WO2004047779A2

WO2004047779A2 - Polymers containing quaternary ammonium salts

Info

Publication number: WO2004047779A2
Application number: PCT/US2003/037618
Authority: WO
Inventors: Joseph J. Fanelli; Jeffrey K. Parkinson
Original assignee: Petroferm Inc.
Priority date: 2002-11-22
Filing date: 2003-11-24
Publication date: 2004-06-10
Also published as: WO2004047779B1; AU2003295904A1; WO2004047779A3

Abstract

A copolymer having surface active properties and comprising: a siloxane portion; and at least one N-containing organic portion which has a carbon atom thereof bonded to a silicon atom in the siloxane portion and includes at least one linking nucleophile with a quaternary ammonium segment bonded thereto, and the use of the copolymer in various exemplary applications , such as a wrinkle-releasing composition, a tissue-softening composition, and bodily treating composition.

Description

Polymers Containing Quaternary Arnmonium Salts

Cross-Reference To Related Application

The present application is based on and claims priority of U.S. provisional Application No. 60/428,447, filed November 22, 2002.

Field of the Invention

The present development relates to organic siloxane copolymers which have surface active properties. More particularly, this invention relates to siloxane copolymers which, because of their surface-active properties, impart to a surface to which they are applied, desirable tactile and/or appearance properties.

The present invention is described initially in connection with wrinkle- releasing properties imparted to cloth by application of at least one copolymer of the invention to the cloth. However, it should be understood that the invention has wider applicability as discussed hereinbelow.

It is accepted generally that wrinkles are imparted to cloth (a material comprising natural or synthetic fibers, for example, in woven or knitted form) when the fibers of the cloth are bent and entangled. It is believed also that, after wrinkling, the wrinkles remain in the cloth due to hydrogen bonding between the molecules which comprise the cloth. It has been observed that the application of a compound which has lubricating properties to the surface of wrinkled cloth imparts to the cloth the ability of the entangled fibers comprising the wrinkle to slip past each other and disentangle when the cloth is smoothed or placed in tension. Such compounds are referred to generally as wrinkle-releasing compounds.

It is believed also that the lubricating effect provided by wrinkle-releasing compounds reduces the tendency of fibers to entangle when the cloth is bent; as such, a wrinkle-releasing compound functions also to reduce the tendency of cloth to wrinkle in the first instance.

Accordingly, a compound providing wrinkle-releasing and/or resistance to wrinkling properties to cloth is referred to herein by the term "wrinkle-releasing compound" and a composition which contains such a compound and has such properties is referred to herein by the term "wrinkle-releasing composition."

In general, art recognized wrinkle-releasing compositions comprise a carrier, for example, a solvent, generally water or a low molecular weight alcohol, and one or more constituents having different surface active properties, for example, a combination of a silicone polymer, a wetting agent, and another surfactant. In such a composition, the silicone polymer provides the lubricating properties necessary to impart wrinkle-releasing properties to the cloth, the wetting agent provides the ability of the silicone polymer to "wet" the cloth's surface, and the surfactant facilitates dissolution or dispersion of the various constituents in the carrier. Other constituents comprising the composition include, for example, materials which impart to the cloth anti-static properties, optical brightening, reduction of yellowing, and a feeling of softness. Such constituents are optional ingredients, but are generally considered to be preferred ingredients.

The present invention relates to a wrinkle-releasing compound and to a composition which contains the compound and to other applications in which the compound of the present invention and compositions containing the compound can be used to impart desirable properties to articles and bodily parts, for example, softness to tissue and tactile properties to bodily parts, for example, a silky feel to hair, a shiny appearance to hair, and a softness to skin.

Reported Developments

Wrinkle-releasing compositions have been reported, for example, in U.S. Patent Nos. 6,624,131 to Murphy et al., 6,616,980 to Tulley et al., 6,569,345 to Hubesch et al, and 5,532,023 and 5,798,107, both to Nogel et al.

The ' 131 patent to Murphy et al. describes laundry detergent compositions which include, as a wrinkle-releasing agent, one or more of a triglyceride oil or a wax. The '980 patent to Tulley et al. describes the preparation of siloxane/polyalcohol copolymers having a polyalcohol segment attached to a siloxane backbone portion, the polyalcohol segment being terminated by an acrylate ester functional group. The Tully et al. patent also describes the use of an aqueous dispersion of the copolymer (which is not water soluble) to impart softening and wrinkle-releasing properties to cloth. The '345 patent to Hubesch et al. describes cloth surface-treating compositions comprising an aqueous carrier, a nonionic polyhydric alcohol, and a salt, selected from a carboxylate, carbonate, sulphate, nitrate, borate, or halogenate salt. The

Hubesch et al. patent describes optionally that wetting agents, softening agents, for example, quaternary ammonium compounds and/or polysiloxane compounds, may be included in the compositions to improve the tactile and appearance porperties imparted to cloth by the composition. The '023 and ' 107 patents, each to Nogel et al., describe a wrinkle-reducing composition comprising a liquid carrier containing a silicone polymer and a "film-forming" polymer. Examples of the film-forming polymer include an acrylate polymer, a vinylic polymer, and a polyalcohol. The silicone polymers used in the compositions of the Nogel et al. patents comprise an alkyl siloxane backbone, optionally a branched siloxane backbone, which has depending from one or more silicone atoms thereof an alkyl amino or alkyl quaternary ammonium moiety. Optionally, the composition can comprise also art-recognized wetting agents, siloxane surfactants, soil-releasing polymers, anti-static agents, and other art-recognized constituents typically included in compositions intended for application to cloth. Examples of the art-recognized optional materials include colorants, perfumes, preservatives, bactericides, optical brighteners, opacifiers, surfactants, anti-shrinkage agents, gemicides, fungicides, and anti-oxidants.

The present invention relates to an Si-containing copolymer which has surface active properties and which can be used, for example, in a variety of applications in which surface active agents are used.

Summary of the Invention

In accordance with this invention, there is provided a copolymer having:

(A) a siloxane portion; and

(B) at least one N-containing organic portion which has a carbon atom thereof bonded to a silicon atom in the siloxane portion and includes at least one linking nucleophile segment with a quaternary ammonium segment bonded thereto.

In preferred form, the siloxane portion of a coplymer of the present development is linear and has about 2 to about 200 silicon atoms, more preferably about 2 to about 17 silicon atoms. Preferred N-containing organic portions of copolymers of the present development comprise four segments, an alkylene segment which has one carbon therein bonded to a silicon atom in the siloxane portion of the copolymer, a polymeric segment bonded to the alkylene segment, a linking nucleophile bonded to the polymeric segment, and bonded to the linking nucleophile segment, a segment containing a quaternary ammonium salt (hereinafter "a quaternary ammonium segment"). Preferred linking nucleophile segments include amino-, diamino-, dicarboxylate-, and phosphate moieties.

Another aspect of the present development is the provision of a composition which comprises the copolymer of the present invention and a carrier. Exemplary embodiments of compositions of the present invention include wrinkle-releasing compositions which are used to treat cloth, compositions which are used to soften tissue, and bodily treating compositions which impart desirable properties to the skin, hair, or nail surfaces of an individual.

An additional aspect of the present invention is the provision of a process for the manufacture of tissue in which the tissue is formed from an aqueous dispersion of fibers by feeding continuously a stream of such aqueous dispersion onto a moving porous support surface, the improvement comprising the use in the aqueous dispersion, in an amount which is effective in softening the feel of the tissue, of a copolymer comprising: a siloxane portion; and at least one N-containing organic portion which has a carbon atom thereof bonded to a silicon atom in the siloxane portion and includes at least one linking nucleophile segment with a quaternary ammonium segment bonded thereto.

Other aspects of the present invention will become evident from a reading of the following detailed description of the invention and examples. Detailed Description of the Invention

The following includes a description of the structure and properties which characterize copolymers of the present development, a description of means for their preparation, and a description of the use of the copolymers.

