) and an organic monoisocyanate; and (5) a reaction product of reactants (a), (b), (d) and an organic monoisocyanate. The reactants are usually used in substantially stoichiometric proportions, that is, the ratio of total equivalents of active hydrogen-containing reactant (whether mono- or polyfunctional) to isocyanate reactant is at least 1:1. be. A slight stoichiometric excess (e.g., about 5-10%) of a monofunctional hydrogen-containing compound can be used to eliminate any unreacted isocyanate functionality that may be present, thereby removing from this source. Avoid toxicity. It is possible to use larger amounts, especially capping hydroxyl compounds, to increase the thickening efficiency. A slight excess of monoisocyanate is often desired when such isocyanate is the capping hydrophobe to ensure capping of all available active hydrogen functionality. A "monofunctional active hydrogen compound" has only one group that is reactive with isocyanate, and therefore such a group contains one active hydrogen atom, even if other functional groups are present. An organic compound that does not react with isocyanates. Such compounds include monohydroxy compounds such as alcohols, alcohol ethers and monoamines,
as well as polyfunctional compounds giving compounds that are only slightly monofunctional to the isocyanate. For example, although primary amines are difunctional in many reactions, they are simply monofunctional with respect to isocyanates, and the hydrogen atoms in the urea group resulting from the reaction are not amino or hindered ( (Unhindered) Relatively unreactive towards isocyanates compared to the hydrogen atoms of alcohols. Reactant (c) is a "capping" compound, meaning that it reacts (caps) with the terminal functional groups of the reaction products of reactants (a) and (b). Polyether polyol reactant (a) is an adduct of an alkylene oxide with a polyhydric alcohol or polyhydric alcohol ether, a hydroxyl-terminated prepolymer of such an adduct and an organic polyisocyanate, or a hydroxyl-terminated prepolymer of such an adduct and an organic polyisocyanate. It is a mixture with such prepolymers. Reactant (d) can be used to terminate isocyanate functionality or to couple isocyanate-terminated reaction intermediates. Reactant (d) can be the same type of polyhydric alcohol or polyhydric alcohol ether used to form the adduct of reactant (a). Polyhydric alcohols or polyhydric alcohol ethers are aliphatic,
Cycloaliphatic or aromatic are possible and it is possible to use alone or as a mixture of either type or of the two types. Organic polyisocyanates include simple di- and triisocyanates, isocyanate-terminated adducts of such polyhydric alcohols with organic di- or triisocyanates, and isocyanate-terminated prepolymers of polyalkylene ether glycols and organic di- or triisocyanates. including. The hydrophobic groups of the polyurethane occur in the residues of reactants (b) and (c) and also in the residues of reactant (d), if present. The terminal (external) hydrophobic moiety is a monofunctional active hydrogen compound, the residue of an organic monoisocyanate, or a combination of residues of such compounds. A variety of polymeric products can be obtained by proper selection of reactants and reaction conditions, including proportions and molecular weights of the reactants. The product has good thickening properties due to the presence and distribution of hydrophilic (polyether) groups (residues of polyol reactants) and hydrophobic groups (residues of hydroxy compounds, amines and/or isocyanates) in it. Show quality. From a structural point of view, the products can be divided into three groups as described below.
Some polymers have an essentially linear structure -
It has a structure whose identity can be easily confirmed, such as, and generally has a star-shaped structure of the formula -. The remaining polymers are a complex mixture. This polymer can replace known thickeners in any aqueous system in which thickeners are commonly utilized, and therefore the thickeners of the present invention find application in numerous industrial and domestic applications. , including pharmaceutical, personal and agricultural compositions. As mentioned above, thickening effects in such compositions include leveling, fluidity,
Improvements in other properties such as stabilization, suspension, high and low shear viscosity control, and bonding properties are also often involved. Although all of Group A, B, and C polymers are useful as thickeners for latex paints and many other aqueous systems, the preferred thickeners for pigment printing pastes and acid dye baths are Groups B and C. belongs to. The term "hydrophobe" in this specification refers not only to the hydrocarbon residues of the hydroxyl, amino, or isocyanate reactants, but also to the adjacent urethane and other groups that remain in the structure after reaction with such residues. including combinations of The term "hydrophobic component" or similar terminology is therefore used herein to mean any part or segment of a polymeric reaction product that contributes to its insolubility in water. All parts or segments of the polyether polyol reactant other than the residues are therefore hydrophobic. Polymer Description The polymeric thickeners useful in this invention are polyurethanes, which can be classified as follows: Group A - Linear Products A-B _p -E _q (-B −E)— _o B _r −E _t −A where each p, q, r and t are independently 0 or 1; at least one of q and r is 1, and if r is 0; t is 0; provided that if q is 1, then a) each of p, r and t is 0 (as in the formula below); or b) p is 0 and r and t are each 1
or c) t is 0 and each of r and p is 1
(as in the equation below); and if q is 0, then r is 1 and each of p and t is 0 (as in the equation below). Polymers falling within the foregoing formulas are: Examples A-E(-B-E) _—o A 1-10 A-E(—B-E) _—o B-E-A 24 -28 A-B-E(-B-E)- _o B-A 29-34 A(-B-E)- _o B-A 11-23 Equivalent weight of total active hydrogen groups to total isocyanate in Group A compounds The ratio is about 1:1 to 2:1. Group B - star-shaped product [H-E-OCH ₂ ] _s L [Q _v (-D _u -E -A)- _w R _z ] _n where L is X, Y or -O-, Q is-
CH ₂ C≡, D is -CH ₂ O-, m is 2
-4, s is 0 to 2, the sum of m and s is the valence of L(2-4), w is 1-3, and each of u and z is independently 0
or 1; and when X is a hydrocarbon group containing at least one carbon atom, preferably 1-4 carbon atoms; Y is -OCONH( _CH2 ) _6N [CONH( _CH2 ) ₆ NHCO−
O]- ₂ , CH ₃ C [CH ₂ O-OCNHC ₇ H ₆ NHCO]- ₃ and CH ₃ CH ₂ C [CH ₂ O-OCNHC ₇ O ₆ NHCO]- ₃ provided that a) if L is X, then u and w are each 1, v and z are each 0, the sum of m and s is 4, and m is at least 2 ( b) If L is Y, then u, v and s are each 0, m is 3, w is 2-3 and z is 0 or 1 (as in the formula below); and c) when L is -O-, v and u are each 1, w is 1-3 and m is 2
and s and z are each 0 (as in the formula below); Polymers falling within the foregoing formula are: Example V. (HE-OCH ₂ ) _s X[CH ₂ O-E-A] _n 35-47. Y [(E-A) _w R] ₃ 48-50. O[ _CH2C { _CH2O -E-A} ₃ ] ₂ 31-63 In each of the polymers in Group A and Group B: A and R are hydrophobic organic groups containing at least one carbon atom. then B is the expression (wherein G is a residue of an organic di- or triisocyanate, and the residue has no residual unreacted isocyanate groups); E is a divalent hydrophilic non-residue; is an ionic polyether group; and n is at least 1, such as about 1-20, preferably 1-10. The equivalent ratio of total active hydrogen to total isocyanate is about 1.2:1 to a stoichiometric excess of isocyanate; be. The values of n given in this specification are averages rather than absolute values, since in reaction products of the type of the present invention the reaction products are often mixtures of several products with different values for n. It will be obvious to polymer chemists that the value of The star-shaped polymer configuration of formula Y- results from polyhydric reactants such as trimethylolpropane or pentaerythritol (residue X in the formula) or triisocyanate (residue Y in the formula); or from polyhydroxy ethers such as dipentaerythritol (Q and D of the formula). L, Q and D form a central hydrophobic core from which the hydrophilic polyether segment E is separated, partially or completely capped with the hydrophobic groups A and R. The tips or arms can have the same or different chain lengths and contain alternating hydrophobic segments with hydrophilic parts. If s is greater than 0, there will be partial capping. A in the formula and in
is a residue of an organic monoisocyanate. Group C - Complex Polymers Group C polymers are complex mixtures of linear, branched and sub-branched products that form a network with hydrophobic components and hydrophobic segments interspersed with hydrophilic segments. The products result from the many different interactions that may occur between the polyfunctional reactants used to form them. The principal reactants are polyfunctional compounds containing at least three hydroxyl or isocyanate groups, difunctional compounds reactive with polyfunctional compounds, and monofunctional reactants such as monohydroxy or monoamino compounds. Each reactant can be present alone or as a mixture of two or more. Difunctional compounds are diisocyanates (for reaction with triols or higher polyols) or diols (for reaction with triisocyanates) and are also present alone or as a mixture of two or more. You can also do that. A monohydroxy or monoamino compound, or a mixture thereof, is added to the reaction mixture to cap the isocyanate of the triisocyanate that has not reacted with the diol to prevent gelation. Monoisocyanates can be added to the reaction mixture if some polyols (diols, triols or higher polyols) remain unreacted or if all the hydroxyl groups need to be capped. It goes without saying that capping of all hydroxyls is not required when making Group C products and Group A and B products. Although not absolutely necessary, capping or hydrolysis of all isocyanates is desirable to avoid toxicity in the polymeric product. Generally no more than about 25% of the hydroxyls should be left uncapped to enhance water solubility and reduce thickening effects. Of course, if the product contains a relatively high proportion of hydrophobic residues, larger amounts of uncapped hydroxyls can be tolerated. Generally speaking, Group C products are polymeric compositions made by reacting: (a) an organic polyol having at least three hydroxyl groups;
