A one-piece oral device for treatment of obstructive sleep disorders such as snoring hypopnea and apnea comprising a mouthpiece portion that fits within the anterior part of the oral cavity of a person much like the mouthpieces used in snorkel and scuba devices when swimming. The anterior or forward part of the mouthpiece protrudes outwardly through the lips of the user and includes a tongue shaped cavity for receiving the tongue. Bite blocks extending interiorly of the mouthpiece maintain the teeth in spaced-apart relation preventing damage to the tongue. A small channel communicates with the tongue shaped cavity and is connected via a length of tubing to an outside source of low suction pressure for holding the tongue forward.

The disruption of sleep causes excessive sleepiness during the working hours. Sleep research in the past few years suggest that snoring even without sleep apnea syndrome may also disturb sleep significantly. Sleepiness is a global epidemic. Fatigue accounts for about 40 percent of commercial trucking accidents, which causes 4,000 deaths and 12,000 injuries per year. It also causes a breakdown in marital and family ties. The true nature of the challenge, i.e., to identify and treat the millions of people who have sleep apnea syndrome, is truly staggering. Patients with sleep apnea syndrome are in danger of harming themselves and may be at risk to others.
The present invention has been developed to aid in the elimination of snoring and the various degrees of hypopnea and apnea that occur due to pathological disturbances in the sleep process. One of the main reasons of the sleep disturbance is the relaxation of the tongue to varying degrees during the several stages of sleep. When fully awake, the tongue has normal tone as air normally passes in and out of the lungs during respiration. However, during sleep, the tongue is lax. As air is drawn into the lungs by the muscles of respiration, the tongue is drawn back against the posterior wall of the pharynx in a fluttering fashion. As the posterior part of the tongue hits the posterior wall of the pharynx with rapidity, the to and fro action of the tongue causes loud and disturbing snoring sounds. When sleeping in a supine position, the effect of gravity makes the snoring worse.
The more serious type of sleep disturbance is obstructive sleep apnea, which occurs when the tongue goes against the posterior wall of the pharynx preventing any air from entering the lungs. The effort of the muscles of respiration causes the blockage to seal even tighter. The apnea causes a drop in the blood oxygenation and increases the blood carbon dioxide level. The heart is affected adversely with the blood pressure and pulse rate increasing. Sometimes arrhythmias may occur. The brain is affected by the carbon dioxide buildup causing the person to be aroused. On awakening there is a return to tonicity of the muscles of the tongue, which allow normal breathing to resume. After some time the person goes back to sleep and the process occurs all over again.
The American Sleep Apnea Association rates obstructive sleep apnea events per hour as the Respiratory Distress Index (RDI). It rates 0-5 RDI""s as normal, 5-20 as mild, 20-40 as moderate, and over 40 as severe. In a few cases RDI""s were above 100; with events lasting 90 to 120 seconds with oxygen saturation going below 70% when normal is 95% to 100%. All aspects of quality of life, from physical and emotional health, to social functioning are impaired by the obstructive sleep apnea.
Much research has been done worldwide on correcting sleep disorders. The most prominent treatment used presently is the Mask and Nasal Continuous Positive Airway Pressure (CPAP). The nasal C-PAP is more accepted than the mask but compliance is poor. Frequent side affects occur such as dryness, mucous congestion, sinusitis, rhino rhea, sneezing, and mucous in the throat. Breathing out against positive air pressure is also discomforting. Other treatments include a tongue retaining device (TRD) made of soft plastic that have a tongue shaped cavity that is supposed to hold the tongue in a forward position after a suction is formed within the mouth by the user. The negative pressure created within the mouth draws the tongue forward into the tongue cavity. With this method, adequate suction is not developed and not maintained for long. Another device clamps the tongue and holds it in a forward position. Some units were uncomfortable to wear. In some experiments, it was worn only half of the night. Despite drawbacks, the TRD was found to decrease the number of apnea events by approximately 50%. Thus far, TRD has not excited a lot of enthusiasm in the research community. The Samelson device (U.S. Pat. No. 4,304,227) holds the tongue forward within a cavity with suction created by the tongue forcing its way into the cavity. However, this suction force does not last for a prolonged period of time. The Samelson device also does not allow any mouth breathing and is not successful if there is any type of obstruction in the nasal passages. Dental devices have been devised to advance the mandible, such as disclosed in U.S. Pat. No. 4,715,368 which enhances the space between the posterior tongue surface and the posterior pharyngeal wall. However, problems arise because of dislocation of the temperomandibular joint causing pain in the joints and sometimes in the teeth. Occasionally a permanent mal occlusion develops.
The present invention differs from the Samelson device by creating a suction with an external source and permitting the user to breathe through the mouth. This is important because even when there is normal nasal anatomy, the nasal passages may become congested, especially when infection or allergies are present.
The embodiment of my invention is a one-piece oral device for treatment of obstructive sleep disorders. The invention includes a mouthpiece portion that fits within the anterior part of the oral cavity of a person much like the mouthpieces used in snorkel and scuba devices when swimming. The anterior or forward part of the invention protrudes outwardly through the lips as illustrated in FIG. 1 and includes a tongue shaped cavity for receiving the tongue. A small channel communicates with the tongue shaped cavity and is connected via a length of tubing to an outside source of low suction pressure. There is no difficulty in swallowing saliva with the tongue being in the forward position throughout the night since the tongue is held forward.
It is one object of the present invention to provide a method and apparatus for reducing or eliminating snoring, hypopnea, or apnea by holding the tongue in a forward position in such a way that no portion of the tongue or other oral soft tissue will vibrate during breathing.
It is a further object of the present invention to provide a method and apparatus for reducing or eliminating snoring, hypopnea, or apnea by not only holding the tongue in a forward position but also permit oral breathing through the mouth particularly should nasal congestion occur.
It is a further object of the present invention to provide a device for reducing or eliminating snoring, hypopnea or apnea which is comfortable to use and easy to manufacture.
These and other objects and advantages of the present invention will become clear from the following description of a preferred embodiment of the invention.

Method and apparatus for treatment of snoring, hypopnea and apnea


The present invention relates to a radiation-curable solvent-free coating composition for optical fiber having a radiation-curable urethane (meth)acrylate oligomer comprising an alkyd backbone, a reactive diluent, a photoinitiator and, optionally, an additive.

The present invention relates to a radiation-curable coating composition for optical fiber, to an alkyd urethane (meth)acrylate oligomer, and to a coated substrate.
Glass optical fibers are widely used in the communications field because of their ability to carry large amounts of information over long distances. In order to protect the fibers from physical damage and from deterioration due to environmental agents such as water, it is conventional to apply at least one protective coating immediately after spinning the molten glass. Generally, two coatings are applied, a soft primary coating of low modulus and low glass transition temperature (Tg) directly on the glass surface, and a harder (higher Tg), higher modulus secondary coating, on the primary coating. The individual fibers generally are combined in larger structures such as cables. Cables may comprise individual fibers, or fiber ribbon structures. The optical fiber ribbon generally is made from 2, 4, 6, 8 or 12 optical fibers, in general arranged in a plane, and bonded together with a so-called matrix material. Several ribbons can be bundled together using bundling materials. Further, individual fibers often are provided with a coloring or ink layer to be able to identify individual fibers.
Resins that cure on exposure to radiation such as ultraviolet radiation are favored in the industry, due to their fast cure, enabling the coated fiber to be produced at high speed. In many of these radiation curable resin compositions, use is made of urethane oligomers having reactive termini (such as f.i. an acrylate or methacrylate functionality) and a polymer backbone, which compositions generally further comprise reactive diluents, photoinitiators to render the compositions radiation-curable, and suitable additives.
There are several properties which are commonly required for all the different coatings. Some of these requirements are low water absorption, low extractables, maintenance of the desirable levels of properties such as modulus, elongation, Tg, and adhesion under aggresive aging conditions (over relatively long periods of time) including high temperatures and/or high humidities, immersion in water and chemical resistance.
As mentioned above, urethane acrylate oligomers are well-known for use in radiation curable coating compositions for optical fibers. As polymer backbone for the urethane oligomer, many materials have been used, such as polyether backbones. Urethane acrylate oligomers are derived from reactants including a hydroxy-functional prepolymer (polyol), an organic diisocyanate and an ethylenically unsaturated monomer containing one or more hydroxyl groups. Polyols that often have been used are f.i. hydrocarbon polyols, polyether polyols such as poly(ethylene)glycol, poly(propylene)glycol and poly(tetrahydrofuran)diols, polyester polyols, polycarbonate polyols and polysiloxane polyols. Polyester polyols are particularly attractive because of their commercial availability, oxidative stability and versatility to tailor the characteristics of the coating by tailoring the backbone. One of the problems encountered in using most polyesters is their hydrolytic instability and oil sensitivity.
In this respect, a continuous search is going on in the field of optical fiber coatings for alternative coatings with suitable properties. In WO 98/56846, it is suggested to improve the resistance to hydrolysis by using (a urethane oligomer with) a polyester backbone consisting mainly of polymerized diol and diacid and/or hydroxy acid components wherein the diol component has at least one carbon at the xcex2-position with respect to the hydroxyl groups which is substituted with a group containing at least one carbon atom. The disadvantage of the polyesters described in WO 98/56846 is that they have a relatively high viscosity and hence, a higher concentration of diluents is needed, thus limiting the selection of properties.