Structural Description of Copolymers of the Present Development

With reference to Structure 1 below, the copolymers of the present development are copolymers which comprise a siloxane portion (region I) which contains at least one silicon atom that has bonded to it at least one N-containing organic portion (region II).

a d

STRUCTURE 1

With further reference to Structure 1, the N-containing organic portion includes an alkylene segment (segment a), preferably a polymeric segment (segment b), a linking nucleophile segment (segment c), and a quaternary ammonium segment (segment d).

In structure 1, X is an anionic moiety which balances the positive charge on the nitrogen atom and each of R¹, R², and R³ is the same or different and comprises an alkyl or alkenyl group which contains 1 to about 36 carbon atoms and which may be linear, branched, or cyclic and substituted or unsubstituted. The valence sites of the atoms of Structure 1 which are occupied by wavy lines indicate that each of these portions of the copolymer can have more than one structure. Copolymers of the present development may have more than one N-containing organic portion bonded to the siloxane portion, for example, up to a ratio of about one of said organic portion for each silicon atom in the siloxane portion. It is preferred that the ratio of the number of silicon atoms in the siloxane portion to the number of N-containing organic portions in the copolymer be in the range of from about 10 silicon atoms to one of said organic portion to about 3 silicon atoms to one of said organic portion.

The details of the structure of the organic and siloxane portions of copolymers of the present development, including the details of the segments making up the organic portion, are described below.

Structural Description of the Siloxane

Portion of a Copolymer of the Present Development

The siloxane portion of a copolymer of the present development comprises a linear (unbranched) chain of alternating silicon and oxygen atoms. Silicon atoms within the chain are generally bound to two substitutents in addition to the oxygen atoms to which they are bonded and those terminating at either end of the chain are bonded to three substitutents in addition to the oxygen atom to which each is bonded. This bonding pattern is illustrated in Structure 2 below.

STRUCTURE 2

With reference to Structure 2, "m" has the value of 0 to about 200, and at least one, preferably more than one, of R⁴, R⁵, and R⁶ (also referred to collectively as "the R moieties"), which may be the same of different, is said N-containing organic portion (region II of Structure 1 above); when only one or two of the "R" moieties is said N- containing organic portion, then the "R" moiety(ies)comprise a linear or branched alkyl or alkenyl moiety, an aryl, or alkyl-substituted aryl moiety, or -OH or -H, or a moiety which has a structure like that of the N-containing organic portion, but without said quaternary ammonium segment or without both of said quaternary ammonium segment and said linking nucleophile segment, with the proviso that no more than about 60% of the "R" moieties in the siloxane portion can be hydroxide and when both hydrogen and hydroxide substituents appear in the siloxane portion, they do not appear on adjacent silicon atoms.

Description of the Organic Portion of a Copolymer of the Present Development

As set forth above, the organic portion of a copolymer of the present development comprises preferably four segments. The description of the various segments follows.

The alkylene segment, that is, ~(CH₂)- (segment "a" of Structure 1), is linear and contains about two to about 6, preferably three carbon atoms.

The polymeric segment (segment "b" of Structure 1) includes both oligomers and polymers and may comprise only lipophilic constituents, for example, a linear alkylene group or it may have both hydrophilic and lipophilic constituents, for example, polyethylene oxide. The polymer segment may be linear in structure, with or without a pendant group(s) which has lipophilic properties, for example, a methyl group(s) on polypropylene oxide or a pendant group(s) which has hydrophilic properties, for example, one or more hydroxyl or carboxylic groups. By selecting the relative size and/or number of hydrophilic and/or lipophilic groups making up the backbone of the polymeric segment and the size and/or number of the hydrophilic and lipophilic groups appended thereto, the polymeric segment of the N-containing organic portion of copolymer of the present development can impart desirable properties to the copolymer, as described further below.

In preferred form, the polymeric segment includes: (A) ethylene oxide groups (-[CH₂-CH₂-0]-), one to about 25, preferably about 5 to about 15 groups; or (B) propylene oxide groups (-[(CH₃)CH₂-CH₂-0]-), one to about 10, preferably 2 to about 5 groups; or (C) a mixture of propylene oxide (PPO) and ethylene oxide (EtO) groups, that is, (EtO)_a(PPO)_b, where "a" is one to about 25, preferably about 5 to about 15 and "b" is one to about 10, preferably 2 to about 5.

In the copolymer of the present development, at least one linking nucleophile segment (segment "c" of Figure 1) is bonded to a carbon atom in the polymeric segment (segment "b" of Figure 1). The end of the linking nucleophile segment which is not bonded to the polymeric segment includes at least one bonding site to which the quaternary ammonium segment (segment "d" of Figure 1) is bonded. The linking nucleophile segment comprises an atom or a mono- or poly- functional group that has an effect on the surface active, solubility, and dispersibility properties of the copolymer of the present invention. Another consideration which enters into the selection of the nucleophile segment is the ability of the parent species (the form of the linking nucleophile when not bonded to the quaternary ammonium segment) to enter into a coupling reaction with a chlorohydrin under the reaction conditions described below.

Suitable linking nucleophiles which comprise an atom are, for example, nitrogen in the form of a secondary, or tertiary amine, or in the form of a quaternary ammonium salt. It will be appreciated that, in the copolymer of the present development: (a) a linking nucleophile in a secondary amine form arises from a reaction that bonds a quaternary ammonium segment to a primary amine; (b) a linking nucleophile in tertiary amine form arises from a reaction that bonds a quaternary ammonium segment to a secondary amine; and (c) a linking nucleophile in quaternary ammonium form arises from a reaction that bonds a quaternary ammonium segment to a tertiary amine.

Examples of functional groups that are suitable "linkers" in the linking nucleophile segment are a carboxylate group (-(C=0)0-, where the acyl carbon thereof is bonded to a carbon in the polymeric segment, and a phosphate group

(-0-)₃P=0, where one of the three oxygen atoms singly bonded to the phosphorous atom is bonded to a carbon in the polymeric segment and the other two singly bonded oxygen atoms are available for bonding with two quaternary ammonium segments or a quaternary ammonium segment and one additional moiety. The following are examples of moieties that can be bonded to such additional bonding site(s) in addition to an additional quaternary ammonium segment: a cation, examples of which are an ammonium ion, a hydrogen atom, and a metal ion, for example, lithium, sodium, or potassium; and an additional N-containing organic moiety, for example, an additional polymeric segment in a N-containing organic portion of the same, or a second example of, a copolymer of the present development.

A linking nucleophile segment can also comprise a difunctional segment having one end bonded to a carbon atom of the polymeric segment of the organic portion of the copolymer and the other end bonded to the quaternary ammonium segment. An example of this is a diester in which the linking nucleophile segment of the copolymer comprises a dicarboxylic acid moiety having one carboxylate group which forms an ester bond that includes a carbon in the polymeric segment and the other carboxylate group forms an ester bond that includes a carbon of the quaternary ammonium segment. It will be appreciated that the scope of such linking nucleophiles includes also oligomeric and polymeric analogs of difunctional moieties and other art- recognized di- and polyfunctional moieties which can undergo coupling with a chlorohydrin, as described below.

Another example of a functional group that is a suitable linker in the linking nucleophile segment is an unsaturated nitrogen heterocycle, for example, an imidazolinyl-based structure of the type shown in Structure 3 below

STRUCTURE 3

wherein R⁷ and R⁸ are different and are either a hydrogen atom or a polymer of the present development minus one quaternary ammonium segment and one linking nucleophile segment, "X^"" is an anion which balances the charge on the hetrocycle nitrogens, and "quat" refers to a quaternary ammonium segment (segment d), as described below.