(b) a difunctional reactant selected from organic diols, organic diisocyanates, and mixtures thereof; Diol is present in the reaction mixture if polyisocyanate is present and diisocyanate is present if polyol is present; (c) unreacted isocyanate remaining from the reaction of reactants (a) and (b) is present in the reaction mixture; a monofunctional hydroxy or amino compound in an amount sufficient to cap this, if any, and prevent gelation of the reaction mixture; and optionally (d) reactants (a) and (b).
a hydrophobic organic monoisocyanate to cap the hydroxyl groups remaining from the reaction of and the average molecular weight of the polyurethane product is approximately
There are 10000−200000. Examples 64-117 below illustrate these products. As a general rule, the above conditions are true for all Group A, B and C polymers. That is, if the polyether segment is at least
having a molecular weight of 1500 (preferably 3000-20000),
the polymer comprises on average at least three hydrophobic groups and at least two water-soluble polyether segments attached to the hydrophobic moiety, the total number of carbon atoms in the hydrophobic groups being at least 20, preferably 30; And if the total molecular weight is about 10,000-200,000, preferably 12,000-150,000, the polymer will provide good thickening. The optimum polyether content will, of course, depend on the bulk and distribution of the hydrophobic groups in the polymer. 4000− if the polymer contains small external and internal hydrophobic components.
A total polyether molecular weight of 5000 may be suitable, but if larger and/or extensively branched hydrophobic groups are to be created in the polyol, such as long chain fatty polyols or amines, the polyether content may be substantially lower. would have to be increased to Approximately 200 carbon atoms in the hydrophobic portion is a practical upper limit, although it is of course a relative matter since the proportion of polyether increases to offset the increasing hydrophobicity. . however,
As the total molecular weight increases, the viscosity increases and the ease of handling decreases, thus substantially reducing the economic utility of the product. The relatively low molecular weight of the polymers, in conjunction with their non-ionic nature, promotes their efficiency as thickeners, as their thickening performance in a given aqueous system compared to known thickeners is for equal molecular weights, and it is believed that polymers thicken through association mechanisms, such as micellar or other forms of association, rather than molecular weight or chain extension alone. be. For example, 1.0% by weight of polymer in an aqueous dispersion will provide the same thickening provided by other nonionic thickeners at higher concentrations. Of course, the ability to obtain good thickening at relatively low molecular weight and solids levels also promotes other properties such as softening effects on the fibers when the polymer is used in fiber finish compositions. Moreover, the use of organic isocyanate residues as internal or external hydrophobic components also makes the polymers relatively stable against hydrolytic degradation, thereby making them more suitable for use as in systems requiring extended shelf life. greatly expands the usefulness of In certain applications, such as latex paints, the polymers of the present invention provide excellent flow and leveling properties as well as thickening. In other applications, such as paper coating compositions, where high shear thickening is important, the polymers of the present invention can be easily selected as superior in this regard, yet also have good thickening performance and low Maintain shear viscosity. Preparation of the Polymeric Product The first reactant (a) used to form the polyurethanes of this invention is a water-soluble polyether polyol. Typically these are aliphatic, such as polyhydric alcohols or polyhydric alcohol ethers,
They may be adducts of cycloaliphatic or aromatic polyhydroxy compounds with alkylene oxides such as ethylene oxide or propylene oxide, or they may be hydroxyl-terminated prepolymers of such adducts and organic polyisocyanates. The adduct or prepolymer may be a mixture of two or more such adducts or prepolymers, and mixtures of such adducts and prepolymers can also be used. Polyhydric alcohols are not just single glycols such as ethylene glycol and propylene glycol, but also polyalkyloalkanes (e.g. trimethylolpropane, pentaerythritol) and polyhydroxyalkanes (e.g. glycerol, erythritol, sorbitol, mannitol, Also included are hydroxy compounds containing three or more hydroxyl groups, such as (and the like). Polyhydric alcohol ethers are usually adducts of polyhydric alcohols and alkylene oxides, but in some cases are present as by-products with other polyhydroxy compounds. For example, commonly produced pentaerythritol contains about 15% ether, dipentaerythritol. Typical alicyclic polyhydric compounds are cyclopentanediol-1,2,
1,4-cyclohexanediol, hexahydroxycyclohexane, and the like. Polyhydroxy compounds also include aromatic compounds such as di- and trihydroxybenzenes and the like. the aforementioned and numerous other hydroxy compounds,
Adducts and prepolymers are well known and thoroughly described in the technical literature, including Whitmore, Organic Chemistry, 2nd ed.
Dover Publishers, New York;
1961, vol. 2, pp. 302-330, 547-559 and 671-
Includes standard textbooks such as 674. A convenient source of hydrophilic polyether polyol adducts is polyalkylene glycols (also known as polyoxyalkylene diols) of about 4000-20000 molecular weight, such as polyethylene glycol, polypropylene glycol or polybutylene glycol. However, adducts of alkylene oxides with monofunctional reactants such as fatty alcohols, phenols or amines, or adducts of alkylene oxides with difunctional reactants such as alkanolamines (e.g. ethanolamine) are also useful. It is. Such adducts are also known as diol ethers and alkanolamine ethers. Suitable compounds that _provide polyether segments also include amino-terminated polyoxyethylenes of the formula _NH2 ( _CH2CH2O ) _XH , where X ranges from about 10 to 200. Such compounds are sold under the trade name "Jeffamine" and a typical compound is "Jeffamine 2000" with a molecular weight of about 2000. The isocyanate used to form the second type of reactant (b), the water-insoluble organic polyisocyanate, or the hydroxyl-terminated prepolymer contained in reactant (a), is an aliphatic,
Cycloaliphatic or aromatic are possible and can be used alone or in mixtures of two or more thereof, including mixtures of isomers: 1,4-tetramethylene diisocyanate 1,6-hexamethylene diisocyanate (“HDI”) 2,2,4-trimethyl-1,6-diisocyanatohexane 1,10-decamethylene diisocyanate 1,4-cyclohexylene diisocyanate 4,4'-methylene bis(isocyanato) cyclohexane) 1-isocyanato-3-isocyanatomethyl-
3,5,5-trimethylcyclohexane m- and p -phenylene diisocyanate 2,6- and 2,4-tolylene diisocyanate (“TDI”) xylene diisocyanate 4-chloro-1,3-phenylene diisocyanate 4,4'-biphenylene diisocyanate 4,4'-Methylene diphenyl isocyanate ("MDI") 1,5-naphthylene diisocyanate 1,5-tetrahydronaphthylene diisocyanate polymethylene polyphenyl isocyanate "Papi", sold under the trade name "PAPI"
135'' (with an equivalent weight of 133.5 and the average isocyanate functionality is 2.7) and ``Papi 901'' (with an equivalent weight of
133 and average isocyanate functionality 2.3). Trimethylolpropane and tolylene diisocyanate aromatic triisocyanate adduct sold under the trade name "Monder CB-75". Aliphatic triisocyanate product from hydrolytic trimerization of 1,6-hexamethylene diisocyanate, sold under the trade name "Desmodur N". C ₃₆ Dimer Acid Diisocyanate Based on the dimer acid sold under the trade name "DDI" and discussed in J. Am. Oil Chem. Soc. 51522 (1974). Representative monoisocyanates of one form of reactant (c) include linear, branched and cyclic isocyanates such as butyl isocyanate, octyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, cyclohexyl isocyanate, and the like. These isocyanates can also be used alone or as mixtures of two or more thereof and are a convenient method for introducing terminal hydrophobic moieties into the polymer. Mono- or polyisocyanates are also polyfunctional isocyanates derived by reacting any of the above-mentioned isocyanates with an active hydrogen compound having at least two functionalities so that at least one isocyanate group remains unreacted. Also includes. Such isocyanates are equivalent to chain extension of isocyanate-terminated isocyanate/diol reaction products by well-known methods in polyurethane synthesis with reactants containing at least two active hydrogen atoms. A variety of other useful mono- or polyisocyanates are described in urethane chemistry, including Advances in the Science and Technology of Urethanes, authors Fritsch and SL Regan, Technomic Publishers, Volumes 1 (1971) and 2 (1973). It is described in the text, and the bibliography is listed here. The isocyanate can contain any number of carbon atoms effective to provide the desired degree of hydrophobic character. Generally about 4
From 30 to 30 carbon atoms are sufficient, the choice depending on the proportion of other hydrophobic groups and hydrophilic polyether in the product. A third type of reactant (c) whose functional group is hydroxyl
Examples of monofunctional active hydrogen compounds are aliphatic ( _C1 - _C24 ) alcohols such as methanol, ethanol, octanol, dodecanol, tetradecanol, hexadecanol, and cyclohexanol; phenol, cresol, octylphenol, Phenols such as nonyl and dodecyl phenols; monomethyl of ethylene glycol;
