The present invention provides a coating composition containing 1) a carbamate-functional resin having in its structure a hyperbranched or star polyol core, a first chain extension based on a polycarboxylic acid or anbydride, a second chain extension based on an epoxy containing compound, and having carbamate functional groups on the core, the second chain extension, or both; and 2) a second resin containing functional groups reactive with the carbamate groups on the carbamate-functional resin. In one embodiment, the coating compositions are used as a cloarcoat to be applied over a basecoat to form a composite coating. The compositions exhibit a combination of desirable properties, such as scratch and mar resistance, resistance to environmental etch, good intercoat adhesion, and high solids.

The present invention relates to carbamate-functional resins and their use in high solids coating compositions. More specifically it relates to carbamate functionalized star or hyperbranched polyols as reactive resins in coatings.
Coating compositions based on carbamate-functional acrylic polymers and aminoplast cross-linking agents are desirable as automotive topcoats because they have excellent durability, hardness, gloss, appearance, and resistance to environmental etch. As such, they are highly suitable for use as a clearcoat layer applied over a basecoat layer in a color plus clear composite coating.
A problem associated with curable coating compositions based on acrylic polymers containing pendant carbamate groups and aminoplast curing agents is that the compositions do not have particularly good intercoat adhesion. This problem presents itself when the compositions are used as clearcoats and composite color plus clear coatings, especially during repair procedures which involve applying the clear film forming composition to a flawed area of a previously applied color plus clear composite coating.
Another area for improvement in the use of carbamate-functional acrylic polymers with amino resins systems as cross-linkers is compatibility with waterborne basecoats. The waterborne basecoats contain amines used to salt the resin into water. During baking, the amine is released from the basecoat and travels through the clearcoat to the surface, where it is released into the atmosphere. The concentration of amine at the bottom of the clearcoat is greater than the concentration at the top, which sets up a pH gradient in the clearcoat. Because the cure rate is a function of the pH, a so called cure gradient forms in the clearcoat. This leads to an appearance defect known as wrinkling.
The curable carbamate-functional compositions are generally formulated with a low-imino amino resin so as to achieve high solids, which is desirable for economic and environmental reasons. If instead high-imino amino resins are used, the cure gradient is minimized along with the wrinkling. This is because the dependency on pH of the cure rate of a high-imino amino resin is not as great as that of a low-imino resin.
However, when high-imino resins are used, the solids content of the coating becomes unacceptably low. Thus, it would be desirable to provide a coating composition based on carbamate-functional resins and amino resin crosslinkers that have a combination of high solids and compatibility with waterborne basecoats. Preferably, such a composition would also exhibit improved intercoat adhesion.
U.S. Pat. No. 5,759,694 to Mayo has addressed the intercoat adhesion problem by providing a polyester made by copolymerizing a diol, optional triol, a hydroxyl functional and acidic functional material, and a polyacid, followed by reaction with a monoepoxide and carbamoylation. The polyester is combined with a carbamate-functional acrylic resin and an aminoplast to yield a film forming composition. Mayo does not directly address the problem of compatibility of the film forming composition with a waterborne basecoat.
U.S. Pat. No. 5,693,723 to Green describes a carbamate-functional resin prepared by reacting a compound having at least one hydroxyl group and one carboxyl group with an epoxy compound, and then carbamoylating the reaction product. High solids coating compositions are obtained, but there is no discussion of how to improve intercoat adhesion.
The present invention provides a coating composition containing
1) a carbamate-functional resin having in its structure a hyperbranched or star polyol core, a first chain extension based on a polycarboxylic acid or anhydride, a second chain extension based on an epoxy-containing compound, and having carbamate functional groups on the core, the second chain extension, or both; and
2) a second resin containing functional groups reactive with the carbamate groups on the carbamate-functional resin.
In one embodiment, the coating compositions are used as clearcoats applied over basecoats to form composite coatings. The compositions exhibit a combination of desirable properties, such as scratch and mar resistance, resistance to environmental etch, good intercoat adhesion, and high solids.
In another embodiment, the coating compositions also contain a carbamate-functional acrylic resin. In this embodiment, the carbamate-functional resin of the invention may act as a reactive diluent. Methods are also provided to synthesize the carbamate-functional resins of the invention.
The terms xe2x80x9ccarbamate groupxe2x80x9d, xe2x80x9ccarbamate-functionalxe2x80x9d, and the like, as used in connection with the present invention refer to a group having a structure:
in which R is H or alkyl, preferably R is H or alkyl of from 1 to about 8 carbon atoms, more preferably R is H or alkyl of from 1 to about 4 carbon atoms, and yet more preferably R is H. When R is H, the carbamate group is referred to herein as a primary carbamate group.
The carbamate-functional resin of the invention is based on a star or hyperbranched core and contains carbamate functionality. The carbamate functionality can be introduced onto the core by reacting the core with a compound containing a carbamate group and a functional group reactive with the hydroxyl groups on the core. Alternatively, it can be introduced by a series of extension steps with a polycarboxylic acid or anhydride and epoxy compound, followed by carbamoylation. The degree of carbamoylation and the number of extensions can be selected so as to obtain desirable properties of coatings prepared from the resin.
The carbamate-functional resins of the invention can be formulated with another resin having functional groups reactive with the carbamate groups to form curable coating compositions particularly useful as a topcoat or as a clearcoat component of a basecoat-clearcoat composite coating. The coating compositions of the invention can further contain a carbamate-functional acrylic resin.