In JP-A-2216947 a urethane acrylate oligomer is suggested in which the backbone can be an alkyd polyester that can be obtained by reacting a fatty acid such as soy oil, linseed oil, safflower oil, palm oil, dehydrated ricinus oil, dehydrocastor oil, or tung oil with a polyacid and a polyol. The radiation-curable optical fiber inner primary composition comprising the urethane acrylate oligomer described in JP-A-2216947 is solvent-based, which clearly is a drawback. Moreover, the oils on which alkyds in JP-A-2216947 are based all contain considerable unsaturation.
Among many other efforts, EP-A1-539030 suggests to use polyester polyols wherein the acid-component and/or the hydroxyl component residues of the polyester polyol are partially comprised of dimer acids. The dimer acids suggested in EP-A1-539030 are usually unsaturated, but can also be hydrogenated to remove a substantial proportion of the unreacted double bonds. However, dimer acids have the disadvantage of swelling in hydrocarbon oil, which is representative of cabling gel filling type compounds. U.S. Pat. Nos. 4,629,287, 4,609,718, and 4,608,409 all mention the use of dimer fatty acids which are dicarboxylic acids formed by dimerizing fatty acids which usually contain 18 carbon atoms, and thus providing a 36 carbon atom dicarboxylic acid.
So far, very few alternatives for fiber optic coatings with appropriate coating characteristics, such as a combination of a low water sensitivity and a low oil sensitivity, have been found.
An object of the present invention therefore is to provide a radiation-curable solvent-free coating composition which exhibits low water sensitivity and low oil sensitivity. The radiation-curable solvent-free coating composition can also exhibit other comparable coating properties as the presently used coatings based on polyether oligomers, such as tetrahydrofuran-based polyether oligomers.
This has been achieved according to the present invention by a radiation-curable solvent-free coating composition for optical fiber comprising
(A) a radiation-curable urethane (meth)acrylate oligomer comprising an alkyd backbone,
(B) a reactive diluent,
(C) a photoinitiator, and optionally
(D) an additive.
The alkyds used as backbones in the urethane acrylate oligomers of the present invention have the advantage that they are conveniently available from renewable resources and are readily manufactured using conventional equipment from readily available starting materials. The alkyd-based compositions are more friendly to the environment than ordinary polyesters.
Furthermore, the alkyd-based compositions of the present invention are essentially free of solvent, meaning that there is less than 2% solvent present in the compositions. This is advantageous because there occurs no evaporation of solvents during film formation. The alkyd-based compositions can be derived from solvent-free reactions and are suitable for use in UV curable coating compositions.
Moreover, the alkyd-based compositions of the present invention show good thermal-oxidative stability as measured by discoloration, also determined as good yellowing resistance under aging conditions such as high temperature and/or high humidity (125xc2x0 C./dry or 85xc2x0 C./85% RH), which means that they result in substantially colorless compositions.
Further, the alkyd-based compositions according to the present invention show good hydrolysis resistance, and acceptable oil and water sensitivity. The mineral oil resistance is better than that of polyesters based on dimer acids.
The radiation-curable urethane (meth)acrylate oligomer includes an alkyd backbone. The alkyd backbone is derived from an alkyd resin. Alkyd resins, or alkyds, are polyesters having pendant ester group protruding off of a main polymer chain of ester linkages. The pendant group of the alkyd can be introduced by including a monofunctional carboxylic acid (monoacid) along with the ordinary components used to prepare a polyester. The pendant ester group contributes to the properties of alkyds and makes them considerably different from conventional polyesters. In other words, alkyds can be distinguished by the presence of a monoacid as an essential part of the composition.
The number average molecular weight of the alkyd backbone is at least about 300, preferably, at least about 500, more preferably, at least about 900. The number average molecular weight is less than about 10,000, preferably less than about 5,000, more preferably less than about 3,000.
The alkyd can be made by any method. Preferably, alkyd resins can be prepared by condensation reactions of polyfunctional alcohols (hereafter referred to as polyols), polyfunctional carboxylic acids (hereafter referred to as polyacids), and oils or fatty acids derived from the oils. The oil can be a natural oil (which consists of an ester, e.g., a triester, of glycerol and fatty acids). For example, a polyol/fatty acid mixture can be prepared in-situ by alcoholysis of a naturally derived oil or by direct esterification of a polyol with a naturally derived long chain fatty acid. The resulting product from either of these reactions can then polymerized with other polyols and polyacids (e.g., diols and diacids) as in conventional polyesterification. More preferably, the alkyd is prepared by alcoholysis of a naturally derived oil, in particular one with a low degree of unsaturation.
The amount of oil present in the alkyd is important in dictating the properties of the final resin. The amount of oil present is traditionally classified in terms of the oil length of the alkyd, a concept originally based on compositions containing only glycerol as the polyol. The longer the oil length of the alkyd, the more oil is present. The alkyd resin can be a long oil alkyd having an oil content (i.e. oil length) of about 60-90%, a medium long oil alkyd, having an oil length of about 40-60% or a short oil alkyd having an oil length of about 10-40%. Similarly, phthalic anhydride content of a long oil is about 25% by weight, while that of a short oil may be as high as 50%. Accordingly, a wide variety of oil lengths can be attained.
Any polyacid, polyol, and monoacid can be used in the manufacture of alkyds. As the polyacid component, polyfunctional carboxylic acids and the corresponding anhydrides can be used, preferably polyfunctional carboxylic acids and the corresponding anhydrides, for example, phthalic acid or anhydride, isophthalic acid, terephthalic acid, maleic acid or anhydride, fumaric acid, itaconic acid or anhydride, succinic acid or anhydride, adipic acid, sebacic acid, azelaic acid, citric acid, trimellitic acid or anhydride, pyromellitic acid or dianhydride, tetrahydrophthalic acid or anhydride, endomethylenetetrahydrophthalic acid or anhydride, cyclohexane dicarboxylic acid, glutaric acid, dodecane dioic acid, dimer-fatty acid and the like. Also, mixtures of acids may be used. In particular preferred are adipic acid, orthophthalic acid, isophthalic acid, and terephthalic acid.
As suitable polyol compounds, polyfunctional alcohols can be used, for example, pentaerythritol, glycerol, trimethylol ethane, trimethylol propane, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol (BEPD), hydroxypivaloyl hydroxypivalate (HPN), polyethylene glycol, polypropylene glycol, ethoxylated bisphenol-A having 2-12 ethylene oxide units, propoxylated bisphenol-A having 2-12 propylene oxide units, dipentaerythritol, sorbitol and the like. Preferably, trialcohol alkanes (such as, for example, glycerol, trimethylol propane (TMP), trimethylol ethane), pentaerythritol (PE), neopentyl glycol (NPG), 2-butyl-2-ethyl-1,3-propanediol (BEPD), and hydroxypivaloyl hydroxypivalate (HPN) are used.
The monoacid is any monocarboxylic acid having between 4 and 28 carbon atoms. Preferably, the monoacid is a fatty acid, more preferably a long chain monoacid. A long chain monoacid, or long chain fatty acid, is characterized as having between 12 and 28 carbon atoms in their chain; more preferably, between 12 and 24 carbon atoms. Most fatty acids have 18 carbon atoms in their chain, but also a higher number of carbon atoms in naturally derived oils is possible. For example, C22 acid, erucic acid (docosenoic acid), is found in some varieties of rapeseed oil. Preferably, naturally derived fatty acids or oils from which fatty acids are derived, as known to those skilled in the art, are fatty acids or oils originating from vegetable or animal sources.
The average chain length of a fatty acid can be determined by the saponification value, which increases as the chain length decreases. For example, when an oil is saponified with an alkali to yield glycerol and a soap, it is possible to determine the saponification value and the free carboxylic acid content of the oil.
The fatty acids or oils suitable in the alkyd backbones according to the present invention can be unsaturated or saturated. Preferably, the fatty acids or oils according to the present invention have a low degree of unsaturation, as defined hereunder. Examples of unsaturated oils or fatty acids (derived from the oils) include castor oil, corn oil, cottonseed oil, rapeseed oil, low eruric rapeseed oil, hempseed oil, kapok oil, linseed oil, wild mustard, oiticica oil, olive oil, palm oil, peanut oil, perilla oil, poppyseed oil, tobaccoseed oil, argentine rapeseed oil, rubberseed oil, safflower oil, sesame oil, soybean oil, sugarcane oil, sunflower oil, tall oil, teaseed oil, tung oil, black walnut oil, or mixtures thereof, and the like.
Examples of fatty acids/oils having a low degree of unsaturation include Coconut oil, Babassu oil, Chinese Tallow oil, Ouri-Curl oil, Palm Kernel oil, caprylic acid, caproic acid, capric acid, coconut fatty acid, lauric acid, myristic acid, palmitic acid, stearic acid, and the like or mixtures thereof, fatty acids derived from the oils, as well as the hydrogenated form of unsaturated oils and fatty acids derived from the oils, such as castor oil, corn oil, cottonseed oil, rapeseed oil, low eruric rapeseed oil, hempseed oil, kapok oil, linseed oil, wild mustard, oiticica oil, olive oil, palm oil, peanut oil, perilla oil, poppyseed oil, tobaccoseed oil, argentine rapeseed oil, rubberseed oil, safflower oil, sesame oil, soybean oil, sugarcane oil, sunflower oil, tall oil, teaseed oil, tung oil, black walnut oil, or mixtures thereof, and the like.