Alcohol ethers such as monoethyl and monobutyl ethers and similar ethers of diethylene glycol; straight or branched (C ₁ -C ₂₂ )
Alkyl and alkaryl polyether alcohols such as alkanol/ethylene oxide and alkylphenol/ethylene oxide adducts (e.g. lauryl alcohol, t-octylphenol or nonylphenol/ethylene oxide adducts containing 1-250 ethylene oxide groups) ); and mixtures thereof with other alkyl, aryl and alkaryl hydroxy compounds such as the _C10 - _C20 normal alcohol mixture known as "Alfol" alcohol. Amino compounds as monofunctional active hydrogen compounds that can be used in place of all or part of the monohydroxy compounds include about 1-20 in the alkyl group.
primary or secondary aliphatic, cycloaliphatic or aromatic amines, such as straight-chain or branched alkyl amines containing 5 carbon atoms, or mixtures thereof. Suitable amines are n- and t-octylamine, n-dodecylamine, _C12 - _C14 or _C18-
C ₂₀ t-alkylamine mixtures and secondary amines such as N,N-dibenzylamine, N,N-dicyclohexylamine and N,N-diphenylamine. If there are enough hydrophobic residues in the products from other sources, such as isocyanates or hydroxyl compounds, to provide a total of at least 10 carbon atoms in the end groups (together) in the polymer product. In some cases it is also possible to use lower alkyl ( _C1 - _C7 ) amines. It is possible for the amino compound to contain one or more active hydrogen atoms as long as it is only slightly monofunctional towards one isocyanate group under normal reaction conditions. Primary amines are an example of such compounds. The foregoing and numerous other useful monohydroxy and amino compounds are described in standard organic textbooks and in the Whitmore text cited above, pages 102-138.
and other referenced articles such as those at 165-170. The polymer is made according to techniques generally known for the synthesis of urethanes, preferably with no unreacted isocyanate remaining. Water should be excluded from the reaction as it will consume the isocyanate functionality. Anhydrous conditions are removed by azeotropic distillation, by heating under nitrogen sparge,
or by pre-drying the reactants. If desired, it is also possible to carry out the reaction in a solvent in order to reduce the viscosity during the reaction in order to lead to higher molecular weight products. High viscosity in the reaction medium causes poor heat transfer and difficult stirring.
Generally, solvents are useful when molecular weights of 30,000 or greater are encountered. No solvent is required for molecular weights below this. If used, the solvent should be inert to the isocyanate and capable of dissolving the polyoxyalkylene reactant and urethane product at the reaction temperature. Suitable non-toxic solvents are benzene, toluene,
Xylene and "Solvesso 100"
or other well-known aromatic-rich solvents such as the solvent sold under the trademark "Solbetsuso 150", as well as inert hydrogen-containing compounds such as ethyl acetate, butyl acetate and acetic acid (Cellosolve). esters and dialkyl ethers of ethylene glycol, diethylene glycol and the like. Many other well known solvents can also be used. Reaction temperature is not critical. Convenient reaction temperatures are from about 40°C to 120°C, preferably about 60°C. ℃ or so
The temperature is 110℃. The reaction temperature should be chosen to avoid undesirable side reactions such as isocyanate-urethane condensation and to obtain reasonably fast reaction rates. The order of reactant charging is not critical in most cases. However, in some cases, when the reactants are of high molecular weight or multifunctional, the order of addition is clearly adjusted to avoid gelation. For example, to avoid high molecular weights while obtaining a good proportion of hydrophobic properties, the hydrophobic component-contributing reactants, such as monohydroxy compounds, amines or monoisocyanates, are charged first, followed by polyoxyalkylene glycols. It is desirable to add If you want a high molecular weight,
It is possible to charge the hydrophobic component-contributing reactants after the polyoxyalkylene glycol, or to charge some of the hydrophobic reactants first and add the remainder after the remaining reactants. The charging may also be continuous or semi-continuous as desired. The order of addition, proportions of reactants and other reaction conditions can thus be varied in accordance with well-known principles of polyurethane to control the configuration, molecular weight and other properties of the product. As is clear from their formulas and the examples below, the polymers of group A form prepolymers of polyoxyalkylene glycols and diisocyanates and then, if the prepolymers have hydroxyl end groups, monoisocyanates or mono- It is conveniently prepared by capping with a di-isocyanate mixture or, if the prepolymer has isocyanate end groups, with a monohydric or amino compound (or an adduct of a monohydric compound and/or an amino compound with an alkylene oxide). Group B polymers are made in a similar manner except that polyfunctional compounds such as trimethylolpropane or triisocyanates are used as reactants. For example, star-shaped polymers generally result when trimethylolpropane-ethylene oxide adducts or triisocyanates are reacted with monoisocyanates or with monohydroxy compound-ethylene oxide adducts, respectively. Suitable polyisocyanates are DESMODIUR N and MONDIUR CB-75 described below. Group C of more complex polymer mixtures involves reaction of polyols (at least three hydroxyl groups) or triisocyanates with diisocyanates and polyether diols, respectively, followed by capping of unreacted isocyanates with monools or monoamines or of unreacted hydroxyls. Resulting from capping with monoisocyanates. Examples of suitable polyols are polyalkyloalkanes such as trimethylolpropane or trimethylolbutane, hydroxy compounds with ether linkages such as erythritol (dipentaerythritol, tripentaerythritol, and the like) and glycerol, butanetetraol. , sorbitol, mannitol, and the like. As already mentioned, not all of the hydroxyl groups have to be capped with the monoisocyanate hydrophobic moiety. The proportions of reactants play an important role in determining the properties of the polymer. For example, if Group A linear polymers are made from isocyanate-terminated polyethylene glycol (PEG molecular weight 6000-7500) prepolymers capped with decyl or dodecyl alcohol and the isocyanate is tolylene diisocyanate (TDI), the alcohol/
A PEG/TDI equivalent ratio of 0.2-0.3/0.8-0.7/1.0 provides a polymer that is an excellent thickener for latex paints. However, the ratio is about 0.1/
When the ratio is 0.9/1.0, the thickening performance is somewhat inferior, but the fluidity and leveling ability in the paint is very good. Further description of these and other properties is given in the subsequent disclosure of polymer preparation below. Prepolymers, adducts or other reactants containing ester groups should be avoided due to the hydrolytic instability of products containing such groups. However, the reactants can include any other groups as long as they are inactive, ie, do not interfere with the formation of the desired product. For example, halogens such as chlorine and bromine will normally not interfere with the formation of useful polymers. Product Consistency The consistency of the polymeric thickener product can be controlled by the solvent reaction medium (described above) or by combining the product with a softener after synthesis. Without such treatment, higher molecular weight products become stiff and difficult to handle. Depending on the molecular weight of the product, the solids content, and the type and amount of additives, the product can be made to vary in consistency from a soft wax to a paste. Such consistency is important for the subsequent handling of the product, including the ease with which it is to be dispersed into the aqueous system to be thickened. Although on a laboratory scale it is possible to adjust the consistency of higher molecular weight products by simply including more solvent during the synthesis, on a manufacturing scale the synthesis is usually reduced in order to maintain reaction vessel volume. Requires the use of a minimum amount of non-polar solvent during the synthesis, followed by the addition of a softener to the mixture towards the end of the synthesis or subsequent to the synthesis. Although it is possible for some polar solvents to be present during the synthesis (solvents that are inert to isocyanates, such as ketones and esters), such presence increases the cost of solvent recovery and the cost of keeping polar solvents anhydrous. Undesirable due to difficulty and phase separation. Desirably, the consistency of the product is controlled by synthesizing the high molecular weight product in the presence of a non-polar solvent and then adding a softener to the reaction product mixture. Useful emollients are polar or non-polar organic solvents, nonionic surfactants such as polyethoxylated alkylphenols, or any mixture of two or more such solvents and/or surfactants. be. It is possible to separate the product prior to treatment with the softener, but this is usually not beneficial due to increased process costs. The amount of softener can vary widely, for example on the order of about 1-50%, and desirably about 2-15% by weight of the reaction product mixture. The softener may also contain small amounts of water, on the order of about 0.5-10%, preferably about 1-2%, based on the total weight of the reaction product mixture. Preferred softeners are mixtures of non-polar aromatic hydrocarbon solvents and polar organic solvents, such as the reaction medium solvents described above, with or without water. Typical mixtures and amounts effective to soften polyurethane products include the following:
100 Non-Polar Fragrance Solvent can be added as part of the softener or may already be present in the reaction product mixture, and during the addition of the softener the polyurethane reaction product mixture is heated to about 80°C. be:

B/Water Latex Coating Composition The present invention includes a latex coating composition containing an emulsion or dispersion of a water-insoluble polymer and a polymeric thickener from the group of polymers described above. The water-insoluble polymer may be of any type conventionally utilized in latex coating compositions and includes natural rubber latex compositions and synthetic latexes in which the water-insoluble polymer is mono- or polyethylenically unsaturated. Emulsion polymers of the olefinic, vinyl or acrylic monomer type, including homopolymers and copolymers of such monomers. Specifically, the water-insoluble emulsion polymer poly(vinyl acetate) and vinyl acetate (preferably at least 50% by weight) and one or more of vinyl chloride, vinylidene chloride, styrene, vinyltoluene, acrylonitrile, methacrylonitrile, copolymers with acrylamide, methacrylamide, maleic acid and their esters, or one or more esters of acrylic acid and methacrylic acid mentioned in U.S. Pat. Well known as a film-forming component of base paints; homopolymers of _C2 - _C40 alpha olefins such as ethylene, isobutylene, octene, nonene, and styrene, and the like; carbonization of one or more of these copolymers of hydrogen with one or more esters, nitriles or amides of acrylic acid or methacrylic acid, or with vinyl esters such as vinyl acetate and vinyl chloride, or with vinylidene chloride; and with one or more butadiene. Diene polymers such as copolymers with one or more of styrene, vinyltoluene, acrylonitrile, methacrylonitrile, and esters of acrylic or methacrylic acid. It is also quite usual to include small amounts of acid monomers, such as 0.5 to 2.5% or more, in the monomer mixture used for the preparation of the above copolymers by emulsion polymerization. The acids used include acrylic acid, methacrylic acid, itaconic acid, aconitic acid, citraconic acid,
Contains crotonic acid, maleic acid, fumaric acid, methacrylic acid duplex, etc. Vinyl acetate copolymers are well known and include vinyl acetate/butyl acrylate/2-ethylhexyl acrylate, vinyl acetate/butyl maleate, vinyl acetate/ethylene, vinyl acetate/vinyl chloride/
Includes copolymers such as butyl acrylate and vinyl acetate/vinyl chloride/ethylene. Throughout this specification, the term "acrylic polymer" means any polymer in which at least 50% by weight is acrylic or methacrylic acid or ester, including mixtures of those acids and esters individually and together. "Vinyl acetate polymer"
The term refers to any polymer containing at least 50% by weight vinyl acetate. Even small particle (approximately 0.1-0.15 microns) acrylic and other latexes are effectively thickened by the thickeners of the present invention and have improved flow and leveling properties. Such latexes are well known for their resistance to modification by conventional thickeners. Aqueous polymer dispersions can be prepared using one or more anionic, cationic or nonionic emulsifiers according to well known procedures. Mixtures of two or more emulsifiers can also be used regardless of their type, but are excluded because mixing any appreciable amount of the cationic type and the anionic type is generally undesirable as they tend to neutralize each other. be done. The amount of emulsifier can range from about 0.1 to 6% by weight, based on the total weight of monomer charge, or in some cases more. When using persulfate type initiators, the addition of emulsifiers is often unnecessary. The omission or use of very small amounts of this emulsifier, e.g. below about 0.5%, is often used from a price point of view, as well as low sensitivity of the dry coating or moisture impregnation, since the coated substrate is therefore less sensitive to moisture. desirable. Generally, the molecular weight of these emulsion polymers is large, e.g.
Most commonly with an average viscosity of 100,000 to 1,000,000
500000 or more. These and other emulsion polymer systems that can be thickened with the polymeric thickeners of the present invention are discussed, for example, in U.S. Pat.
3037925, and is described in a wide range of literature on the subject. One of the significant benefits when using the polymeric thickeners of the present invention is the ability to obtain an optimum value and balance of viscosity of aqueous dispersions containing polymers under high and low shear conditions, as well as film-forming ability, flowability. and the ability to precisely tailor the structure of the polymer to obtain leveling properties and other properties particularly desired in latex coating compositions. This is achieved by establishing a particular type and size of hydrophobic groups in the polymeric thickener and by selecting the hydrophilic molecular weight to provide an effective distance between the hydrophobic components to obtain good thickening by a cooperative mechanism. achieved. Hydrophobic groups most readily amenable to such adjustment are based on aliphatic or aromatic monohydroxy or monoamino compounds (alcohols, phenols, amines) and organic monoisocyanates, preferably containing about 4-20 carbon atoms. It is a terminal hydrophobic group. It is particularly surprising that such modulation can be effected by small, relatively low molecular weight hydrophobic capping groups. Polymeric thickeners can be added to polymer latex systems at any time during their preparation, including before or after polymerization or copolymerization, and by single or multiple additions. Usually from about 0.1 to about 10% by weight, preferably 1-3% by weight, based on polymeric latex solids, of polymeric thickener is suitable to provide suitable thickening levels and other properties. However, the amount can be higher or lower depending on the particular system, other additives present, and similar reasons understood by the formulator. Because polymeric thickeners are nonionic, they are particularly useful in latex paints and other latex compositions with an alkaline PH. They are also compatible with many types of latex composition additives, such as antifoams, pigment dispersants, and all types of surfactants, and extend shelf life. The thickener can be mixed with the paint or other composition components at any point during their manufacture and even be a final addition to the composition. Polymeric thickeners such as hydroxyethyl cellulose, casein, alginate and starch are preferred in terms of performance and resistance to degradation, allowing adaptation of thickeners to obtain an optimal balance of properties in coating compositions. Offers substantial benefits over natural or semi-synthetic thickeners. Other applications Other aqueous systems in which polymeric thickeners are useful include aqueous coating compositions for the paper, leather and textile industries;
Oil well water increasing compositions and drilling mud, cleaning agents, adhesives,
waxes, polishes, cosmetics and toiletries,
Includes topical pharmaceuticals, and pesticides or agricultural compositions for controlling insects, rodents, fungi, parasitic plants of all kinds, and undesirable plant growth. However, this polymer is also useful for thickening water alone, and the resulting solution is then useful for addition to other systems to be thickened. For example, adding a suitable amount of a water-soluble alcohol such as methanol to water containing 25% by weight thickener forms a "clear concentrate" useful in making pigment printing pastes. In the textile field, the thickeners are useful as warp sizes, textile finishes, adhesives for both woven and nonwoven fabrics, tie coats, and for thickening dyeing and coloring compositions of all types. For printing paste emulsions and dispersions, Group B and Group C polymers (Example 35-117) are A
Group B and C polymers contain more hydrophobic groups and/or higher molecular weight hydrophobic groups. The textile printing paste can be a mere aqueous dispersion or an oil-in-water emulsion. Any water soluble or insoluble coloring materials can be used, such as inorganic pigments and vat dyes. For example, the thickeners of the present invention are described in US Pat.
It can be used as a substitute for the thickeners described in the dye or coloring aid compositions of Nos. 3468620, 3467485 and 3391985. Although organic isocyanates are essential reactants for forming the polymeric thickeners of this invention, any residual isocyanate is easily removed by dispersing the thickener in water. This removes any isocyanate toxicity from thickeners and thereby various types such as hand creams, hand lotions, cleaning creams, hair creams, cold waving lotions, shampoos, cream rinses and the like. It is suitable as an additive for cosmetics. The thickeners of the present invention are also used in U.S. Pat.
The polyoxyethylene-polyoxypropylene gels of No. 3740421 form "ringing" gels in aqueous solutions and, like the gels of that patent, can be used in cosmetic and pharmaceutical compositions. . The following examples further illustrate the invention in one or more of its various aspects. All parts and percentages in the examples are by weight unless otherwise specified. Molecular weights of polyalkylene ether reactants or residues are based on hydroxyl number unless otherwise specified. Example 1-34 Group A - Linear Polymer Example 1 Tolylene diisocyanate (TDI)-polyethylene glycol (PEG) prepolymer capped with dodecyl isocyanate A mixture of 60 g of PEG (molecular weight 6000) and 200 g of toluene was azeotropically distilled. It was shaken and dried. The mixture was cooled to 75° C. and 0.06 g dibutyltin dilaurate and 1.4 g TDI were added. 2
After an hour at 75°C 1.7 g of dodecyl isocyanate was added. This mixture was then heated to 60°C for 4
I kept it for days. The resulting solid polymer was removed from the slab mold after toluene evaporation and determined by gel permeation chromatography to determine its weight average molecular weight (M _w ).
71,100 and a number average molecular weight ( _o ) of 15,900. Examples 2 and 3 TDI-PEG prepolymers capped with dodecyl isocyanate and octadecyl isocyanate A mixture of 400 g of PEG (molecular weight 4000) and about 600 g of toluene was dried by azeotropic distillation. The mixture was cooled to 75°C and 0.4 g of dibutyltin dilaurate was added. Approximately 1/3 of this reaction mixture
6.34g dodecyl isocyanate (Example 2)
added. 8.9 g of octadecyl isocyanate (Example 3) was added to another third of the reaction mixture.
The solid polymer product was isolated as described in Example 1. The structures of the polymer products of Examples 1-3 are listed below along with Table 1. This table also includes similar products made essentially as described above, with major changes as indicated.