Embodiments of the present invention include also a linking nucleophile segment which contains multiple atoms or poly-functional groups that can bond to a quaternary ammonium moiety. Examples include embodiments in which the linking nucleophile segment comprises a diamine or a saturated nitrogen heterocyclic structure bonded to a carbon atom of the polymeric segment. Examples of such saturated nitrogen heterocycles include piperazinyl or piperdinyl moieties and the structures described in U.S. Patent Nos. 6,171,515 to Evans et al. and 6,255,429 to Griffin et al., the disclosures of which are incorporated herein by reference. As mentioned above, the copolymer of the present invention includes preferably a polymeric segment. The present invention includes within its scope, nevertheless, embodiments in which the alkylene segment is bonded directly to the linking nucleophile segment, that is, the copolymer does not include a polymeric segment. Such copolymers can be prepared by a hydrosilation reaction, as described below for the preparation of a Si-containing precursor, in which one of the reactants is a siloxane polymer having a suitably located Si-H bond and the other is an alkenyl moiety comprising an alkylene segment terminated at one end by a quaternary ammonium segment bonded to the alkylene segment through a linking nucleophile and at the other by a carbon/carbon double bond.

It will be appreciated that appropriate alkenyl moieties can be synthesized by adapting the reactions described below for the synthesis of the N-containing portion of a copolymer of the present invention as well as by using other art-recognized organic synthesis reactions.

The copolymers of the present development contain at least one quaternary ammonium segment (segment d) which includes a carbon bonded to the linking nucleophile segment. The quaternary ammonium segment is a quaternary ammonium salt which includes a positively charged nitrogen atom having bonded to it four carbon moieties and a negatively charged moiety balancing the positive charge on the nitrogen atom. One of the carbon moieties (hereafter "the bridging group") is a linear carbon chain having one of its terminal carbons bonded to the nitrogen of the quaternary ammonium segment and the other bonded to the linking nucleophile segment of the organic portion of the copolymer. The other three carbon moieties bonded to the quaternary ammonium nitrogen may be a linear or branched, substituted or unsubstituted alkyl group or a linear or branched, substituted or unsubstituted alkenyl group, each having up to about 36 carbon atoms, preferably 1 to about 22 carbon atoms. The bridging group and the alkyl or alkenyl groups bonded to the quaternary ammonium nitrogen may additionally contain pendant functional groups, for example, hydroxyl groups.

A preferred quaternary ammonium segment of the present invention is shown in Structure 4 below.

STRUCTURE 4

In Structure 4, each of R⁹ and R¹⁰ is methyl, and R¹¹ is selected from linear or branched, alkyl or alkylene moieties having from about 12 to about 18 carbon atoms and "X" is a moiety that balances the positive nitrogen charge and can be: a halogen, for example, chlorine, bromine, and iodine; a carboxylate, for example, acetate; an organo-sulfate, for example, methosulfate (which has the formula (CH₃0)-S(=0)₂0-) and ethosulfate (which has the formula (H₃C-H₂CO)-S(=0)₂0-); and hydroxide ion.

Influence of Portions of the Copolymer of the Present Invention on Properties of the Copolymer

Each of the portions of the copolymers of the present invention has an effect on properties of the copolymer, including, for example, the surface active and solubility characteristics of the copolymer and the ability of the copolymer to form emulsions. Generally speaking, the properties affected by incorporating a particular structural feature into a copolymer of the present invention can be predicted from the knowledge of the art. Such knowledge can be used to tailor-make copolymers that have a desired combination of properties, as explained generally below.

The siloxane portion of a copolymer of the present invention that is applied to fabric imparts hydrophobicity, lubricating, and softening properties to the fabric. The surface active and solubility properties of the copolymer and its ability to form an emulsion can be influenced by selection of the number and/or size of the carbon-based moieties and of the non-carbon constituents attached to the silicon atoms of the siloxane portion.

The polymeric segment of the organic portion of a copolymer of the present invention (segment "b") may be characterized additionally by its HLB value, which refers to the balance of hydrophilic and lipophilic groups comprising it. The HLB value is an arbitrary number developed originally for polyoxyethylene ethers as the mole percent of hydrophilic groups occurring in a molecule divided by 5, with a compound having only polar groups being assigned an HLB value of 20. For compounds other than polyoxyethylene ethers, the HLB value is derived from other physical properties in comparison to the ethers. HLB values for various compounds are published. The meaning and measurement of HLB values are known in the art and are described further by Becher et al., Nonionic Surfactant Physical Chemistry, Marcel Dekker, NY 1987, pages 439-456.

The polymeric segment (designated above as segment "b" in Structure 2) in the organic portion of a copolymer of the present development has an HLB value that is preferably no greater than about 14, and more preferably is about 6 to about 12.

The properties imparted by the N-containing organic portion of the copolymer are derived from the properties imparted by the individual segments which comprise it. For example, with reference to Structure 1, alkylene segment "a", a lipophilic segment which serves to link the organic and the siloxane portions of the copolymer, augments the lipophilic/hydrophobic behavior of the copolymer imparted primarily by the siloxane portion of the copolymer. The polymeric segment (segment "b") can include, for example, both lipophilic and hydrophilic moieties, either as the "backbone" of the segment, in the form of an oligomer or polymeric chain, with or without pendant group(s) thereon. Including both kinds of moieties in the polymeric segment provides the copolymer with a degree of solubility in oils (by including lipophilic moieties) and with aqueous dispersibility (by including hydrophillic moieties), notwithstanding that other portions of the copolymer may have lipophobic or hydrophobic properties.

The linking nucleophile (segment "c") of the organic portion of the copolymer of the present development imparts surface active properties which are characteristics of other compounds containing the same type of functional group. For example, as described above, a linking nucleophile can be a phosphate-, carboxylate-, or an amino- functional group. Typically, when applied to fabric, compounds containing a phosphate-functional group impart antistatic properties to the fabric, compounds containing a carboxylate-functional group impart wrinkle-releasing properties to the fabric, and compounds containing an amino-functional group provide softening properties to the fabric. Such properties are imparted to fabric by application thereto of a copolymer of the present development containing, as linking nucleophiles, the aforementioned functional groups.

As described above, when an amino group is the linking nucleophile, it can be quaternized using reactions well known in the art, yielding a copolymer having, in its organic portion, two quaternary ammonium moieties separated by an alkyl or substituted alkyl bridge. An organic portion containing multiple quaternary ammonium centers is thought to enhance the softening effect the copolymer imparts when applied to cloth. Preparation of Copolymers of the Present Invention

There follows a description of the synthesis of copolymers of the present development. The synthesis includes a description of:

(A) the preparation of a Si-containing precursor comprising a siloxane portion, an alkylene segment, and a polymeric segment;

(B) the preparation of a linking precursor comprising the Si- containing precursor of (A) above and a linking nucleophile segment; and

(C) the preparation of a copolymer of the present invention comprising the linking precursor of (B) above and a quaternary ammonium segment.

Preparation of a Si-containing Precursor

There follows a description of reactions by which organic moieties can be bonded to a siloxane polymer to form a precursor that can be used to synthesize a copolymer of the present development.

To synthesize the Si-containing precursor, a siloxane polymer with a suitably located Si-H bond can be reacted initially with a linear alkylene moiety terminated at one end by a site of unsaturation and at the other by an epoxide group. Examples of reactions of this type are described in U.S. Patent Nos. 4,083,856 to Mendicino, 5,869,727 to Crane et al., and 4,348,454 to Eckberg. The product of this type of reaction is a siloxane portion having bonded thereto an alkylene group that contains a reactive terminal group, for example, as described in the Mendicino patent, an alkylene group terminated by an epoxide group. The epoxide group can be employed in well known reactions to attach additional segments, for example, a polymeric segment, to the alkylene segment. Examples of such reactions include the formation of ethers or polyether chains which include the oxygen atom of the epoxide. Reactions such as these are described also in other of above-referenced patents.

The polymeric segment which is attached to the alkylene segment includes at least one reactive moiety. Examples of suitable reactive moieties include sites of unsaturation, for example, a carbon-carbon double bond, and hydroxy groups, for example, those having polymeric segments comprising alkanols, polyethers and polyols, for example, those described in U.S. Patent Nos. 5,981,613 to Cobb et al., 5,830,970 to Cobb et al., 5,489,617 to Miller et al., 5,175,327 to Parkinson et al., and 3,528,288 to Haluska.