The unsaturation in the fatty acid side chains of an alkyd generally is indicated by the Iodine or hydrogen value, which value increases with an increase in unsaturation. The iodine value of the oils or fatty acids is a commonly used parameter to indicate their degree of unsaturation. The iodine value is the number of grams of iodine absorbed by 100 grams of oil. This test measures the unsaturation of oils by determination of the amount of iodine reacted at the double bonds. The Wijs method is most commonly used. Iodine absorption is determined by titrating unreacted reagent with sodium thiosulphate, and can be expressed as follows:                               Iodine                                xe2x80x83                              value                =                              (                          12.69              xc3x97              mL                                            xe2x80x83                                          thiosulphate              xc3x97              normality                        )                                mass                                      xe2x80x83                                    of                                      xe2x80x83                                    sample                                      xe2x80x83                                                  (              g              )                                                          (        1        )
The iodine value of the oils or fatty acids generally will be less than 210 centigrams Iodine/gram sample, preferably, less than 150 centigrams Iodine/gram sample, more preferably less than 100 centigrams Iodine/gram sample. For the oils or fatty acids having a low degree of unsaturation, the iodine value generally will be less than 40 centigrams Iodine/gram sample, preferably less than 25 centigrams Iodine/gram sample and more in particular less than 15 centigrams Iodine/gram sample. According to a preferred embodiment of the present invention the alkyd backbone comprises fatty acid side chains with a low degree of unsaturation and thus, the iodine value of the alkyd should preferably be lower than 25 centigrams Iodine/gram sample, more preferably lower than 10 centigrams Iodine/gram sample so as to minimize the effect on yellowing.
The hydroxyl value is a measure of the amount of hydroxyl groups, measured by titrating back the reaction product of the alkyd with acetic anhydride, and is expressed as:                               Hydroxyl                                xe2x80x83                              value                =                              the                                      xe2x80x83                                    number                                      xe2x80x83                                    of                                      xe2x80x83                                    mg                                      xe2x80x83                                    of                                      xe2x80x83                                    potassium                                      xe2x80x83                                                  hydroxide                                                              xe2x80x83                                                                  xe2x80x83                                            (              KOH              )                                            mass                                      xe2x80x83                                    of                                      xe2x80x83                                    resin                                      xe2x80x83                                    or                                      xe2x80x83                                    polymer                                      xe2x80x83                                                  (              g              )                                                          (        2        )
The hydroxyl value of the alkyd oligomer of the present invention generally is at least about 15, preferably at least about 20 and generally is less than about 200, preferably less than about 170, more preferably less than about 150.
The alkyds of the present invention generally will have an average hydroxyl functionality of between 1.5 and 5 preferably between 1.8 and 3. It is most preferred, to use substantially linear polymers (i.e. an average functionality between 1.8 and 2.2).
The acid value is a measure of the free carboxylic acids content of a resin and is expressed as the number of milligrams of potassium hydroxide required to neutralize the free carboxylic acids in one gram of the resin. A weighed quantity of the resin is dissolved in a solvent such as toluol together with neutralized ethyl alcohol and titrated with carbonate-free decinormal sodium hydroxide solution to a phenolphthalein end point. The acid value can be expressed by:                               Acid                                xe2x80x83                              value                =                                            (                              56.1                xc3x97                mL                                                  xe2x80x83                                                NaOH                xc3x97                normality                            )                                      mass                                            xe2x80x83                                          of                                            xe2x80x83                                          resin                                            xe2x80x83                                                          (                g                )                                                                    (                          mg                                            xe2x80x83                                          KOH                                            /                                          g                                            xe2x80x83                                          resin                        )                                              (        3        )
The acid number of the alkyd resins of the present invention is preferably minimized, and is generally lower than about 10 mg KOH/g, preferably lower than about 5 mg KOH/g. An alkyd resin having a low acid number will positively influence aging properties, minimize the water sensitivity and will not slow down the urethane reaction.
(A) The Oligomer System
In general, an oligomer system is first prepared, optionally in the presence of a reactive diluent. Then, the oligomer formulation is further formulated by mixing with other ingredients such as reactive diluents, one or more photoinitiators, and additives. If multiple oligomers are desired, individual oligomers can be synthesized separately, and then mixed, or they can be synthesized together in a single, one-pot synthesis. In either case, the synthesis of oligomers often produces a statistical distribution of different types of oligomers which can be represented by idealized structures.
If some ingredients from the reactive diluent system (see below) are present during oligomer synthesis, they are not considered part of the pre-polymer system because, in general, reactive diluents do not react substantially during oligomer preparation and merely function as solvents for the purpose of viscosity control. In general, a reactive diluent can be distinguished from an oligomer because it will have a lower molecular weight than an oligomer, and will serve to decrease the viscosity of an oligomer. However, some reactive diluents can have repeating units such as repeating alkoxy units. However, for this invention, if the diluent functions to decrease the viscosity of the oligomer, then it is a called a diluent rather than an oligomer.
The amount of the oligomer system (A) can be, for example, about 10 wt. % to about 90 wt. %, and preferably, between about 15 wt. % to about 80 wt. %, and more preferably, about 20 wt. % to about 70 wt. %. If more than one oligomer is present, then the wt. % of each oligomer is added.
There is no particular limitation on the molecular weight of the oligomer, but the number average molecular weight of the oligomer in general can be less than about 25,000 g/mol, and preferably, less than about 10,000 g/mol, and more preferably, less than about 5,000 g/mol. Molecular weight is preferably greater than about 500 g/mol.
(A). 1. Preparation of Alkyd:
Hydroxy terminated alkyds have been made by each of two distinct methods of synthesis. In one method an appropriate oil is first reacted with a multi-functional alcohol in a reaction known as alcoholysis. The triglyceride oil is reduced to a monoglyceride and produces a fatty acid ester of the alcohol as a coproduct. This mixture is then reacted in a conventional polyesterification with another diol and suitable diacids, producing the hydroxy-terminated alkyd. In the alternative method, known as direct esterification, the isolated fatty acid is added directly to a polyol and diacid mixture and polymerized, as in conventional polyesterification producing the hydroxy-terminated alkyd.
(A).2. Preparation of Alkyd Urethane Acrylate Oligomer:
The hydroxy-functional alkyd is reacted with a polyisocyanate and a compound providing the reactive termini in order to yield the urethane oligomer.
Polyisocyanates suitable for use in making the compositions of the present invention can be aliphatic, cycloaliphatic or aromatic and include diisocyanates, such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3xe2x80x2-dimethyl-4,4xe2x80x2-diphenylmethane diisocyanate, 4,4xe2x80x2-diphenylmethane diisocyanate, 3,3xe2x80x2-dimethylphenylene diisocyanate, 4,4xe2x80x2-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexyl)isocyanate, 2,2,4-trimethylhexamethylene diisocyanate, bis(2-isocyanate-ethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, and 2,5(or 6)-bis(isocyanatomethyl)-bicyclo[2.2.1 ]heptane. Among these diisocyanates, 2,4-toluene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and methylenebis(4-cyclohexylisocyanate) are particularly preferred. These diisocyanate compounds are used either individually or in combination of two or more.
The compound providing the reactive termini may comprise an ethylenic unsaturation such as acrylate or methacrylate, which will further be denoted as (meth)acrylate. The reactive termini can be introduced by reacting a hydroxyl functional compound with an isocyanate compound. Examples of the (meth)acrylate compounds having a hydroxyl group which are suitable for use in the present invention include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenyloxypropyl (meth)acrylate, 1,4-butanediol mono(meth)acrylate, 2-hydroxyalkyl(meth)acryloyl phosphate, 4-hydroxycyclohexyl (meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, (meth)acrylates represented by the following structural formulas,
CH2xe2x95x90C(R1)xe2x80x94COOCH2CH2xe2x80x94(OCOCH2CH2CH2CH2CH2)nxe2x80x94OH
CH2xe2x95x90C(R1)xe2x80x94COOCH2CH2(OH)CH2xe2x80x94Oxe2x80x94(C6H5)
CH2xe2x95x90C(R1)COO[CH2CH(R2)Oxe2x80x94]nH
wherein R1 is a hydrogen atom or a methyl group, R2 is hydrogen or C1-C4 alkyl group, and n denotes an integer of 1-15. In addition, compounds obtained by an addition reaction between a compound containing a glycidyl group, such as, alkyl glycidyl ether, allyl glycidyl ether, or glycidyl (meth)acrylate, and (meth)acrylic acid can also be used. Among these (meth)acrylates having a hydroxyl group, particularly desirable are 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate. These (meth)acrylates having a hydroxyl group may be used either individually or in combination of two or more.
Preferred alkyd urethane acrylate oligomers are alkyds derived from coconut oil or coconut fatty acid (with an Iodine value of less than about 10), an aliphatic diisocyanate and an hydroxy functional acrylate.
(B) The Reactive Diluent System
The compositions according to the invention also comprise a reactive diluent system (also called monomer or monomer diluent) which comprises at least one reactive diluent. The reactive diluent can be used to adjust the viscosity of the coating composition. Thus, the reactive diluent can be a low viscosity monomer containing one functional group capable of polymerization when exposed to actinic radiation or diluents having a plurality of functional groups.