Table 1) The diisocyanate providing this residue throughout all examples of this application was a commercial mixture of the 2,4- and 2,6-isomers of tolylene diisocyanate. The value of X in all examples was based on the nominal molecular weight of commercially available polyethylene glycol products rather than on lot-by-lot analysis. 2) The diisocyanate providing this residue throughout all examples of this application is “DDI”, i.e.
It was a C ₃₆ dimer acid based diisocyanate from Mils Corporation. 3) The diisocyanate providing this residue throughout all examples herein was 4,4'-methylenebis(isocyanatocyclohexane), commercially available as "Hylene W". Example 11-23 Isocyanate-terminated Prepolymer of Polyethylene Glycol and Diisocyanate Capped with Aliphatic Alcohol or Amine The reactions tabulated in Table 2 below are based on 50 g of PEG.
(molecular weight 4000 to 20000), a mixture of 0.05 g dibutyltin dilaurate and 50 g toluene was previously dried by azeotropic distillation. The reaction mixture was cooled to 60°C and the aliphatic alcohol or amine was added followed by the diisocyanate listed in the table. After maintaining the reaction temperature at 60°C for 3-5 days, the solid thickener was evaporated in a slab mold to separate the solid polymer. The structure of the product is shown below along with Table 2.

Table: Examples 24-28 Diisocyanate-polyethylene glycol prepolymer capped with ethylene oxide-monohydric compound adduct. The mixture was reacted at 60°C for 24 hours. At that point the toluene solution was divided into six equal parts: to these four were separately added 15 meq of pre-dried alcohol of the following structure: (a)
Octylphenol-ethylene oxide adduct with a molecular weight of 3000, (b) hexadecyl alcohol-ethylene oxide adduct with a molecular weight of 3000, (c) dodecyl alcohol-ethylene oxide adduct with a molecular weight of 2600, and (d)
Octadecanol-ethylene oxide adduct with a molecular weight of 2800. The reaction temperature was maintained at 60° C. for 4 days, and the solution was poured out and air dried. The resulting polymers are shown below and in Table 3 (Example 24,
26, 27 and 28).