The aforementioned '727 patent to Crane et al. describes the addition of polyethers that have in their structure a site of unsaturation which terminates the polyether chain. Use of such polyethers in the reaction described in Mendicino patent yields directly a precursor having a siloxane portion and bonded thereto an organic portion comprising both an alkylene segment and a polymeric segment having a reactive moiety.

Examples of suitable commercially available copolymers having one or more organic portions containing an OH group suitable for use in reactions adding linking nucleophiles are Q4-3667 polyether silicone copolymer (Dow Corning) and MFF-159 (Lambent Technology Corporation). Preparation of a Linking Precursor

A linking precursor of (B) above can be prepared by reacting the Si-containing precursor of (A) above which, as mentioned above, includes a reactive moiety with a compound that is reactive therewith and which comprises an atom or a functional group, as referred to above in connection with the description of the linking nucleophile segment of the copolymer of the present invention. There follows a description of the exemplary types of reactions that can be used to add a linking nucleophile segment to the reactive moiety of the aforementioned Si-containing precursor.

An example of adding a linking nucleophile to a reactive moiety contained in a Si-containing precursor is the conversion of an alcohol functional group to a halide by treating the Si-containing precursor with a phosphorous halide, for example PBr₃, followed by reaction with ammonia, a primary amine, or a secondary amine to form a linking nucleophile segment which comprises respectively, a primary, secondary, or tertiary amine.

Examples of art-recognized reactions which provide a monofunctional group as a linking nucleophile segment are those which convert a site of unsaturation in the precursor, for example, a carbon/carbon double bond, to a carboxylic acid or to an alkyl halide followed by its conversion to a carboxylic acid, amide, or nitrile functional group. It will be appreciated that such reactive moieties within a Si- containing precursor may be employed in similar addition reactions between the precursor and a compound reactive with a reactive moiety which also contains a saturated nitrogen heterocycle, for example piperazine an or unsaturated nitrogen heterocycle, for example, an imidazoline. Examples of reactions which provide a difunctional linking nucleophile segment are the conversion of hydroxy groups to, for example, esters of either a phosphate acid, for example, phosphoric acid, or a dicarboxylic acid, for example, succinic acid, (the latter providing a linking nucleophile segment having a free carboxylic acid site on one end and having the other end bonded to a carbon in the polymeric segment via an ester group).

Exemplary reaction conditions which can be used to add carboxylate linking nucleophiles to copolymers using dicarboxylic acids are described in U.S. Patent No. 5,296,625 to O'Lenick et al. The addition of a phosphate-linking nucleophile to Si- containing precursor copolymers are described in U.S. Patent No. 5,070,171 to O'Lenick.

A di- or polyfunctional linking nucleophile group can be added directly to the siloxane portion of a copolymer of the present invention using the above-described hydrosilation reaction. For example, a silicon hydride site (Si-H) on a siloxane polymer can be added across the site of unsaturation of a reactive species which contains a carbon-carbon double bond and also a di- or polyfunctional linking nucleophile moiety. An example of a suitable ractive species is a diamine having the structure:

Structure 5

This example reaction will yield a difunctional linking nucleophile bonded directly to a silicon atom of a siloxane portion of the copolymer, providing an organic portion which does not contain a polymer segment. It will be appreciated that this same technique may be employed to provide attachment of organic portions which contain all of the segments described above in addition to a di- or polyfunctional linking nucleophile segment.

Addition of a Quaternary Ammonium Segment to the Linking Precursor of (B Above

A quaternary ammonium segment can be added to the linking precursor by reacting the linking precursor with a chlorohydrin compound containing a quaternary ammonium moiety. The reaction can be carried out in aqueous media having a pH higher than about pH 6 and lower than about pH 8. Equation 1, below, shows the general scheme of this reaction.

[linking precursor]

Equation 1

[linking precursor]

Equation 1, each of R¹, R², and R³ and "X" is defined as set forth in Structure 1 above and "p" has a value of 1 to about 34.

Equation 1 shows interconversion of the chlorohydrin-containing the quaternary ammonium segment between its chlorohydrin and epoxide forms. This interconversion is known in the art to be facile under basic conditions. Under suitable reaction conditions, either form will undergo a coupling reaction involving a linking nucleophile and a linking precursor copolymer, forming a bond to the terminal carbon. It should be appreciated that when "p" = 1, an n-(2-hydroxy)-propylene bridge between the linking nucleophile and the quaternary ammonium nitrogen is formed as a consequence of the reaction. Any chlorohydrin species which contains a quaternary ammonium moiety, as described above in the section detailing the structure of the quaternary ammonium segment, can be used in the above-described reaction to yield a copolymer of the present development

Chlorohydrins suitable for use in the above-described reaction are available commercially. A preferred chlorohydrin has the structure [N-[(3-chloro, 2-hydroxy)- propyl]], N, N -dimethyl, N -alkyl] ammonium chloride (with reference to Equation 1, each of R¹ and R² is methyl, R³ is an alkyl, the description of which follows, and "p" = 1). They include Quab 342^® (R³ alkyl is predominantly dodecyl) and Quab 426^® (R³ alkyl is predominately Stearyl), both available from Degussa.

In various chlorohydrins which are available commercially, the R alkyl group can be a mixture of species with one species predominating, for example, the "stearyl" group of Quab 426^® is typically 45 wt. % linear, unsaturated 18 carbon chain alkyl species, with the balance distributed between unsaturated species having 18 carbons and linear or branched species having between 12 and 16 carbon atoms.

Chlorohydrins containing any desired alkyl substituents may be synthesized, for example, by heating a tertiary amine having the desired alkyl substituents in the presence of 1,3 dicloro-2-propanol, yielding a quaternary ammonium salt containing chlorohydrin of the structure shown in Equation 1, where R^1"3 corresponds to the alkyl substituents of the starting amine. Species of linking precursors comprising the Si-containing precursor of (A) above and a linking nucleophile segment are known materials and can be used in a chlorohydrin coupling reaction, which is described below, to prepare copolymers of the present invention. For example: (1) a linking precursor containing amino- or diamino- linking nucleophiles, for example, those described in U.S. Patent Nos.

5,856,544 to Czech et al., 5,593,611 to Czech, 5,474,835 to McCarthy et al, 4,247,592 to Kalinowski, and 4,409,267 to Ichinohe et al.; (2) those containing phosphate- linking nucleophiles, for example, those described in U.S. Patent Nos. 5,093,452 and 5,070,171, both to O'Lenick; and (3) those containing carboxylate linking nucleophiles, for example, those described in U.S. Patent Nos. 5,296,625 and 5,292,847, both to O'Lenick.

Suitable copolymers containing linking nucleophiles for use in the chlorohydrin reaction described above are commercially available, for example, those containing amine-based linking nucleophiles, for example, Magnasoft Ultra^® (Compton Corp.) and Q2^® materials (Dow Corning), and those containing carboxylate-based linking nucleophiles, for example, CSI-DT^® (Lambent Technology Corporation).

Copolymers of the present invention are surface-active properties which enable them to be used in the wide variety of applications in which surface active agents are used. The copolymer can be used in neat form or in the form of a composition in which the copolymer is combined with one or more other materials. In neat form, the copolymer can exist as a liquid, including, for example, a highly viscous liquid, or as a solid, including, for example, a semi-solid, with the specific form of the copolymer depending, for example, on the monomeric constituents comprising the copolymer and the molecular weight of the copolymer.

The present invention includes within its scope a composition comprising a major amount of a carrier and a minor amount of one or more copolymers of the present invention. The copolymer can be present in the composition in dissolved or dispersed form, for example, as liquid droplets or as solid particles of copolymer dispersed in a continuous phase of the carrier, typically a liquid phase of the carrier. It is believed that the most widely used compositions of the present invention will be in liquid form and will comprise an aqueous solution of the copolymer(s), with the copolymer being miscible with water or being water-soluble. Although it is believed that water will be the carrier used most widely in compositions of the present invention, other materials in which the copolymer is soluble or dispersible can be used, for example, an alkylene glycol, for example polyproplylene glycol and polyethylene glycol, and an alcohol, for example ethanol.