The reactive diluent is preferably added in such an amount that the viscosity of the coating composition at room temperature is in the range of about 500 to about 20,000 mPa.s, preferably in the range of about 1,000 to about 10,000 mPa.s.
Suitable amounts of the reactive diluent have been found to be about 10 wt % to about 90 wt %, and more preferably about 20 wt. % to about 80 wt. %, and more preferably, about 30 wt. % to about 70 wt. %.
A reactive diluent preferably has a molecular weight of not more than about 550 or a viscosity at room temperature of not more than about 300 mPa.s (measured as 100% diluent).
The radiation-curable functional group present on the reactive diluent may be of the same nature as that used in the radiation-curable oligomer. Preferably, the radiation-curable functional group present in the reactive diluent is capable of 5 copolymerizing with the radiation-curable functional group present on the radiation-curable oligomer. Ethylenic unsaturation is preferred. In particular, (meth)acrylate unsaturation is preferred.
Preferably, the reactive diluent system comprises a monomer or monomers having an acrylate or N-vinyl functionality and a C4-C20 alkyl or polyether moiety. Examples of such reactive diluents include hexylacrylate, 2-ethylhexylacrylate, isobomylacrylate, decylacrylate, laurylacrylate, stearylacrylate, ethoxyethoxyethylacrylate, laurylvinylether, 2-ethylhexylvinyl ether, N-vinyl formamide, isodecyl acrylate, isooctyl acrylate, N-vinyl-caprolactam, N-vinylpyrrolidone and the like.
Another type of reactive diluent is a compound comprising an aromatic group. Examples of diluents having an aromatic group include:
ethyleneglycol phenylether acrylate,
polyethyleneglycol phenylether acrylate,
polypropyleneglycol phenylether acrylate, and
alkyl-substituted phenyl derivatives of the above monomers, such as polyethyleneglycol nonylphenylether acrylate.
Furthermore, a reactive diluent can contain two groups capable of polymerization using actinic radiation. A diluent having three or more of such reactive groups can be present as well. Examples of such monomers include:
C2-C18 hydrocarbon diol diacrylates,
C4-C18 hydrocarbon divinylethers,
C3-C18 hydrocarbon triol triacrylates,
the polyether analogs thereof, and
the like, such as
1,6-hexanedioldiacrylate,
trimethylolpropane triacrylate,
hexanediol divinylether,
triethyleneglycol diacrylate,
pentaeritritol triacrylate,
tripropyleneglycol diacrylate
alkoxylated bisphenol A diacrylate.
Preferably, the oligomer and the reactive diluent each contain an acrylate group as a radiation-curable group.
Among this list, isobornyl acrylate, ethoxylated bisphenol A diacrylate, hexane diol diacrylate and trimethylolpropane triacrylate are particularly preferred.
The alkyd-based coating compositions of the present invention are essentially free of solvent, in particular, organic solvents, meaning that there is less than 2% solvent present in said coating compositions, preferably less than 1%, more preferably less than 0.5%.
(C) The Photoinitiator System
The composition may (optionally) further comprise at least one photoinitiator. A photoinitiator is required for a fast UV cure but may be omitted for electron beam cure. Conventional photoinitiators can be used. Examples include benzophenone- and/or acetophenone derivatives, such as alpha-hydroxy alkylphenyl ketones, benzoin alkyl ethers and benzil ketals, monoacylphosphine oxides, and bisacylphosphine oxides. Preferred photoinitiators are 1-hydroxy-cyclohexyl phenyl ketone (Irgacure 184, Ciba Geigy), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173), and (2,4,6-trimethylbenzoyl)diphenyl phosphine oxide (Lucirin TPO).
Often mixtures of photoinitiators provide a suitable balance of properties, for example Irgacure 1700, also called BAPO, (25% bis(2,6-dimethoxybenzoyl)-2,4-,4-trimethyl pentyl phosphine oxide and 75% 2-hydroxy-2-methyl-1-phenyl-propan-1-one), and the like.
The amount of photoinitiator system is not particularly limited but will be effective to provide fast cure speed, reasonable cost, good surface and through cure, and lack of yellowing upon aging. Typical amounts can be, for example, about 0.3 wt. % to about 10 wt. %, and preferably, about 1 wt. % to about 5 wt. %.
(D) Additives
Conventional additives can be used in effective amounts. For example, additives such as stabilizers to prevent gellation, UV screening compounds, leveling agents, polymerization inhibitors, adhesion promoters, light stabilizers, chain transfer agents, colorants including pigments and dyes, plasticizers, fillers, wetting improvers, release additives (in particular, in inks and matrix materials) preservatives, and the like can be used. For inner primary coatings, an adhesion promoter may be added. Examples of suitable adhesion promoters include acid functional materials or organofunctional silanes. Organofunctional silane adhesion promotors are preferred, because acid-functional materials possibly show corrosivity towards the materials and tendency to loose their adhesion properties on exposure to moisture. Various suitable organofunctional silanes include but are not limited to amino-functional silanes; acrylamido-functional silanes; alkyl-functional silanes; vinyl-functional silanes; (meth)acrylate-functional silanes; and mercapto-functional silanes. The adhesion promoters preferably are methoxy- or ethoxy-substituted.
Other polymers and oligomers can be added to the compositions. Moisture content in the coatings is preferably minimized.
Coatings and Coating Properties
The composite oligomer can be incorporated into inner primary coating compositions, outer primary coating compositions, ink compositions, matrix forming compositions, and bundling materials, which can be colored or non-colored. The composite oligomer also can be incorporated into so-called single coating systems. It is preferred to use alkyd-based urethane acrylate oligomers in harder coatings such as outer primary coatings, ink compositions, matrix and bundling materials.
Specifically, the hydrocarbon nature of the alkyds offers a lower surface energy material which results in compositions/materials with good release properties. Preferably, inks, matrix material and/or the bundling materials are formed from the alkyd-based urethane acrylate oligomers to provide systems with improved break-out characteristics. In addition, the use of alkyd-based urethane acrylate oligomers in inks and/or other compositions incorporating colorants, such as dyes and particularly pigments, provide better wetting and/or compatibility of the colorant.
In general, the coating substrate, which includes optical fiber, will be an inorganic or glass substrate, although in principle, other substrates such as polymeric substrates may also be effectively used. In a preferred application, the coating substrate is an optical glass fiber, and in particular, a freshly drawn, pristine optical glass fiber. Freshly prepared optical glass fiber is known in the art to be responsive to glass coupling agents.
The radiation-curable composition of the present invention may be formulated such that the composition after cure has a modulus as low as 0.1 MPa and as high as 2,000 MPa or more. Those having a modulus in the lower range, for instance, from 0.1 to 10 MPa, preferably 0.1 to 5 MPa, and more preferably 0.5 to less than 3 MPa are typically suitable for inner primary coatings for fiber optics. In contrast, suitable compositions for outer primary coatings, inks and matrix materials generally have a modulus of above 50 MPa, with outer primary coatings tending to have a modulus more particularly above 100 MPa up to 1,000 MPa and matrix materials tending to be more particularly between about 50 MPa to about 200 MPa.
Elongation and tensile strength of these materials can also be optimized depending on the design criteria for a particular use. For cured coatings formed from radiation-curable compositions formulated for use as inner primary coatings on optical fibers, the elongation-at-break is typically greater than 80%, more preferably the elongation-at-break is at least 110%, more preferably at least 150% but not typically higher than 400%. For coatings formulated for outer primary coatings, inks and matrix materials the elongation-at-break is typically between 3% and 100%, and preferably higher than 30%.
The glass transition temperature (Tg), measured as the peak tan-delta determined by dynamic mechanical analysis (DMA), can be optimized depending on the particulars of the application. The glass transition temperature may be from 10xc2x0 C. down to xe2x88x9270xc2x0 C. or lower, more preferably lower than xe2x88x9210xc2x0 C. for compositions formulated for use as inner primary coatings and 10xc2x0 C. to 120xc2x0 C. or higher, more preferably above 30xc2x0 C., for compositions designed for use as outer primary coatings, inks and matrix materials.
The compositions of the present invention will preferably have a cure speed of 1.0 J/cm2 or less(at 95% of maximum attainable modulus). For a coating, ink or matrix material, cure speed is preferably about 0.5 J/cm2 or less (at 95% of maximum attainable modulus), and more preferably, about 0.3 J/cm2 or less, and even more preferably, about 0.2 J/cm2 or less.
As an example, a coating formulation resulting in outer primary type mechanical properties is given. The components of the formulation are an oligomer, isobomylacrylate, ethoxylated bisphenol-A acrylate (BPAEDA), and an additional crosslinking monomer as either hexanediol diacrylate (HDDA) or trimethylolpropane triacrylate (TMPTA).
The radiation-curable coating compositions of the present invention, when tested in accordance with the method set forth in the Examples, show a hydrolysis resistance of less than 30%, preferably less than 20%, more preferably less than 16%.
The coating compositions of the present invention, after cure, show a dynamic water sensitivity of less than 2%, preferably less than 1.6%, and more preferably less than 1.4%.
The radiation curable coating compositions according to the present invention, when cured, show very good yellowing resistance, measured by xcex94E, after exposure to 125xc2x0 C. for 8 weeks, preferably xcex94E is less than 70, more preferably less than 60.
The present invention will be further explained by use of the following non-limiting examples.