【table】

Table Example 29-34 Polyethylene glycol-diisocyanate prepolymer reacted with diisocyanate and capped with monohydric alcohol Azeotropic distillation of a mixture of 120 g PEG (molecular weight 20000), 480 g toluene, and 0.12 g dibutyltin dilaurate It was dried by At 75℃
2.16g of "DDI" diisocyanate was added.
Adding 2.2 g of 4,4'-biscyclohexylmethane diisocyanate (at 75°C) during 2 hours;
The reaction mixture was then stored at 60°C for 3 days. The mixture was then divided into three equal parts. Mixture A contained 0.355 g of n-butanol and Mixture B contained 0.625 g of n-butanol.
octanol, and for mixture C 0.90 g of n
-Dodecanol was added. After 4 days at 60°C the samples were poured out and air dried. The polymer product is further illustrated with another product made in a substantially similar manner having the following structure as defined in Examples 29-31 of Table 4.

[Table] Example 35-63 Group B - Star Polymer Example 35 In a suitable reaction vessel, 70 g of trimethylolpropane-ethylene oxide and hydroxyl number 12.5 (equivalent
4500 per OH) and about 100 g of toluene were dried by azeotropic distillation. Then 0.07
g of dibutyltin dilaurate and 6.34 g of octadecyl isocyanate were added. After 4 days at 60°C the samples were dried in slab molds. The structure of this polymer product is shown below along with Table 5, which also shows a similar polymer product made in essentially the same manner as the product of Example 35 with the major changes indicated in the table. I raised it.

【table】

[Table] Example 48-50 Ethoxylation Dodecanol capped triisocyanate and methoxy capped polyethylene glycol 40 g each of ethoxylated dodecanol with a molecular weight of 7300, 11.8 g of monomethoxy with a molecular weight of 5000
Two mixtures of cap polyethylene glycol, 80 g toluene and 0.08 g dibutyltin dilaurate were dried by azeotropic distillation. 60℃
After cooling to 2.54 g of Mondial CB-75 (Example 48) or 0.09 g of Desmodyur N (Example 49) was added to the reaction mixture. After 3 hours at 60°C, an infrared spectrum showed the reaction was complete and the reaction mixture was poured into a slab mold to separate the solid polymer. The structures of these polymers and other polymers made in essentially the same manner are shown below along with Table 6.

[Table] Examples 51-63 Example 51 Dipentaerythritol-ethylene oxide adduct capped with octadecyl isocyanate Dipentaerythritol-ethylene oxide adduct with 18.1 hydroxyl number (3100 equivalents) was heated under nitrogen sparge to remove water. Excluded. Utilizing dibutyltin dilaurate as a catalyst, 70 g of the adduct was reacted with 7.06 g of octadecyl isocyanate,
It gave an NCO/OH ratio of 1.06/1 equivalent. reaction is 60
℃ for 4 days. The polymer product was then poured into slab molds and allowed to dry and solidify. The structure of this product is shown below by formula along with Table 7, which shows similar polymers made in essentially the same manner as above and NCO/OH ratios in equivalent weights.

Table Example 64-117 Group C - Complex Polymers As mentioned above, the difunctional reactants (polyether diols or diisocyanates) in the reaction mixture are replaced by trifunctional reactants such as triisocyanates or trihydroxy compounds, respectively. (or higher functionality) results in complex branching in the product and leads to different polymer products whose identity cannot be determined satisfactorily. However, the polymeric reaction mixture contains the necessary proportions of hydrophobic and hydrophilic substances for good thickening properties and is therefore a useful product. Table 8 below summarizes a number of possible reactant combinations which provide equivalent amounts of such polymeric reaction products and the proportions of reactants useful in such reactions. The Examples and Tables that follow more specifically illustrate these reactions.

[Table] Surplus Examples 64-72 Example 64 Alcohol-capped trimethylolpropane-PEG to provide multi-branched polymer
- TDI prepolymer 2.24g trimethylolpropane and 19.56g TDI in 150g toluene were mixed at 78°C. 15
Dilaurin dibutyltin 0.3 minutes after this mixture
300 g of PEG (molecular weight 6000) which had been previously dried in 300 g of toluene. After 2 hours at 75°C, the mixture was cooled to room temperature and kept there for 72 hours. The solution was then warmed to 80°C and divided into three equal parts. Part A was treated with 2.93 g octanol, part B was treated with 4.27 g dodecanol, and part C was treated with 6.1 g octadecanol. After 24 hours at 60℃, samples A and B
and C (Examples 64-66) were isolated after evaporating the toluene from the slab mold. Example 67 Multi-branched polymer from trimethylolpropane-ethylene oxide adduct, TDI, PEG and octadecanol 61 g with hydroxyl number 18.2 (3100 equivalents)
A mixture of trimethylolpropane-ethylene oxide adduct, 240 g PEG (molecular weight 6000) and 5.4 g octadecanol was dried by azeotropic distillation of a solution in 539 g toluene. Mixture at 60℃
11.3g TDI and 0.3g dibutyltin dilaurate were added and the temperature was raised to 70°C. After 3 hours 4.1g of octadecanol was added and the temperature was raised to 80°C. After 3 hours at 80°C, the reaction mixture was poured into a slab mold and the toluene was evaporated off. Example 68 Multi-branched polymer from trimethylolpropane, TDI, PEG and octadecanol The procedure of Example 67 was followed except that the trimethylolpropane-ethylene oxide adduct of Example 67 was
Replaced with 0.9g of TMP. Example 69 Monohydric Triol-PEG Adduct
The alcohol and diisocyanate were reacted and capped with monohydric alcohol. 10.5 g of "Pullacol" TP-1540 (triol adduct of propylene oxide and trimethylolpropane), 244.5 g of PEG-6000 (equivalent weight 3700), 0.3 g
of dibutyltin dilaurate, 5.4 g of octadecanol and 400 g of toluene were dried by azeotropic distillation. At 60°C 11.3g of toluene diisocyanate was added. After 3 hours at 70°C, an additional 4.05 g of octadecanol was added. After an additional 3 hours at 80°C, the mixture was poured out and air dried. Table 9 lists the aforementioned and other reactants used to make other polymers essentially as described above. Equivalent proportions of reactants are given in parentheses. In this and subsequent examples "TMP" is trimethylolpropane, "EO" is ethylene oxide and "PO" is propylene oxide. E.O.
or the following for PO is EO in the reactants or
Represents the number of PO units.