The amount of copolymer comprising the composition of the present invention will typically comprise, as mentioned above, a minor amount of the composition. The particular amount used in the composition will depend on the nature of the application in which the composition is used. Amount ranges and specific amounts of the copolymer comprising various types of compositions of the present invention are exemplified below. As discussed below also, the composition of the present invention can include other ingredients, the nature of which will depend on the particular application in which the composition is used. Such ingredients will generally comprise a minor amount of the composition.

EXAMPLES

The following examples illustrate the formation of copolymers of the present development. Following the preparatory examples are additional examples which illustrate the use of one of the particular copolymers to impart wrinkle-releasing properties to cloth and which illustrate their use in other applications. In the following preparatory examples, the preparation of a copolymer of the present development using a commercially available linking precursor and a commercially available chlorohydrin in a chlorohydrin coupling reaction is decribed initially. There then follows a description of the preparation of copolymers of the present development from chlorohydrin coupling reactions using a linking precursor which contains phosphate-containing linking nucleophile segments and which is prepared from a commercially available Si-containing precursor. Thereafter, there is described the preparation of a copolymer of the present development via a chlorohydrin coupling reaction using a linking precursor which is prepared stepwise from a siloxane polymer.

The chlorohydin which is referred to in all of the examples is [N-(3-chloro-2- hydroxy)-propyl, N,N-dimethyl, N-stearyl] -ammonium chloride, which is commercially available (Deguassa, Quab 426^®).

Upon completion of each coupling reaction, the reaction mixture is titrated with a 0.1N silver nitrate solution according to the Mohr method, as described in "Fundamentals of Analytical Chemistry," 3^rd ed., D. Skoog and D. West, (1976) pg 726, to assay the number of moles of chloride present in the copolymer product in the form of a quaternary ammonium salt. It is assumed that the only quaternary ammonium chloride present in the mixture is bonded to the copolymer.

Example No. 1 - Copolymer Containing Dicarboxylate Linking Nucleophile Segments

A copolymer of the present invention having the structure shown in Structure 6 (below) was prepared by coupling the chlorohydrin with a commercially available linking precursor polymer sold under the trademark Lambent CSI-DT^®. The chlorohydrin contributes the portion of Structure 6 shown in braces (which is the structure of the starting chlorohydrin with the chlorine atom replaced by the oxygen atom of the ester linkage) and the linking precursor polymer contributes the portion of Structure 6 outside of the braces (minus two protons on the oxygen atoms forming the ester linkages).

Structure 6

The copolymer of Structure 6 was prepared by adding, with continuous stirring, 1180 g of the linking precursor to a vessel equipped with a heating mantle and a mechanical stirrer and containing 1668 g of tap water under ambient conditions, nominally 25 °C. The linking precursor/water reaction mixture was stirred for 15 minutes following the addition of the copolymer.

With continued stirring, 118.6 g of an aqueous solution containing 45 wt. % potassium hydroxide were added to the reaction mixture over 10 minutes. This addition produced a reaction mixture pH of between about 7 and about 8. After potassium hydroxide addition, the reaction mixture was stirred for an additional 15 minutes, following which 1006 g of an aqueous solution containing 40 wt.% of the chlorohydrin were added with continued stirring. After 15 minutes of additional stirring, the reaction mixture was heated to 80 °C and held at that temperature for 3 hours with continued stirring. Over the three hour heating period, 36.6 g of additional 45 wt.% KOH aqueous solution were added in 5 approximately equal aliquots, one every 30 minutes, maintaining the pH of the reaction mixture more basic than about pH 6.0. After 3 hours of stirring at 80 °C, a sample of the reaction mixture was titrated with 0.1 N silver nitrate using the procedure described above. The tiration showed that the copolymer contained one quaternary ammonium moiety for each carboxylate linking nucleophile present in the copolymer.

Following this, the reaction mixture was cooled to below about 50°C.

Approximately 16 g of Dantogard (Lonza) and 4g of Kathon CG-ICP (Rohm & Haas) were added as a biocide and 5.2 milliliters of water were added to adjust the solids content to about 40 vol % to yield a surface treating composition useful for imparting wrinkle-resistance to cloth.

There is described next the preparation of a linking precursor copolymer (which contains phosphate-containing linking nucleophile segments) from a commercially available Si-containing precursor copolymer available as Q4-3667 from Dow Corning and the use of this linking precursor copolymer in the preparation of copolymers of the present development containing one (Example No. 2) and two

(Example No. 3) quaternary ammonium segments per phosphate-linking nucleophile segment present in the linking precursor. Preparation of the linking precursor polymer from the Si-containing precursor polymer takes advantage of the fact that the Si- containing precursor contains within the polymeric segment thereof hydroxyl groups which can be reacted to bond thereto linking nucleophile segments. The Si-containing precursor copolymer is functionalized with phosphate-linking nucleophiles as described below. Into a vessel equipped with a heating mantle and a mechanical stirring apparatus were placed 97 g of the hydroxyl copolymer, described above. Over a 15 minute period, 3 g of 115% polyphosphoric acid (an item of commerce) were added to the copolymer with continuous stirring. After the addition of polyphosphoric acid, the reaction mixture was heated to 120°C using the heating mantle. The reaction mixture was maintained at 120°C with continued stirring for an additional 30 minutes. The reaction mixture containing the linking precursor comprising phosphate-linking nucleophile segments (hereinafter, "phosphate-linking precursor") thus formed was used directly to prepare the copolymers of Example Nos. 2 and 3, as described below.

Example No. 2 - Copolymer Containing One Quaternary Ammonium Segment Per Phosphate-linking Nucleophile Segment

The phosphate-linking precursor prepared above was utilized in a chlorohydrin coupling reaction by placing 1136 g of it into a vessel fitted with a heating mantle and a mechanical stirrer and containing 2,286 g of tap water at ambient temperature, nominally 25 °C. This addition was carried out over 5 minutes. The copolymer/water reaction mixture was stirred continuously during the polymer addition and for 15 minutes thereafter. With continued stirring, approximately 106.2 g of an aqueous solution containing 45 wt. % potassium hydroxide were added to the reaction mixture over 10 minutes. This addition yielded a reaction mixture pH of between about 7 and about 8 and raised the temperature of the reaction mixture by about 10 to 15 C°. This mixture was then stirred for about 15 minutes after the addition of potassium hydroxide solution, following which 452 g of an aqueous solution containing 40 wt.% of the chlorohydrin described above were added with continued stirring, over 5 minutes. Stirring of the reaction mixture was continued for an additional 15 minutes.

The reaction mixture was then heated to 80 °C and held at that temperature for 3 hours with continued stirring. Over this three-hour period, 16.6 g of additional 45 wt.% KOH aqueous solution were added in 5 approximately equal aliquots, one every 30 minutes. This addition scheme maintained the pH of the reaction mixture more basic than about pH 6.0.

After 3 hours of being maintained at 80 °C, an aliquot of the reaction mixture was sampled and titrated with silver nitrate, as described above. The titration demonstrated that the copolymer product contained one quaternary ammonium moiety for each phosphate-linking nucleophile present in the copolymer.

Following this, the reaction mixture was cooled to below 50 °C. Approximately 16 g of Dantogard (Lonza) and 4g of Kathon CG-IP (Rohm and Haas) were added as biocides, and the solids content was adjusted to about 33 vol % by addition of 10.6 grams of tap water to form a surface treating composition used for imparting wrinkle resistance to cloth.

Example No. 3 - Copolymer Containing Two Quaternary

Ammonium Segments Per Phosphate-Linking Nucleophile Segment

Example No. 3 describes the preparation that incorporates two quaternary ammonium moieties for each phosphate-linking nucleophile contained in the copolymer. This copolymer was prepared by reacting the phosphate-linking precursor prepared as described above with two equivalents of the chlorohydrin described above for each equivalent of phosphate-linking nucleophile segment contained in the linking- precursor copolymer.