Radiation-curable compositions comprising oligomers having an alkyd backbone


A water-soluble or water-dispersible material for deposition onto a fabric substrate during a treatment process. The material comprises a xcex21-4-linked polysaccharide structure having at least one substituent benefit agent group and optionally, one or more other substituent groups. The average degree of substitution of all substituent groups is from 0.01 to 1.2, preferably from 0.1 to 1.2, more preferably from 0.4 to 1.2. The polysaccharide structure has one or more regions with at least 3, preferably at least 4 consecutive unsubstituted saccharide rings.

The present invention relates to a material comprising a benefit agent and a deposition aid for deposition of the benefit agent onto a fabric. It further relates to a method of depositing a benefit agent from solution or dispersion, onto a fabric.
The deposition of a benefit agent onto a fabric is well known in the art. In laundry applications typical xe2x80x9cbenefit agentsxe2x80x9d include fabric softeners and conditioners, soil release polymers, sunscreens; and the like. Deposition of a benefit agent is used, for example, in fabric treatment processes such as fabric softening to impart desirable properties to the fabric substrate.
Conventionally the deposition of the benefit agent may rely upon the attractive forces between the oppositely charged substrate and the benefit agent. Typically this requires the addition of benefit agents during the rinsing step of a treatment process so as to avoid adverse effects from other charged chemical species present in the treatment compositions. For example, cationic fabric conditioners are incompatible with anionic surfactants in laundry washing compositions.
Such adverse charge considerations can place severe limitations upon the inclusion of benefit agents in compositions where an active component thereof is of an opposite charge to that of the benefit agent. For example, cotton is negatively charged and thus requires a positively charged benefit agent in order for the benefit agent to be substantive to the cotton, i.e. to have an affinity for the cotton so as to absorb onto it. Often the substantivity of the benefit agent is reduced and/or the deposition rate of the material is reduced because of the presence of incompatible charged species in the compositions.
The deterging nature of laundry wash compositions also places severe limitations upon the inclusion of neutral but hydrophobic or oily benefit agents which are not effectively deposited in the presence of surfactant.
Alternatively, when deposition of a conventional benefit agent is effected by mechanisms that do not rely upon charge interaction but upon other non-covalent forces, for example soil release polymers, other problems may occur, namely where interaction of an anionic surfactant with the benefit agent can also make the material so negatively charged and/or soluble as to overcome the other attractive interactions.
Furthermore, there is frequently another complication in achieving optimum deposition of a benefit agent onto a fabric, in that, the need for solubility of the benefit agent in the medium used to treat the substrate is in principle, incompatible with the requirement for of the benefit agent to deposit/adsorb onto the substrate.
The present invention is directed towards materials for solving one or more of the above problems.
WO-A-98/00500 discloses detergent compositions comprising a peptide or protein deposition aid having a high affinity for fibres or a surface, and a benefit agent attached/adsorbed to the deposition aid. However, the peptide or protein is a relatively expensive material and the need still exists to find a more cost effective alternative material as a vehicle for depositing a benefit agent.
Our unpublished copending European Patent Application No. 98300292.4 discloses polysaccharide or oligosaccharide conjugates with an attached entity (e.g. a protein or an enzyme) having a molecular weight of at least 5,000. Although the poly/oligosaccharide is capable of binding to cellulose, there is no teaching of the molecular requirements for optimising the balance between water solubility and fabric affinity.
GB-A-948 678 discloses a process for dyeing and printing textiles using an aqueous preparation containing organic dyestuff residues linked by a covalent bond to high molecular weight polymers such as cellulose ethers, cellulose derivatives, starches, gums and other related naturally occurring polymers. Cellulose derivatives with a degree of substitution of 0.1 for carboxymethyl substituents are recited explicitly. However, these carboxymethyl groups and the dyestuff residues are not xe2x80x9cbenefit agent groupsxe2x80x9d within the sense intended herein.
U.S. Pat. No. 4,668,779 discloses a gel in the form of a complex between a metallic oxide and a semi-synthetic polygalactan. This is described for use in microbiological analysis. There is no disclosure of chemical bonding between a substance and the polysaccharide and certainly no substituent group which is in any way a benefit agent group for conferring a benefit to a fabric.
U.S. Pat. No. 5,160,641 and U.S. Pat. No. 5,540,850 disclose cellulose ether derivatives for use as anti-redeposition agents in fabric washing compositions. Substantially all of the saccharide rings are substituted. Furthermore, there is no mention of substituents which are themselves, benefit agent groups.
WO-A-95/30042 discloses a gel composition for use in the manufacture of treated fabrics. It comprises a cellulose based carrier with a solvent and a material for conferring a speciality finish, e.g. waterproofing, softening or anti-static effect. However, the speciality finish agent is not bonded to the cellulosic gel. Further, there is no disclosure or suggestion of use during washing, rinsing or drying of fabric by a consumer.
WO-A-98/29528 discloses cellulose ethers in which some substituents are (poly)alkoxylated, analogues of the latter in which the (poly)alkoxylated groups are terminated with a cationic moiety in the form of a quaternary ammonium group, and cellulose ethers in which some substituents are carboxylic acids in the salt form (i.e. the materials are essentially carboxymethylcellulose variants). As defined by the general formulae in WO-A-98/129528, none of these molecules has regions of unsubstitution, as required by the present invention.
WO-A-99/14245 discloses laundry detergent compositions containing cellulosic based polymers to provide appearance and integrity benefits to fabrics. These polymers are cellulosic polymers in which the saccharide rings have pendant oxygen atoms to which substituents xe2x80x98Rxe2x80x99 can be hydrogen, lower alkyl or alkylene linkages terminated by carboxylic acid, ester or amide groups. Optionally, up to five alkyleneoxy groups may be interspersed between the groups are the respective oxygen atom. WO-A-99/14295 discloses structures analogous to those described in WO-A-99/14245 but in one alternative, the substituents xe2x80x98Rxe2x80x99 together with the oxygen on the saccharide ring, constitute pendant half-esters of certain dicarboxylic acids. As described in both of these documents, none of the pendant groups is a benefit agent group.
The present invention relates to materials for achieving initial solubility or dispersibility in the medium used to treat the fabric and effective deposition of one or more benefit-endowing groups thereon.
Accordingly, a first aspect of the present invention provides a water-soluble or water-dispersible material for deposition onto a fabric substrate during a wash and/or rinse and/or drying process, wherein the material comprises a xcex21-4-linked polysaccharide structure having at least one substituent benefit agent group and optionally, one or more other substituent groups, wherein the average degree of substitution of all substituent groups is from 0.01 to 1.2, preferably from 0.1 to 1.2, more preferably from 0.4 to 1.2, the polysaccharide structure having one or more regions with at least 3, preferably at least 4 consecutive unsubstituted saccharide rings.
A second aspect of the present invention also provides a method of depositing a benefit agent onto a fabric by its incorporation in a material according to the first aspect of the invention and applying said material to the fabric.
A third aspect of the present invention also provides compositions comprising a material according to the first aspect of the present invention. In particular, such compositions preferably comprise one or more surfactants.
The Material
The material of the present invention is water-soluble or water-dispersible in nature and comprises a xcex21-4-linked polysaccharide structure and at least one substituent benefit agent for deposition onto a fabric during a treatment process.
A polysaccharide comprises a plurality of saccharide rings which have pendant hydroxyl groups The benefit agent group(s) and optionally, any other substituent(s) can be bonded chemically to these hydroxyl groups by any means described hereinbelow. The xe2x80x9cdegree of substitutionxe2x80x9d means the average number of substituents per saccharide ring for the totality of polysaccharide molecules in the sample and is determined for all saccharide rings whether they form part of a linear backbone or are themselves pendant side groups in the polysaccharide.
Preferably, the substituent benefit agent group(s) is/are attached to the polysaccharide by a hydrolytically stable bond. That means that the bonding of the substituted benefit agent(s) should be sufficiently stable so as not to undergo substantial hydrolysis in the environment of the treatment process for the duration of that process. For example, in laundry cleaning applications, the material should be sufficiently stable so that the bond between the benefit and deposition enhancing part does not undergo hydrolysis in the wash liquor, at the wash temperature, before the benefit agent has been deposited onto the fabric.
Preferably, the bond between the substituent benefit agent(s) and the polysaccharide is such that the decay rate constant (kd) of the material in an aqueous solution at 0.01 wt % of the material together with 0.1 wt % of anionic surfactant at a temperature of 40xc2x0 C. at a pH of 10.5 is such that kd less than 10xe2x88x923sxe2x88x921.
By water-soluble, as used herein, what is meant is that the material forms an isotropic solution on addition to water or another aqueous solution.
By water-dispersible, as used herein, what is meant is that the material forms a finely divided suspension on addition to water or another aqueous solution.
Deposition onto a substrate includes deposition by adsorption, co-crystallisation, entrapment and/or adhesion.
Polysaccharide
The xcex2-1,4-linked polysaccharide structure is chosen for having an affinity for cellulose, viscose and similar fibres. Suitable such polysaccharides include cellulose, mannan and glucomannan. It may be straight or branched. Many naturally occurring polysaccharides have at least some degree of branching, or at any rate, at least some saccharide rings are in the form of pendant side groups on a main polysaccharide backbone. The polysaccharide may be charged or uncharged, although uncharged types are generally preferred.