Table: Examples 73, 74 Multi-branched polymers from triols, diols, monofunctional amines and diisocyanates Example 73 2.68 g trimethylolpropane (60 meq), 360 g PEG-6000 (120 meq), 0.36 g
of dibutyltin dilaurate and 500 g of toluene were azeotropically distilled to remove water. Then 270 meq (23.5 g) of TDI was added at 50°C. 3 at 75℃
After leaving it for a while, take out 1/3 of the solution and 5.7g (30g)
Primene 81-R (milliequivalent),
_C12 - _C14 t-alkyl primary amine.
After 48 hours at 60°C, the polymeric mixture was separated by distillation of toluene. Examples 75-81 Multi-branched polymers from PEG, trimethylolpropane-ethylene oxide adduct, octadecyl isocyanate and diisocyanate Example 75 A mixture of 225 g PEG (molecular weight 20 000) and 400 g toluene was prepared by azeotropic distillation at 70°C. I hung it to dry. Then 0.225g dityltin dilaurate and 3.34g octadecyl isocyanate were added. After 2 hours, still at 70°C, 7.4g of "DDI" was added. Hydroxyl number within 1 hour
17.5 g of pre-dried trimethylolpropane-ethylene oxide adduct with an equivalent weight of 3300 were added.
After 5 days at 60°C, the mixture was dried in a slab mold. Table 10 lists other reactants that provide the foregoing and other polymeric products made in essentially the same manner. Equivalent proportions of reactants are given in parentheses.

[Table] Examples 82-92 Reaction of polyethylene glycol and monohydric alcohol with diisocyanates and triisocyanates Example 82 296.3 g of PEG (molecular weight 7400 and equivalent weight in hydroxyl number 3700), 8.1 g octadecanol,
A mixture of 400 g toluene and 0.4 g dibutyltin dilaurate was dried by azeotropic distillation. 60
7.83 g of tolylene diisocyanate and 5.2 g of "Desmodyur N" were added at <0>C. 70
After 3 hours at 80°C and 3 hours at 80°C, the polymeric reaction product was poured out and air dried. lower number
Table 11 lists the reactants described above and other reactants used to make the polymers in essentially the same manner. Equivalent proportions are given in parentheses.

[Table] Examples 93-97 Reaction of trimethylolpropane-ethylene oxide adduct with octadecyl isocyanate and diisocyanate Example 93 150 g and 200 g of trimethylolpropane-ethylene oxide adduct with hydroxyl number 9.7 (equivalent weight 5800)
of toluene was dried by azeotropic distillation. Then 0.15g dibutyltin dilaurate,
6.11g octadecyl isocyanate and 3.09
'DDI' was added at 60°C. After 5 days at 60°C, the polymer product was separated after evaporating the toluene from the slab mold. Table 12 below lists the reactants described above and other reactants used in the polymer made essentially as described with respect to Example 93. Reactant proportions are given in equivalents in parentheses.

[Table] Examples 98-103 Polymer capped with monoisocyanates from triisocyanates Example 98 A mixture of 150 g of polyoxyethylene glycol (molecular weight 6000), 150 g of toluene and dibutyltin dilaurate catalyst was azeotropically distilled. Dry. At 70°C 5.93g of dodecyl isocyanate was added. After 2 hours at 70 DEG C., isocyanate consumption was complete and 4.49 g of 75% Desmodyur-N triisocyanate was added. The reaction mixture was kept at 60° C. for 18 hours and then dried in a slab mold. Table 13 below lists the reactants described above and other reactants used to make the polymers in essentially the same manner. Give the equivalent proportion in parentheses.

【table】

[Table] Examples 104-113 Alcohol-capped polymers from triisocyanates Examples 104-105 A mixture of 70 g of dodecyl alcohol-ethylene oxide adduct (molecular weight 4800) and 90 g of toluene is azeotroped until the evolution of water stops. Distilled. then 60
0.07 g of dibutyltin dilaurate and 6.01 g of desmodyur-N triisocyanate were added at <0.0>C. After 80 minutes at 60°C, infrared spectra showed complete digestion of hydroxyl. 85 g of the resulting reaction mixture was dissolved in 50 g of toluene.
Add 27g of %PEG (molecular weight 6000) solution (A); 45g
59 g of a solution of 40% PEG (molecular weight 20,000) dissolved in toluene was added to the reaction mixture (B). Further 60℃
After 3 hours at room temperature, polymer samples A and B (Examples 104, 105) were poured out and allowed to air dry. Table 14 below lists the foregoing reactants and other reactants used to make the products essentially as described above. Percentages in equivalents are given in parentheses.

【table】

TABLE Examples 114-117 Multibranched Polymers from Triols, Monols and Diisocyanates ) to prepare a polymeric reaction product.

Table 118-127 A Preparation of Aqueous Solutions of Thickeners Table 16 below shows Bruckfield viscosity measurements for 3% aqueous solutions of various polymeric thickeners identified under the Examples herein above. shows. Solutions were made by standard mixing techniques. B. Preparation of Polymer Emulsions Table 16 below also reports the Bruckfield and ICI viscosities of various polymer emulsions made by standard mixing techniques from the formulations below, where the thickener was Identified further above under Examples: Parts by weight Acrylic copolymer (46.5% solids) ¹⁾ 80.0 Water 11.2 Aqueous solution of thickener ²⁾ , 3% 24.8 C Preparation of latex coating composition Table 16 below Also shown are the properties of coating compositions containing the polymeric thickener or hydroxyethylcellulose (HEC) of the previous examples. The prescription for the paint composition is as follows. The pigment grind, premix and thickener solution are made separately and then mixed with the other ingredients in the order given. Mixing techniques and equipment are conventional. The thickener solution contained 3.2% by weight of HEC or 6% by weight of the thickener of the present invention and the final coating was formulated to contain 1% by weight of thickener based on the emulsion polymer solids. . Pigment grinding part: parts by weight Dispersant [Tamol 731] 10.8 Defoamer [Nopco NDW] 2.0 TiO ₂ (TiPure-R-900) 296.0 Reduction part: Propylene glycol 57.8 Polymer emulsion ¹⁾ A or B 557.9 Premix: Preservative (Super A ^d - I _t ) 1.0 Water 15.2 Flocculant [Texanol] 15.7 Anionic surfactant [Triton GR
-7] 2.0 Defoamer (Nopco NDW) 2.9 Thickener solution: 80.4 Table 16 shows that although HEC effectively thickens water, it is not suitable for latex based on water thickening alone. Efficient thickening of paints and simple polymer emulsions is shown to be unexpected.
The table also shows that in many cases the polymeric thickeners of the present invention will thicken latex paints equally or more efficiently (improved viscosity relative to the amount of thickener) than HEC, and that Examples 118 and 121 show that good performance (thickening, fluidity and leveling, film formation in terms of high ICI viscosity) is obtained from polyurethanes with a large number of hydrophobic groups.