Thus, with stirring, 888 g of the phosphate-linking precursor were placed into a vessel fitted with a heating mantle and a mechanical stirrer and containing 1850 g of tap water at ambient temperature (about 25°C). Addition was carried out over 5 minutes and stirring was continued for 15 minutes after the copolymer addition. With continued stirring, 83.0 g of an aqueous solution containing 45 wt. % potassium hydroxide were added over 15 minutes. This addition yielded a reaction mixture with a pH of between about 7 and about 8 and caused the reaction mixture temperature to rise to about 40 °C. Stirring was continued for about 15 minutes after the sodium hydroxide solution addition. With continued stirring, 706 g of an aqueous solution containing 40 wt.% of the chlorohydrin were added over 10 minutes. Stirring of the reaction mixture was continued for an additional 15 minutes.

The reaction mixture was then heated to 80 °C and held at that temperature for 3 hours with continued stirring. Over this three-hour period, 16.6 g of additional 45 wt.% KOH aqueous solution were added in 5 approximately equal aliquots, one every 30 minutes. This addition scheme maintained the pH of the reaction mixture more basic than about pH 6. After 3 hours of being maintained at 80 °C, an aliquot of the reaction mixture was titrated with silver nitrate according to the procedure described above. The titration showed that the copolymer product contained two quaternary ammonium moieties for each phosphate-linking nucleophile present in the copolymer. Following this, the reaction mixture was cooled to below 50 °C. Approximately 16 g of Dantogard (Lonza) and 4g Kathon CG-IP (Rohm and Haas) were added as biocides to yield a surface treating composition useful for imparting wrinkle resistance to cloth. The solids content was found to be about 33 wt. %, requiring no adjustment.

Example No. 4 - Copolymer Prepared From an Alkyl-Siloxane Polymer

This example describes the preparation of a copolymer of Structure 7 (below) by adding to a dihydrosiloxane polymer of the formula

H(CH₃)₂Si[(CH₃)₂SiO]₁₃Si(CH₃)₂H (segment I); (A) the combined alkylene segment (segment II) and polymeric segment (segment III); (B) a linking nucleophile segment (segment IN); and (C) a quaternary ammonium segment (segment N) in steps. Structure 7

A copolymer of Structure 7 above is prepared by adding, via a chlorohydrin coupling reaction (described above), one quaternary ammonium segment to each linking nucleophile segment of the linking precursor comprising segments I-IN of Structure 7, (prepared as described below) using a ratio of 1 mole of chlorohydrin (Quab 426^®, Degussa) for each mole of phosphate-linking nucleophile segment present in the linking precursor. Thus, the copolymer is prepared by introducing over a 5-minute period 1150 g of the linking precursor into a vessel fitted with a heating mantle and a mechanical stirrer and containing 2,234 g of tap water at ambient temperature (about 25 °C) while the reaction mixture is stirred continuously during the polymer addition and for 15 minutes thereafter. With continued stirring, approximately 90.1 g of an aqueous solution containing 45 wt. % potassium hydroxide are added to the reaction mixture over 10 minutes. This addition yields a reaction mixture having a pH of between about 7 and about 8 and a temperature of between about 35 and about 40°C. This mixture is then stirred for about 15 minutes after the addition of potassium hydroxide solution, following which 420 g of an aqueous solution containing 40 wt. % of the chlorohydrin are added with continued stirring over about 5 minutes. The reaction mixture is then heated to 80°C and held at that temperature for 3 hours with continued stirring. Over this three-hour period, an additional 16.6 g of additional 45 wt. % KOH aqueous solution are added in 5 approximately equal aliquots, one every 30 minutes; this maintains the pH of the reaction mixture higher than about pH 6.0.

After 3 hours of being maintained at 80 °C, the reaction mixture is sampled and titrated with silver nitrate, as described above. The titration shows that the product polymer contains one quaternary ammonium moiety present for each phosphate- linking nucleophile present in the polymer.

A Si-containing precursor comprising segments I-III of Structure 7 is prepared by adding to the terminal silicon hydride groups of the dihydro-methyl-siloxane polymer of the formula H(CH₃)₂Si[(CH₃)₂SiO]₁₃Si(CH₃)₂H an allyl-polyethylene oxide moiety of the formula (CH₂)₃-0-[(CH₂)₂-0]₁₂H using the procedure described in aforementioned U.S. Patent 5,869,727 to Crane (hereinafter "the Crane patent"). This patent describes the use of chloroplatinic acid to couple a dihydro-siloxane polymer and two allyl-polyethylene oxide moieties. The synthesis of a dihydrosiloxane polymer and allyl-polyethylene oxide is also described in the Crane patent as well as in aforementioned U.S. Patent No. 4,348,454 to Eckberg, and U.S. Patent No. 5,082,735 to Revis et al. , the disclosure of which is incorporated herein by reference.

A phosphate-linking nucleophile segment is added to the Si-containing precursor described above to yield a linking precursor comprising segments I-IN of Structure 7 by treating the Si-containing precursor described above with 2 moles of 115% phosphoric acid/mole of Si-containing precursor as described above.

Comparison of Properties Imparted to Cloth by

Art Recognized and Present Development Compositions

Compositions comprising copolymers of the present development can impart wrinkle-releasing properties and resist heat-yellowing when applied to cloth. Example Nos. 5 and 6 which follow compare respectively the wrinkle-releasing and yello wing- resistance properties imparted to cloth by a formulation comprising a copolymer of the present development (hereinafter "the quat solution") with a formulation corresponding to a typical commercial fabric softening formulation (hereinafter "the commercial solution") and with a formulation containing the linking precursor copolymer from which the present development copolymer comprising the "quat solution" was made (hereinafter "the non-quat solution").

The "quat" solution was prepared by adding 10 g of the surface-treating composition prepared according to Example No. 1 to 990 g of tap water. The "non- quat" solution was prepared by adding 10 g of the carboxylate functionalized copolymer Lambent CSI-DT^® (the linking precursor used in preparing the quaternary ammonium functionalized polymer of Example No. 1) to 990 grams of tap water.

The "commercial" solution was an aqueous solution comprising a mixture of an alkylamino-siloxane polymer and a methacrylate polymer. The commercial solution was prepared according to the procedure described in U.S. Patent No. 5,798,107 to Nogel et al. for the preparation of the solution of Example "A".

Example No. 5 - Comparison of Wrinkle-Releasing Properties

Imparted To Cloth By Solutions Comprising Organic Siloxane Copolymers

Comparison of the wrinkle-releasing properties of the "quat", "non-quat", and "commercial" solutions prepared as described above was carried out on test cloth. The comparison was carried out by preparing test swatches of standard cloth, 6"x6", 65/35 polyester/cotton blend sheeting (Test Fabrics #7409) for use in evaluating the wrinkle-releasing properties of the compositions by ironing the test cloth samples until a wrinkle-free finish was obtained. The swatches were then soaked in deionized water, wrung, and then wrinkled by placing the wet cloth in a piston-cylinder apparatus with a 500 gram load placed on a piston having a compression face of 23.2 cm², thus compressing the wrung fabric. The cloth was compressed for 60 seconds, then removed from the cylinder, and hung in a fume hood to dry for three hours.

The wrinkle-releasing properties of the solutions were demonstrated by spraying five ml of each of the tliree solutions onto separate samples of the wrinkled swatches from a Calmar® trigger sprayer. Each swatch was then tugged axially, across both diagonals of the test swatch, and smoothed with one swipe of a hand, and then returned to a fume hood to dry, typically one to two hours at ambient temperature (about 25 °C).