The polysaccharide may be a synthetic polysaccharide, a naturally occurring polysaccharide or a modified naturally occurring polysaccharide. Preferably, it has a weight average molecular weight (Mw), as determined by GPC, of at least 1,000. In the case of naturally occurring polysaccharides, the Mw range will be typically from 100,000 to 2,000,000. For synthetic or modified naturally occurring materials, the Mw will typically be from 10,000 to 50,000.
Preferably, at least 5% of the saccharide rings are in the consecutive unsubstituted region(s). Most preferably, at least 80% of the unsubstituted region(s) contain no more than 100, especially no more than 50 consecutive unsubstituted saccharide rings. For example, no more than 50% of the saccharide rings are in such regions. Also, for example, no region may have more than 100 (more preferably more than 50) consecutive unsubstituted saccharide rings.
Benefit Agent Group
The benefit agent group may be any group which is used to impart desirable properties to the fabric upon which the material of the present invention is to be deposited. In practice, a material according to the present invention may comprise two or more benefit agent groups on the same molecule, either of the same kind or of different kinds.
Preferably, the benefit agent group(s) is/are selected from any of the following:-
(a) fabric softening and/or conditioning agents;
(b) lubricants for inhibition of fibre damage and/or for colour care and/or for crease reduction and/or for ease of ironing;
(c) UV absorbers such as fluorescers and photofading inhibitors, for example sunscreens/UV inhibitors and/or anti-oxidants;
(d) fungicides and/or insect repellents; and
(e) perfumes.
Suitable fabric softening and/or conditioning agent groups are preferably chosen from those of the cationic detergent active type, and silicones. Those of the cationic detergent active type are preferably selected from quaternary ammonium cationic molecules, for example those having a solubility in water at pH 2.5 and 20xc2x0 C. of less than 10 g/l.
It is preferred for the ester-linked quaternary ammonium compounds to contain two or more ester groups. In both monoester and the diester quaternary ammonium compounds it is preferred if the ester group(s) is a linking group between the nitrogen atom and an alkyl group. The ester groups(s) are preferably attached to the nitrogen atom via another hydrocarbyl group.
As used herein the term xe2x80x98ester groupxe2x80x99, when used in the context of a group in the quaternary ammonium material, includes an ester group which is a linking group in the molecule.
Typical are quaternary ammonium compounds containing at least one ester group, preferably two, wherein at least one higher molecular weight group containing at least one ester group and two or three lower molecular weight groups are linked to a common nitrogen atom to produce a cation and wherein the electrically balancing anion is a halide, acetate or lower alkosulphate ion, such as chloride or methosulphate. The higher molecular weight substituent on the nitrogen is preferably a higher alkyl group, containing 12 to 28, preferably 12 to 22, e.g. 12 to 20 carbon atoms, such as coco-alkyl, tallowalkyl, hydrogenated tallowalkyl or substituted higher alkyl, and the lower molecular weight substituents are preferably lower alkyl of 1 to 4 carbon atoms, such as methyl or ethyl, or substituted lower alkyl. One or more of the said lower molecular weight substituents may include an aryl moiety or may be replaced by an aryl, such as benzyl, phenyl or other suitable substituents.
More preferably, the quaternary ammonium material comprises a compound having two long chain alkyl or alkenyl chains with an average chain length equal to or greater than C14. Even more preferably each chain has an average chain length equal to or greater than C16. Most preferably at least 50% of each long chain alkyl or alkenyl group has a chain length of C18. It is preferred if the long chain alkyl or alkenyl groups are predominantly linear.
It is particularly advantageous if the cationic softening compound is a quaternary ammonium compound with two C12-C22 alkyl or alkenyl groups connected to a quaternary ammonium group via at least one ester link, preferably two ester links, or else a compound with a single long chain with an average chain length greater than or equal to C20. Examples of cationic softeners are described in U.S. Pat. No. 4,137,180 and WO-A-93/23510.
The most preferred type of ester-linked quaternary ammonium material that can be used as benefit agent group(s) is represented by the formula (A):
wherein R1, n, R2 and Xxe2x88x92 are as defined above.
It is advantageous for environmental reasons if the quaternary ammonium material is biologically degradable.
Preferred materials of this class such as 1,2 bis[hardened tallowoyloxy]-3-trimethylammonium propane chloride and their method of preparation are, for example, described in U.S. Pat. No. 4,137,180. Preferably these materials comprise small amounts of the corresponding monoester as described in U.S. Pat. No. 4,137,180 for example 1-hardened tallow-oyloxy-2-hydroxy-3-trimethylammonium propane chloride.
Another class of preferred ester-linked quaternary ammonium materials for use as benefit agent group(s) can be represented by the formula:
wherein each R1 group is independently selected from C1-4alkyl, hydroxyalkyl or C2-4 alkenyl groups; and wherein each R2 group is independently selected from C8-28 alkyl or alkenyl groups; Xxe2x88x92 is any suitable counter-ion, i.e. a halide, acetate or lower alkosulphate ion, such as chloride or methosulphate.
n is an integer from 1-5 or is 0
It is especially preferred that each R1 group is methyl and each n is 2.
Of the compounds of formula (B), Di-(tallowyloxyethyl)-dimethyl ammonium chloride, available from Hoechst, is the most preferred. Di-(hardened tallowyloxyethyl)dimethyl ammonium chloride, ex Hoechst and di-(tallowyloxyethyl)-methyl hydroxyethyl methosulphate are also preferred.
Another preferred class of quaternary ammonium cationic fabric softening agent for use as the benefit agent group(s)is defined by formula (C):-
where R1, R2 and X are as hereinbefore defined.
A preferred material of formula (C) is di-hardened tallow-diethyl ammonium chloride, sold under the Trademark Arquad 2HT.
It is also possible to use certain mono-alkyl cationic surfactants which on their own can be used in main-wash compositions for fabrics. Cationic surfactants that may be used include quatenary ammonium salts of the general formula R1R2R3R4N+Xxe2x88x92) wherein the R groups are long or short hydrocarbon chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a counter-ion (for example, compounds in which R1 is a C8-C22 alkyl group, preferably a C8-C10 or C12-C14 alkyl group, R2 is a methyl group, and R3 and R4, which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters).
If the fabric softening and/or conditioning group(s) is/are silicones, these may for example be selected from those disclosed in GB-A-1 549 180, EP-A459 821 and EP-A459 822.However, these silicones if used for other benefits listed under the class (b) above, can be regarded as xe2x80x9clubricantsxe2x80x9d. Other suitable lubricants include any of those known for use as dye bath lubricants in the textile industry.
Suitable photofading inhibitors of the sunscreen/UV inhibitor type are preferably molecules with an extinction co-efficient greater than 2000 l molxe2x88x921 cmxe2x88x921 at a wavelength of maximal absorption. Typically for a sunscreen maximal absorption occurs at wavelengths of 290-370 nm, more usually 310-350 nm, especially 330-350 nm.
Examples of suitable sunscreens are given in Cosmetic Science and Technology Series, Vol. 15; Sunscreens; 2nd edition; edited by Lowe, Shoath and Pathak; Cosmetics and Toiletries; Vol. 102; March 1987; pages 21-39; and Evolution of Modern Sunscreen Chemicals; pages 3-35 both by N. A. Saarth.
In particular, suitable sunscreens include carboxylic acids or carboxylic acid derivatives, for example acrylates, cinnamates and benzoates or derivatives thereof, such as 4-methoxy cinnamate salicylates, PABA, 4-acetoxy benzoate dibenzoylmethanes, phenyl benzoimidazoles, aminobenzoates, benzotriazoles and benzophenones.
Suitable photofading inhibitors of the anti-oxidant type include benzofurans, coumeric acids or derivatives thereof, for example 2-carboxy benzofuran and bis(p-amine sulphonates) triazine, DABCO derivatives, tocopherol derivatives, tertiary amines and aromatic substituted alcohols eg butylated hydroxytoluene (BHT), Vitamin C (ascorbic acid) and vitamin E.
Suitable fungicides include 6-acetoxy-2,4-dimethyl-m-dioxane, diiodomethyl-p-tolysulphone, 4,4-dimethyloxaolidine, hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine, sodium dimethyldithiocarbamate, sodium 2-mercaptobenzothioazole, zinc dimethyldithiocarbamate, zinc 2-mercaptobenzothiazole, sodium 2-pyridinethiol-1-oxide, sodium 2-pyridinethiol-1-oxide and N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide.
Suitable insect repellents include N-alkyl neoalkanamides wherein the alkyl is of 1 to 4 carbon atoms and the neoalkanoyl moiety is of 7 to 14 carbon atoms preferably N-methyl neodecanamide; N,N-diethyl meta toluamide (DEET), 2-Hydroxyethyl-n-octyl sulphide (MGK 874); N-Octyl bicycloheptene dicarboximide (MGK 264); hexahydrodibenzofuran (MGK 11), Di-n-propyl isocinchomerate (MGK 326); 2-Ethyl-1,3-hexanediol, 2-(n-butyl)-2-ethyl-1,3-propanediol, dimethyl phthalate, dibutyl succinate, piperonyl butoxide, pyrethrum, Cornmint, Peppermint, American spearmint, Scotch spearmint, Lemon oil, Citronella, cedarwood oil, pine oil, Limonene, carvone, Eucalyptol, Linalool, Gum Camphor, terpineol and fencholic acid.