[Table] 1) Polymer emulsion A is Rhoplex AC-490 copolymer acrylic emulsion (46.5% solids): Polymer B
is Roplex AC-61 copolymer acrylic emulsion (46.5% solids). 2) Thickener solids content relative to emulsion polymer solids content is 2%. 3) Krebs units--low shear viscosity. 4) Simulating the shearing force exerted on the paint during brush painting.
High shear viscosity measured on an ICI cone and plate viscometer (Research Equipment Limited, London) operating at a shear rate of 10000 s ^-1 . Generally, as ICI viscosity increases, film thickness (built-up) also increases. Good coating thickness exhibits enhanced hiding power of the paint and also contributes to improved flow and leveling properties. 5) Line up the withdrawals of the controlled paint (containing HEC as a thickener) and the test paint containing the thickener of the invention (the "Test") in the Leneta form.
Form) 1B "Penopac" Chart. 6) Visual inspection of the brush marks on the Reneta Foam 12H coverage chart. The grade is 0-10
A grade of 10 represents exceptional flow and leveling properties and 0 represents completely unacceptable flow and leveling properties. Examples 128-130 Table 17 below compares the properties of latex coating compositions containing thickeners of the present invention or hydroxyethyl cellulose (HEC). Examples 128 and 129
The formulation of Example 128 is similar to the coating examples in Table 16, but the coating formulation of Example 128 is as follows (made by standard mixing in the order given) where the amount of thickener is equal to that of the emulsion. 2% based on polymer solids: Pigment grinding part: parts by weight Water 85.0 Dispersant (Tamol 731) 8.0 Dispersant (tetrasodium pyrophosphate) 0.3 Surfactant [Tergitol NPX]
2.0 Mildewcide (Super-A ^d I _t ) 1.0 Ethylene glycol 20.0 Flocculant (hexylene glycol) 15.0 2-ethylhexyl acetate 5.0 Defoamer (Nopco NDW) _2.5 TiO 2 -Rutile (TiPure-R-901) 175.0 TiO ₂ -anatase [Titanox]
1000] 50.0 Mica, wet milled (325 mesh) 25.0 Talc [Nytol 300] 125.0 Reduced portion: Water 36.1 Polymer emulsion 400.0 Defoamer (Nopco NDW) 2.5 Thickener solution 170.9 Table 17 shows hydroxyl The deviscosity agents of the present invention are desirable for utility in latex coating compositions because the thickeners of the present invention exhibit a superior balance between thickening efficiency, flowability, and leveling properties when compared to coatings containing ethylcellulose. Illustrate.

[Table] Acrylic

[Table] Niru Aku
Lil type
Example 131 Pigment Printing Paste Pigment printing pastes are typically composed of three main components: pigment, thickener, and binder. Before mixing these ingredients to form the printing paste, a “cut clear” is applied from the thickener and thick pigment.
clear)” is formed. Typically, cut clears are prepared by dissolving 6% by weight of a thickener, such as the polymeric thickener of Example 68, in water and mixing for about 30 minutes.
Forms a translucent gel with a viscosity of over 100,000 cps. The cut clear acts as a viscosity enhancer in the paste. Next, create a concentrated pigment, e.g. 45.2% press cake dispersion (pigment dispersion in water), 18% cut clear, and 36.8% water over a period of about 15 minutes into a fluid cream paste with a viscosity of about 1900 cps. Blend until . The printing paste is formed by mixing 10% pigment concentrate and 10% emulsion binder (approximately 40-50% solids). The preferred binder was Roplex E-32 acrylic polymer emulsion, 46.0% solids. The resulting composition is
The paste has a viscosity of 28,000 cps and is ready for use in printing on cotton, polyester, cotton-polyester fiber blends and the like. If desired, the pigment printing pastes may be formulated as oil-in-water emulsions by the method of DE 2054885 by addition of water-immiscible organic solvents such as toluene. It is also possible for the printing paste to contain dispersion aids, such as any of the well-known ionic or nonionic surfactants, and auxiliary thickeners, such as "Carbopol" carboxyvinyl polymers. Example 132 Acid Dye Printing Paste A typical acid dye printing paste formulation utilizing the polymeric product of the present invention is as follows: wt% Dye Solution - Acid Blue - 25; 6% Cut Clear (6%) of Example 131 %) 25.0 Formic acid 1.8 Nopco "Foam Master"
DF-160L Defoamer 0.2 Water 60.5 The ingredients were mixed in about 15 minutes to form a smooth creamy paste with a pH of 2.0-2.3 and a viscosity of about 1600 cps. This paste can be applied to fabrics such as carpets by conventional techniques such as by the use of Zimmer flat bedding. Example 135 Fiber Coating Formulation The polymer thickeners of the present invention are useful in a variety of fiber polymer coatings. A typical formulation useful as a hair transplant adhesive is as follows. Roplex HA-8 acrylic polymer (46
% solids) 300.0 parts by weight catalyst solution NH ₄ NO ₃ (25% solids) 60.0 Cut Clear of Example 131 (6%) 30.0 The formulation has a cream consistency of about 40,500 cps and is not suitable for padding, dipping or rolling. It can be applied to the textile fabric by customary methods such as coating or other coating or impregnating techniques. Example 134 Pigmented Paper Coatings The polymeric thickeners of the present invention are useful in pigmented paper coatings in place of natural products such as sodium alginate and carboxymethylcellulose. A typical recipe is as follows. 72.6% by weight clay (70% solids) in a suitable container, 18.3% Dow-620 carboxylated styrene-butadiene polymer emulsion (50% solids) as pigment binder, 1% Cut Clear of Example 131. and 8.1% water. When pigmented, the formulation can be applied in a known manner by means of a trailing blade. It has a consistency of about 1800cps.

Claims (1)

[Claims] 1. Containing an emulsion polymer and from about 0.1 to about 10% by weight, based on the solids content of the emulsion polymer, of a nonionic water-soluble or water-solubilizable polyurethane thickener composition. a latex composition, wherein the polyurethane thickener composition has at least three hydrophobic groups, and at least two of the hydrophobic groups are terminal groups, and the hydrophobic groups are together at least 20 in total
carbon atoms, each of the hydrophobic groups being linked through a hydrophilic polyester group having a molecular weight of at least 1500, and the molecular weight of said polyurethane being at least 10000;
The polyurethane composition is selected from the following reaction products 1) to 5), in which reactant (a) is at least one water-soluble polyether polyol, and reactant (b) is at least one water-soluble polyether polyol. , reactant (c) is at least one monofunctional hydrophobic organic compound selected from monofunctional active hydrogen-containing compounds and organic monoisocyanates, and reactant (d) is at least is a kind of polyhydric alcohol or polyhydric alcohol ether: 1) the reaction product of reactant (a) containing at least three hydroxyl groups and the organic monoisocyanate; 2) the reaction product of reactant (a) and two 3) a reaction product of the reactant (b) containing an isocyanate group and the active hydrogen-containing compound; 3) a reaction product of the reactant (a), the reactant (b) containing at least three isocyanate groups, and the active hydrogen-containing compound; a reaction product; 4) a reaction product of the reactant (a), the reactant (b), and the monoisocyanate; and 5) a reaction product of the reactant (a), the reactant (b), the monoisocyanate, and the reactant (d). A latex composition characterized by a reaction product with ). 2. The latex composition according to claim 1, wherein the emulsion polymer is an acrylic emulsion polymer. 3. The latex composition according to claim 1, wherein the emulsion polymer is a vinyl acetate emulsion polymer. 4. A latex composition according to claim 1, wherein the amount of thickener is from 1 to 3% by weight, based on emulsion polymer solids. 5. The emulsion polymer according to claim 4, wherein the emulsion polymer comprises 1) a vinyl acetate polymer or 2) a copolymer of one or more acrylic ester monomers or one or more methacrylic ester monomers. Latex composition. 6. The latex composition of claim 2, wherein the acrylic polymer comprises a copolymer of one or more acrylic ester monomers or one or more methacrylic ester monomers. 7. A latex composition according to claim 1, wherein the amount of thickener is from 1 to 3% by weight, based on emulsion polymer solids. 8. The emulsion polymer according to claim 7, wherein the emulsion polymer comprises 1) a vinyl acetate polymer or 2) a copolymer of one or more acrylic ester monomers or one or more methacrylic ester monomers. Latex composition. 9. The latex composition of claim 2, wherein the acrylic emulsion polymer comprises a copolymer of one or more acrylic ester monomers or one or more methacrylic ester monomers.