After drying, each sample swatch was evaluated visually by three observers, and their subjective rating of the amount of wrinkling retained by the samples was averaged. The following scale was used as a guide for evaluating the amount of wrinkling retained by the swatch:

0 = No Wrinkle Release

1 = Slight Wrinkle Release

2 = Most Wrinkles Released

3 = Entirely Wrinkle Free

The results of this evaluation are reported below in Table 1 below. These results demonstrate that application of compositions utilizing copolymers of the present development ("quat" solution) impart superior wrinkle-releasing properties to cloth when compared with the wrinkle-releasing properties of the "commercial" and "non- quat" solutions. Table 1

Although the wrinkle-releasing properties of copolymers of the present development have been exemplified by direct application to cloth, it will be appreciated that similar wrinkle-releasing properties can be imparted by including the copolymer in washing or rinse treatment compositions.

Example No. 6 - Anti- Yello wing Properties of

Polymeric Compounds Of The Present Development

After being evaluated for wrinkle-releasing properties, the test swatches which had been treated with the "quat", "non-quat", and "commercial" solutions were placed under a 350 °F iron for 3 minutes to evaluate their resistance to heat-yellowing. The amount that each swatch yellowed was then evaluated subjectively by comparison between the treated test samples which had been heated and the untreated test swatch which had not been heated. Evaluators compared the four swatches visually, arranging them in order of the intensity of their hue relative to the other samples; thus, up to four categories of "yellowness" were possible among the four samples. Three categories were identified: category 1, occupied by the untreated sample alone; category 2, occupied by the samples treated with the "quat" and "commercial" solutions; and category 3, occupied by the sample treated with the "non-quat" solution. Category 1 represented the least yellow sample and category 3 the most yellow sample of this lot. The samples in category 2 appeared to be of the same hue. These results are summarized below in Table 2 below. Table 2

10

This comparison demonstrates that copolymers of the present development resist heat- yellowing as well as commercial fabric-softening preparations and better than a solution comprising the linking precursor copolymer.

As mentioned above, copolymers of the present invention can be used also to impart a soft feel to tissue. In accordance with art-recognized evaluations, softness in tissue is determined generally by a subjective manual test using a panel of testers. The test is carried out using a roughness standard, as testers rate the roughness of the sample of tissue on a scale of one to five in comparison with the standard. In general, the standard is assigned a value of 3. The higher the value assigned a sample, the greater the degree of roughness. Conversely, the lower the value assigned to a sample, the lower the degree of roughness, that is, the softer the feel of the tissue.

The manufacture of soft absorbent paper such as tissue is well known. For example, in one type of continuous process, an aqueous suspension comprising paper- making fibers, for example, cellulose fibers, is deposited onto a moving porous support, for example, a forming fabric. The suspension contains generally other art- recognized ingredients, for example, a binder, a strengthening constituent, and a debonding constituent. As water drains through the porous support, a wet web of fibers is formed. Tissue is formed from the wet web by drying it. Tissue formed in this manner has typically an undesirable rough feel.

The tactile characteristics of tissue prepared in this manner can be altered to provide a smoother feel (tissue softening) by utilizing one or more copolymers of the present invention in the tissue-making process. For example, one or more copolymers of the present invention can be included in the aqueous fiber suspension before it is deposited onto the moving porous support. Alternatively, tissue softening may be achieved by application, at some other stage of the tissue-forming process, of one or more copolymers of the present invention to the surface of the material from which tissue is formed. For example, the copolymer may be applied to the surface of the dewatered wet web before drying. In another exemplary embodiment of the invention, tissue-softening may be achieved by application of one or more copolymers of the invention to the surface of the dried tissue. For surface application of the copolymer, suitable processes including, for example, spraying, rotogravure printing, blade coating, and flexographic printing can be used.

The copolymer of the present invention should be included in the tissue in a tissue-softening amount, that is, an amount at least sufficient to reduce the roughness of the tissue. It is believed that, for most applications, the weight of copolymer in the finished tissue will comprise from about 0.01 to about 10 wt. % of the weight of fibers in the finished tissue. Preferably, the amount of copolymer comprises from about 0.1 to about 3 wt. % of the weight of fibers present in the finished tissue. It will be appreciated that greater or lesser amounts of a tissue-softening copolymer of the present invention can be utilized depending upon various factors, for example, the amount of softening effect desired and the use of other tissue-softening materials in the tissue. Although copolymers of the invention can be utilized in a tissue softening application without dilution (that is, in neat form), it is believed that they will be used most widely in the form of a tissue-softening composition in which one or more of the copolymers are dissolved in a solvent, typically water, but also including, for example, glycols and alcohols. For most applications, it is believed that the copolymers will be present in solution in an amount of at least about 1 wt. %. The use of an aqueous solution containing about 1 wt.% to about 40 wt. % of copolymer is recommended. Inasmuch as various of the copolymers of the present invention are soluble in water in the amounts desired for use in aqueous solutions, it is not necessary to use one or more other materials for the purpose of dissolving the copolymer.

The next example is illustrative of the use of a copolymer of the invention to improve the softness of tissue.

Example No. 7 - Tissue Softening

The tissue-softening composition of this example is prepared by dissolving the silicone polymer prepared in accordance with Example 1 in water in an amount sufficient to provide a 40 wt. % aqueous solution of the copolymer. The tissue to be treated in accordance with the present invention comprises a two-ply crimped tissue in which each ply comprises an outwardly facing eucalyptus hardwood fiber layer (about 60 wt. % of the ply's tissue fiber) and an inwardly facing northern softwood kraft pulp layer (about 40 wt. % of the tissue fiber). Accordingly, each outer surface of the tissue comprises the eucalyptus hardwood fiber. A sheet of the air-dried tissue has a total basis weight of about 7.3 pounds/2880 ft². The outer surfaces of the tissue have a "rough" feel when rubbed on the skin.

Each outer surface of a sample of the tissue has applied thereto by rotogravure printing the softening composition described above in an amount such that the copolymer comprises about 1 % by weight of the total weight of fibers contained in the two-ply tissue. The treated tissue is allowed to dry. The sample of dried tissue has a softer feel compared to that of a tissue sample to which the tissue-softening formulation is not applied.

As mentioned above, copolymers of the present invention can be included also in a composition intended for the application to a bodily surface, for example, the surface of hair, nail, and skin. A few examples of such compositions include hair- cleansing and -treating compositions, for example, shampoos and conditioners, and bodily cleansing compositions, for example, bubble bath. Such a composition is referred to herein, for convenience, as a "bodily treating composition"; it can be used to impart desirable tactile properties, for example, a silky feel, and desirable appearance properties, for example, a shiny appearance, to bodily surfaces to which they are applied.

In addition to the copolymer of the present invention, a bodily treating composition comprises a carrier (typically water) for the copolymer and constituents which provide cleansing or additional conditioning of the bodily surface to which the compositions is applied. They may also comprise dispersants or constituents which modify the physical form of the composition, for example, viscosity enhancers. The amount of copolymer included in the bodily treating composition will vary depending upon a number of factors, for example, the particular function of the bodily treating composition, the particular copolymer used, and other ingredients used in the composition. Although greater or lesser amounts can be used, it is believed that, in general, a bodily treating composition will include from about 1 wt. % to about 5 wt. % of one or more of the copolymers of the invention to provide the desired properties.

The next three examples are illustrative of the use of bodily treating compositions of the present invention. Except for the copolymers of the invention, the constituents of the compositions described in the Examples are art-recognized materials used in compositions intended for bodily contact. Unless otherwise noted, all constituents of the Examples are pharmaceutical grade materials, articles of commerce, used as received.

Example No. 8 - Hair-Conditioning Composition

A hair conditioning composition is prepared by dissolving sequentially in 91 g of water, with stirring at ambient temperature, 5 g of benzyldimethyl (octadecyl) ammonium chloride (steralkonium chloride, a preservative), 1 g of hexadecane-1-ol (cetyl alcohol, an emollient and emulsifying agent), 2 g of hydroxypropyl cellulose (a viscosity enhancer), and 1 g of the silicone polymer prepared according to Example No. 1. After all of the constituents are dissolved, the pH of the solution is adjusted to about 7 by addition of aliquots of citric acid. When applied to hair, the composition imparts to the hair a silky feel.