Suitable perfumes are commercially available and have an undisclosed molecular structure.
Other Substituents
In addition to the benefit agent group(s), the materials according to the present invention optionally may also have one or more other pendant groups. Those are also taken into account when determining the degree of substitution. These may be the same or different and may for example be non-functional groups which are present as artefacts in the naturally occurring material or from the process used to obtain a synthetic or modified naturally occurring material. However, it is possible for one or more of the non-benefit agent pendant groups to be provided for other purposes, e.g. for enhancing the solubility of the molecule. Examples of solubility enhancing substituents include carboxyl, sulphonyl, hydroxyl, (poly)ethyleneoxy- and/or (poly)propyleneoxy-containing groups, as well as amine groups.
The other pendant groups preferably constitute from 0% to 65%, more preferably from 0% to 10% (e.g. from 0% to 5%) of the total number of pendant groups. The minimum number of the other pendant groups may, for example, be 0.1% or 1% of the total. The water-solubilising groups could comprise from 0% to 100% of those other groups but preferably from 0% to 20%, more preferably from 0% to 10%, still more preferably from 0% to 5% of the total number of other pendant groups.
Synthetic Routes
If the benefit is attached to the deposition polysaccharide this may be chemically bonded via a linking agent. However, direct chemical bonding may also be used, as described in more detail hereinbelow.
Suitable linking agents are molecules which show a high affinity for the benefit agent group. It is preferred if the linking agent is covalently attached to the backbone of the deposition enhancing part. It is also advantageous if the linking agent is covalently bound to the benefit agent group.
There are basically two general methods for preparing a water-soluble or water dispersable material comprising a xcex21-4-linked polysaccharide and a substituent benefit agent.
According to one such method, the benefit agent(s) is/are grafted onto the polysaccharide.
In a second alternative method, the benefit agent is grafted onto a precursor of the xcex21-4-linked polysaccharide; and then the precursor is converted into the desired (modified) polysaccharide.
For both methods, the general method for preparing the polysaccharide may be achieved by a number of different synthetic routes, for example:-
(a) polymerisation of suitable monomers, for example, enzymatic polymerisation of saccharides, e.g. per S. Shoda, and S. Kobayashi, Makromol. Symp. 1995, 99, 179-184 or oligosaccharide synthesis by orthogonal glycosylation e.g. per H. Paulsen, Angew. Chem. Int. Ed. Engl. 1995, 34 1432-1434.;
(b) derivatisation of a polysaccharide chain (either naturally occurring, especially polysaccharides, especially beta-1,4-linked polysaccharides, especially cellulose, mannan, glucomannan, galactomannan, xyloglucan; or synthetic polymers) up to the required degree of substitution with functional groups, using a reagent (especially acid halides, especially carboxylic acid halides, anhydrides, carboxylic acid anhydrides, carboxylic acids, carbonates) in a solvent which either dissolves the backbone, swells the backbone, or does not swell the backbone but dissolves or swells the product).
(c) hydrolysis of polymer derivatives (especially esters) down to the required degree of substitution; or
(d) a combination of any two or more of routes (a)-(c).
Many suitable xcex21-4-linked polysaccharides are commercially available.
The degree and pattern of substitution from routes (a) or (c) may be subsequently altered by partial removal of functional groups by hydrolysis or solvolysis or other cleavage. In addition, or alternatively, the degree of polymerisation of the polysaccharide may be reduced before, during, or after the derivatisation with functional groups. For example, the relative proportions of reactants and/or the reaction time can be used to control the degree of substitution. The number of unsubstituted regions may be controlled by choice of the solvent in which the reaction(s) is/are performed, for example exploiting the polarity of the solvent and/or the degree to which reactant are soluble or misable in it (i.e. the degree to which the reaction mixture is homogenous or heterogenous). These techniques and how to apply then will be readily apparent to those skilled in the art of polymer chemistry. The degree of polymerisation of the polysaccharide may be increased by further polymerisation or by cross linking agents before, during, or after the derivatisation step.
For both of the aforementioned methods, grafting the benefit agent onto the polysaccharide can be effected either:-
(a) by physical attraction between the benefit agent and the polysaccharide, especially the use of a block copolymer where one block has a physical affinity for the benefit agent and the other block can undergo a chemical change during treatment which increases its affinity for the fabric; or
(b) by grafting the benefit agent onto the polysaccharide using a bond which is relatively hydrolytically stable. For example, an ester bond can be used which is more stable than the one intended to undergo the chemical change but which is not be completely stable. For example a conjugated or aromatic ester. Such grafting can be accomplished by reacting the polysaccharide or already-pre-modified polymeric backbone (especially cellulose esters, especially cellulose acetates) with a benefit-agent reagent (especially acid halides, especially carboxylic acid halides, anhydrides, carboxylic acid anhydrides, carboxylic acids, isocyanates, triazine derivatives, amines, hydrazines) in a solvent which dissolves the polysaccharide, swells the polysaccharide, or does not swell the polysaccharide (depending on whether grafting the benefit agent first or last) but dissolves or swells the final product.
For the grafting, typically, radiation methods may be used, for example:-
1. Grafting by Mutual Irradiation (The Direct Radiation Grafting of the Benefit Group onto the Polysaccharide).
The mutual irradiation method is the simplest radiation-chemical method for producing graft copolymers. The procedure involves the irradiation of a polymeric substrate in the presence of a benefit group-containing monomer solution, preferably in the absence of oxygen at around ambient temperature for a giving time and irradiation dose. It is known that most radiation-initiated polymerization proceeds by free radical mechanisms, and that it is initiated by the free radicals arising from the radiolysis of the either polymer or monomer, although the mutual irradiation is the most efficient method of achieve grafting.
2. Grafting on to Radiationxe2x80x94Peroxided Polysaccharide.
In this method, the polymeric samples of polysaccharide are first irradiated, typically in the presence of air or pure oxygen atmosphere at around ambient temperature in the absence any monomer or solvent to produce peroxide or hydroperoxides linkages by gamma irradiation. Subsequently, the graft copolymerization is initiated by the free radicals produced from the thermal decomposition of peroxide or hydroperoxides linkages under heating with a benefit agent monomer in the appropriate solvent.
Two different situations arise, depending on whether peroxides or hydroperoxides are formed in the irradiated polymer. Either, the peroxidation leads to peroxidized polymer or else it leads to hydroperoxides.
Grafting may also be effected by means of chemical grafting, for example using ceric ions (A. Habeish et al, J. Appl. Polym. Sci. 1971,15, 11-24) or using other conventional radical initiators such as potassium persulphate, e.g. per R. K. Samal, et al J. Polym. Mater. 1987, 4(3), 165-172.
In one example hereinbelow there is described a method of producing carboxymethyl cellulose with grafted fluorescer groups. There are a number of ways one can introduce fluorescent molecules onto carboxymethylcellulose. Generally most fluorescent molecules contain an amine functionality. A simple method will be the amidation of these two molecules. If desired a water soluble coupling agent can also be employed.
Another method will be via a linking group such as cyanuric chloride (2,4,6-trichloro-1,3,5-triazine) as shown below. This can be conducted by reacting SCMC with cyanuric chloride, followed by reaction with the fluorescent molecule. The reaction sequences can also be altered, i.e. reacting the fluorescent molecule with cyanuric chloride first and then reacting the adduct with SCMC. As fluorescent molecules are sensitive to light, the reaction is best to be carried out with a blacked out apparatus.
Compositions
The material according to the first aspect of the present invention may be incorporated into compositions containing only a diluent (which may comprise solid and/or liquid) and/or also comprising an active ingredient. The compound is typically included in said compositions at levels of from 0.01% to 25% by weight, preferably from 0.5% to 20%, most preferably from 1% to 15%.
The active ingredient in the compositions is preferably a surface active agent or a fabric conditioning agent. More than one active ingredient may be included. For some applications a mixture of active ingredients may be used.
The compositions of the invention may be in any physical form e.g. a solid such as a powder or granules, a tablet, a solid bar, a paste, gel or liquid, especially, an aqueous based liquid.
The compositions of the present invention are preferably laundry compositions, especially main wash (fabric washing) compositions or rinse-added softening compositions. The main wash compositions may include a fabric softening agent and rinse-added fabric softening compositions may include surface-active compounds, particularly non-ionic surface-active compounds, if appropriate.
The detergent compositions of the invention may contain a surface-active compound (surfactant) which may be chosen from soap and non-soap anionic, cationic, non-ionic, amphoteric and zwitterionic surface-active compounds and mixtures thereof. Many suitable surface-active compounds are available and are fully described in the literature, for example, in xe2x80x9cSurface-Active Agents and Detergentsxe2x80x9d, Volumes I and II, by Schwartz, Perry and Berch.
The preferred detergent-active compounds that can be used are soaps and synthetic non-soap anionic and non-ionic compounds.
The compositions of the invention may contain linear alkylbenzene sulphonate, particularly linear alkylbenzene sulphonates having an alkyl chain length of C8-C15. It is preferred if the level of linear alkylbenzene sulphonate is from 0 wt % to 30 Wt %, more preferably 1 wt % to 25 wt %, most preferably from 2 wt % to 15 wt %.
The compositions of the invention may contain other anionic surfactants in amounts additional to the percentages quoted above. Suitable anionic surfactants are well-known to those skilled in the art. Examples include primary and secondary alkyl sulphates, particularly C8-C15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates. Sodium salts are generally preferred.
The compositions of the invention may also contain non-ionic surfactant. Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C8-C20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
It is preferred if the level of non-ionic surfactant is from 0 wt % to 30 wt %, preferably from 1 wt % to 25 wt %, most preferably from 2 wt % to 15 wt %.
Cationic surfactants can also be used for fabric softening and/or rinse conditioning. These may for example be of the type mentioned hereinbefore for use as benefit agent groups.
The choice of surface-active compound (surfactant), and the amount present, will depend on the intended use of the detergent composition. In fabric washing compositions, different surfactant systems may be chosen, as is well known to the skilled formulator, for handwashing products and for products intended for use in different types of washing machine.
The total amount of surfactant present will also depend on the intended end use and may be as high as 60 wt %, for example, in a composition for washing fabrics by hand. In compositions for machine washing of fabrics, an amount of from 5 to 40 wt % is generally appropriate. Typically the compositions will comprise at least 2 wt % surfactant e.g. 2-60%, preferably 15-40% most preferably 25-35%.
Detergent compositions suitable for use in most automatic fabric washing machines generally contain anionic non-soap surfactant, or non-ionic surfactant, or combinations of the two in any suitable ratio, optionally together with soap.
The compositions of the invention, when used as main wash fabric washing compositions, will generally also contain one or more detergency builders. The total amount of detergency builder in the compositions will typically range from 5 to 80 wt %, preferably from 10 to 60 wt %.
Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB 1 437 950 (Unilever); crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB 1 473 201 (Henkel), amorphous aluminosilicates as disclosed in GB 1 473 202 (Henkel) and mixed crystalline/amorphous aluminosilicates as disclosed in GB 1 470 250 (Procter and Gamble); and layered silicates as disclosed in EP 164 514B (Hoechst). Inorganic phosphate builders, for example, sodium orthophosphate, pyrophosphate and tripolyphosphate are also suitable for use with this invention.
The compositions of the invention preferably contain an alkali metal, preferably sodium, aluminosilicate builder. Sodium aluminosilicates may generally be incorporated in amounts of from 10 to 70% by weight (anhydrous basis), preferably from 25 to 50 wt %.
The alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula: 0.8-1.5Na2O.Al2O3.0.8-6SiO2.
These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g. The preferred sodium aluminosilicates contain 1.5-3.5 SiO2 units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1 429 143 (Procter and Gamble). The preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.
The zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders. However, according to a preferred embodiment of the invention, the zeolite builder incorporated in the compositions of the invention is maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP 384 070A (Unilever). Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.
Especially preferred is zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00. The calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per g of anhydrous material.
Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di and trisuccinates, carboxymethyloxy succinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.
Especially preferred organic builders are citrates, suitably used in amounts of from 5 to 30 wt %, preferably from 10 to 25 wt %; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt %, preferably from 1 to 10 wt %.
Builders, both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
Compositions according to the invention may also suitably contain a bleach system. Fabric washing compositions may desirably contain peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.
Suitable peroxy bleach compounds include organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates. Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.
Especially preferred is sodium percarbonate having a protective coating against destabilisation by moisture. Sodium percarbonate having a protective coating comprising sodium metaborate and sodium silicate is disclosed in GB 2 123 044B (Kao).
The peroxy bleach compound is suitably present in an amount of from 0.1 to 35 wt %, preferably from 0.5 to 25 wt %. The peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures. The bleach precursor is suitably present in an amount of from 0.1 to 8 wt %, preferably from 0.5 to 5 wt %.
Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and pernoanoic acid precursors. Especially preferred bleach precursors suitable for use in the present invention are N,N,Nxe2x80x2,Nxe2x80x2,-tetracetyl ethylenediamine (TAED) and sodium noanoyloxybenzene sulphonate (SNOBS). The novel quaternary ammonium and phosphonium bleach precursors disclosed in U.S. Pat. No. 4,751,015 and U.S. 4,818,426 (Lever Brothers Company) and EP 402 971A (Unilever), and the cationic bleach precursors disclosed in EP 284 292A and EP 303 520A (Kao) are also of interest.
The bleach system can be either supplemented with or replaced by a peroxyacid. examples of such peracids can be found in U.S. Pat. No. 4,686,063 and U.S. 5,397,501 (Unilever). A preferred example is the imido peroxycarboxylic class of peracids described in EP A 325 288, EP A 349 940, DE 382 3172 and EP 325 289. A particularly preferred example is phtalimido peroxy caproic acid (PAP). Such peracids are suitably present at 0.1-12%, preferably 0.5-10%.
A bleach stabiliser (transition metal sequestrant) may also be present. Suitable bleach stabilisers include ethylenediamine tetra-acetate (EDTA), the polyphosphonates such as Dequest (Trade Mark) and non-phosphate stabilisers such as EDDS (ethylene diamine di-succinic acid). These bleach stabilisers are also useful for stain removal especially in products containing low levels of bleaching species or no bleaching species.
An especially preferred bleach system comprises a peroxy bleach compound (preferably sodium percarbonate optionally together with a bleach activator), and a transition metal bleach catalyst as described and claimed in EP 458 397A, EP 458 398A and EP 509 787A (Unilever).
The compositions according to the invention may also contain one or more enzyme(s). Suitable enzymes include the proteases, amylases, cellulases, oxidases, peroxidases and lipases usable for incorporation in detergent compositions. Preferred proteolytic enzymes (proteases) are, catalytically active protein materials which degrade or alter protein types of stains when present as in fabric stains in a hydrolysis reaction. They may be of any suitable origin, such as vegetable, animal, bacterial or yeast origin.
Proteolytic enzymes or proteases of various qualities and origins and having activity in various pH ranges of from 4-12 are available and can be used in the instant invention.
Examples of suitable proteolytic enzymes are the subtilins which are obtained from particular strains of B. Subtilis B. licheniformis, such as the commercially available subtilisins Maxatase (Trade Mark), as supplied by Gist Brocades N.V., Delft, Holland, and Alcalase (Trade Mark), as supplied by Novo Industri A/S, Copenhagen, Denmark.
Particularly suitable is a protease obtained from a strain of Bacillus having maximum activity throughout the pH range of 8-12, being commercially available, e.g. from Novo Industri A/S under the registered trade-names Esperase (Trade Mark) and Savinase (Trade-Mark). The preparation of these and analogous enzymes is described in GB 1 243 785. Other commercial proteases are Kazusase (Trade Mark obtainable from Showa-Denko of Japan), Optimase (Trade Mark from Miles Kali-Chemie, Hannover, West Germany), and Superase (Trade Mark obtainable from Pfizer of U.S.A.).
Detergency enzymes are commonly employed in granular form in amounts of from about 0.1 to about 3.0 wt %. However, any suitable physical form of enzyme may be used.
The compositions of the invention may contain alkali metal, preferably sodium carbonate, in order to increase detergency and ease processing. Sodium carbonate may suitably be present in amounts ranging from 1 to 60 wt %, preferably from 2 to 40 wt %. However, compositions containing little or no sodium carbonate are also within the scope of the invention.
Powder flow may be improved by the incorporation of a small amount of a powder structurant, for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate copolymer, or sodium silicate. One preferred powder structurant is fatty acid soap, suitably present in an amount of from 1 to 5 wt %.
Other materials that may be present in detergent compositions of the invention include sodium silicate; antiredeposition agents such as cellulosic polymers; soil release polymers; inorganic salts such as sodium sulphate; lather control agents or lather boosters as appropriate; proteolytic and lipolytic enzymes; dyes; coloured speckles; perfumes; foam controllers; fluorescers and decoupling polymers. This list is not intended to be exhaustive. However, many of these ingredients will be better delivered as benefit agent groups in materials according to the first aspect of the invention.
The detergent composition when diluted in the wash liquor (during a typical wash cycle) will typically give a pH of the wash liquor from 7 to 10.5 for a main wash detergent.
Particulate detergent compositions are suitably prepared by spray-drying a slurry of compatible heat-insensitive ingredients, and then spraying on or post-dosing those ingredients unsuitable for processing via the slurry. The skilled detergent formulator will have no difficulty in deciding which ingredients should be included in the slurry and which should not.
Particulate detergent compositions of the invention preferably have a bulk density of at least 400 g/l, more preferably at least 500 g/l. Especially preferred compositions have bulk densities of at least 650 g/liter, more preferably at least 700 g/liter.
Such powders may be prepared either by post-tower densification of spray-dried powder, or by wholly non-tower methods such as dry mixing and granulation; in both cases a high-speed mixer/granulator may advantageously be used. Processes using high-speed mixer/granulators are disclosed, for example, in EP 340 013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever).
Liquid detergent compositions can be prepared by admixing the essential and optional ingredients thereof in any desired order to provide compositions containing components in the requisite concentrations. Liquid compositions according to the present invention can also be in compact form which means it will contain a lower level of water compared to a conventional liquid detergent.
Treatment
The treatment of the fabric with the material of the invention can be made by any suitable method such as washing, soaking or rinsing of the fabric.
Typically the treatment will involve a washing or rinsing method such as treatment in the main wash or rinse cycle of a washing machine and involves contacting the fabric with an aqueous medium comprising the material of the invention.

Unilever Home and Personal Care USA division of Conopco