Example No. 9 - Shampoo Composition

A shampoo composition is prepared by dissolving sequentially in 59.5 g of water, with stirring at ambient temperature, 35 g of sodium lauryl sulfate (an emulsifying agent), 3 g of N, N-bis (2-hydroxyethyl) dodecanamide (lauramide DEA, an antistatic agent and viscosity controlling agent), 0.5 g of cocamide DEA (a viscosity control agent and surfactant), and 2 g of the silicone polymer prepared according to Example No. 1. After addition of all of the constituents, the pH of the solution is adjusted to about 7 by addition of aliqouts of citric acid. The use of the composition to wash hair imparts to the hair a silky feel which is not observed when utilizing a composition which is identical except for the addition of the copolymer of Example No. 1. Example No. 10 - Bodily Cleansing Composition

A bodily cleansing composition suitable for addition to bath water, known also as a bubble bath composition, is prepared by dissolving sequentially in 36 g of water, with stirring at ambient temperature, 46.5 g of sodium laureth sulfate (a surfactant), 14 g of cocamidopropyl betane (also a surfactant), 2 g of cocamide DEA (an emulsifyer and emulsion stabilizing agent), and 1.5 g of the silicone polymer prepared according to Example No. 1. When all of the constituents are dissolved in the solution, the pH is adjusted to about 7 by the addition of aliqouts of citric acid. It is found that, when added to bath water in a skin-softening amount, the bodily cleansing composition of this example imparts to the skin a feeling of softness which is not imparted by a bubble bath composition which is identical except for the addition of the silicone copolymer of Example No. 1.

It should be appreciated that the present invention provides a class of copolymers which can be used to advantage in a variety of applications to the benefit of the user.

Claims

ClaimsWhat is claimed is:

1. A copolymer having:

(a) a siloxane portion; and

(b) at least one N-containing organic portion which has a carbon atom thereof bonded to a silicon atom in the siloxane portion and includes at least one linking nucleophile with a quaternary ammonium segment bonded thereto.

2. The copolymer of Claim 1 having the structure:

wherein x has a value from about 0 to about 200, each of R¹, R², and R³ can be the same or different and are selected from the group consisting of methyl, OH, H, said N- containing organic portion, and an organic portion having an alkylene segment, a polymeric segment, and optionally a linking nucleophile segment with the proviso that among all R¹, R², and R³ groups at least one is said N-containing organic portion, and no more than 60% are selected to be H or OH, and R¹, R², and R³ are selected such that -H and -OH do not appear on adjacent silicone atoms.

3. The copolymer of claim 2 wherein said N-containing organic portion comprises:

(a) an alkylene segment bonded to a silicon atom in the siloxane portion; (b) bonded to a carbon atom in the alkylene segment, a polymeric segment;

(c) bonded to a carbon atom in the polymeric segment, a linking nucleophile segment; and (d) a quaternary ammonium segment having a carbon atom therein bonded to the linking nucleophile.

4. The copolymer of claim 2 wherein said N-containing organic portion comprises: (a) an alkylene segment bonded to a silicon atom in the siloxane portion;

(b) bonded to a carbon atom in the polymeric segment, a linking nucleophile segment; and

(c) a quaternary ammonium segment having a carbon atom therein • bonded to the linking nucleophile.

5. The copolymer of claim 3 wherein said N-containing organic portion comprises a polymeric segment of the formula:

wherein "z" is 1 to about 200 and when "z" is one, R⁴ is -H or CH₃, and when "z" is more than one, R⁴ is selected independently for each occurrence from the group consisting of -H and -CH₃.

6. The copolymer of Claim 3 wherein "x" is at least about eight and wherein the compound contains no more than about ten N-containing organic portions.

7. The copolymer of Claim 3, wherein said linking nucleophile segment contains a moiety selected from the group consisting of amino, amido, phosphate, diamino, and dicarboxylate moieties.

8. The copolymer of Claim 1 having the structure:

wherein x has a value from about 1 to about 200 and R is said N-containing organic portion.

9. The copolymer of Claim 8 wherein said N-containing organic portion comprises an alkylene segment containing a carbon atom bonded to a silicon atom in the siloxane portion, a polymeric, segment bonded to the alkylene segment, a linking nucleophile segment bonded to the polymeric segment, and a quaternary ammonium segment bonded to the linking nucleophile segment.

10. The copolymer of claim 8 where said N-containing organic portion comprises an alkylene segment bonded to a silicon atom in the siloxane portion, a linking nucleophile segment bonded directly to the alkylene segment and bonded to the linking nucleophile segment a quaternary ammonium segment.

11. The copolymer of claim 9 wherein the N-containing organic portion has the structure:

wherein "-O-Nu:" is a linking nucleophile segment bonded to a quaternary ammonium segment, each of R⁵ is either the same or different and is selected from the group consisting of -H and -CH₃, and "Si" indicates the bonding site at which the N-containing organic portion is bonded to the siloxane portion of the copolymer.

12. The copolymer of Claim 11, where said linking nucleophile segment contains a functional group selected from the group consisting of amine, amide, phosphate, and dicarboxylate moieties.

13. The copolymer of claim 12 wherein x = 13.

14. The copolymer of Claim 1 , having a quaternary ammonium segment of the structure:

wherein each of R\ R², and R³ is the same or different and is selected from the group consisting of saturated or unsaturated, linear and branched alkylene having from one to about 36 carbon atoms, and X is selected from the group consisting of halide, acetate, methosulfate, ethosulfate, and hydroxide.

15. A copolymer of the structure:

wherein "stearyl" is selected from the group consisting of saturated or unsaturated, linear or branched hydrocarbon moieties having between about 12 and about 20 carbon atoms.

16. A copolymer of the structure:

17. A copolymer of the structure:

18. A composition comprising a major amount of a carrier and a minor amount of a copolymer having:

(a) a siloxane portion; and

19. A composition according to Claim 18 wherein the copolymer comprises:

(a) a linear siloxane portion; and (b) bonded to each silicon atom terminating said siloxane portion, an N-containing linear organic portion comprising:

(i) a linear alkylene segment bonded to one terminal silicon atom;

(ii) polymeric segment comprising a polyalkylene oxide bonded to a carbon of the linear alkylene segment;

(iii) a dicarboxylate linking nucleophile segment bonded to the polymeric segment; and

(iv) a quaternary ammonium segment bonded to each linking nucleophile via an ester bond.

20. A composition according to Claim 18 in the form of an aqueous solution of the copolymer.

21. A wrinkle-releasing composition according to Claim 18.

22. A tissue-softening composition according to Claim 18.

23. A bodily treating composition according to Claim 18.

24. A composition according to Claim 23 in the form of a shampoo.

25. A composition according to Claim 23 in the form of a bubble bath.

26. A composition according to Claim 23 in the form of a hair conditioner.

27. A method of treating cloth to deter the formation in the cloth of wrinkles or to remove wrinkles from the cloth comprising contacting the cloth with a copolymer of Claim 1.

28. A method of softening tissue comprising contacting the tissue with a copolymer of Claim 1.

29. In a process for the manufacture of tissue in which the tissue is formed from an aqueous dispersion of fibers by feeding continuously a stream of such aqueous dispersion onto a moving porous support surface, the improvement comprising the use in the aqueous dispersion, in an amount which is effective in softening the feel of the tissue, of a copolymer comprising: a siloxane portion; and at least one N-containing organic portion which has a carbon atom thereof bonded to a silicon atom in the siloxane portion and includes at least one linking nucleophile segment with a quaternary ammonium segment bonded thereto.

30. A method of treating the surface of a bodily part to impart thereto a desired property comprising treating the surface of the bodily part with a copolymer of Claim 1.

31. Tissue including a copolymer of Claim 1.

32. A method of making the compound of Claim 1 comprising contacting a linking precursor with a chlorohydrin containing ammonium moiety under aqueous conditions at a pH of not less than about 6.