The star core is a structure based on a star polyol. A star polyol is a monomeric polyol containing three or more primary or secondary hydroxyl groups. In a preferred embodiment, the star polyol has four or more hydroxyl groups. Examples of star polyols include, without limitation, glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tetrakis (2-hydroxyethyl)methane, diglycerol, trimethylolethane, xylitol, glucitol, dulcitol, and sucrose. Mixtures of star polyols may also form the star core of the carbamate-functional resin of the invention.
A hyperbranched core is a structure based on hyperbranched polyols. Hyperbranched polyols are prepared by the reaction of a first compound having two or more hydroxyl groups and a second compound having one carboxyl group and two or more hydroxyl groups. The first and second compounds can be reacted to form a first generation hyperbranched polyol. Alternatively, the second compound can be reacted with the first generation hyperbranched polyol to form a second generation and, if desired, subsequent generations. Preferably, a first generation or second generation hyperbranched polyol is used as the hyperbranched core of the carbamate-functional resin of the invention.
The first compound can suitably be an aliphatic, a cycloaliphatic, or an aromatic diol, triol, or tetrol, a sugar alcohol such as sorbitol and mannitol, dipentaerythritol, an xcex1-alkylglucoside such as xcex1-methylglucoside, or an alkoxylate polymer having a molecular weight of at most about 8,000 that is produced by a reaction between an alkylene oxide or a derivative thereof and one or more hydroxyl groups from any of the alcohols mentioned above. Mixtures of these can also be used as the first compound.
Diols suitable as the first compound include straight diols with 2-18 carbon atoms. Examples include, without limitation, 1,3-propanediol, 1,2-ethanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.
The diols can also be branched such as, for instance, dimethylolpropane, neopentyl glycol, 2-propyl-2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethylpentane-1,3-diol, trimethylhexane-1,6-diol, and 2-methyl-1,3-propanediol. Other suitable diols include, without limitation, diethylene glycol, triethylene glycol, polyethylene glycols, dipropylene glycol, tripropylene glycol and polypropylene glycols.
Cycloaliphatic diols such as cyclohexane dimethanol and cyclic formals of pentaerythritol such as, for instance, 1,3-dioxane-5,5-dimethanol can also be used.
Aromatic diols, for instance 1,4-xylylene glycol and 1-phenyl-1,2-ethanediol, as well as reaction products of polyfunctional phenolic compounds and alyklene oxides or derivatives thereof, can furthermore be employed. Bisphenol A, hydroquinone, and resorcinol may also be used.
Diols of the ester type, for example neopentylhydroxypivalate, are also suitable diols.
As substitute for a 1,2-diol, the corresponding 1,2-epoxide or an xcex1-olefin oxide can be used. Ethylene oxide, proplyene oxide, 1,2-butylene oxide, and styrene oxide can serve as examples of such compounds.
Suitable triols can contain three primary hydroxyl groups. Trimethylolpropane, trimethylolethane, trimethylobutane, and 3,5,5-trimethyl-2,2-dihydroxymethylhexane-1-ol are examples of this type of triols. Other suitable triols are those having two types of hydroxyl groups, primary as well as secondary hydroxyl groups, as for instance glycerol and 1,2,6-hexanetriol. It is also possible to use cycloaliphatic and aromatic triols and/or corresponding adducts with alkylene oxides or derivatives thereof.
Suitable tetrols for use as the first compound include, without limitation, pentaerythritol, ditrimethylolpropane, diglycerol and ditrimethylolethane. It is also possible to use cycloaliphatic and aromatic tetrols as well as corresponding adducts with alkylene oxides or derivatives thereof.
The second compound used to prepare the hyperbranched polyol can be a monofunctional carboxylic acid having at least two hydroxyl groups. Examples include, without limitation xcex1,xcex1-bis(hydroxymethyl)propionic acid (dimethylol propionic acid), xcex1,xcex1-bis(hydroxymethyl)butyric acid, xcex1,xcex1,xcex1-tris(hydroxymethyl)acetic acid, xcex1,xcex1-bis(hydroxymethyl)valeric acid, xcex1,xcex1-bis(hydroxyethyl)propionic acid or xcex1-phenylcarboxylic acids having at least two hydroxyl groups directly pendant to the phenyl ring (phenolic hydroxyl groups) such as 3,5-dihydroxybenzoic acid.
The hyperbranched polyols can be prepared by reacting the first compound and second compound under esterification conditions. The temperature of reaction is generally from 0 to 300xc2x0 C., preferably 50 to 280xc2x0 C., and most preferably 100 to 250xc2x0 C.
A first generation intermediate is prepared by reacting the first compound and second compound in an equivalent molar ratio of hydroxyls on the first compound to carboxyl groups on the second compound of between about 1:2 and about 2:1. Preferably the equivalent ratio will be from about 1:1.5 to about 1.5: 1, and even more preferably from about 1:1.2 to about 1.2:1.
The functionality and polydispersity of the first generation intermediate, and of any subsequent generation, depend on the equivalent ratio of hydroxyl groups to carboxyl groups of the reactants in each step. The functionality of the hyperbranched polyol, whether first generation or subsequent generation, should be four hydroxyl groups or greater. Hyperbranched polyols with a wide range of polydispersities are useful. It is preferred that the polydispersity be less than about 2.5, preferably less than about 2.0, and most preferably less than about 1.8.
To make the resins of the invention, the core polyol, either star or hyperbranched as described above, is next reacted with a polycarboxylic acid or anhydride to form a first chain extension containing an ester linkage and a free carboxyl group. Preferred as the polycarboxylic acid or anhydride are cyclic carboxylic anhydrides. Anhydrides are advantageous for this step because the ring-opening esterification is faster than reaction of remaining hydroxyl groups on the core polyol with the carboxyl group liberated by the ring opening reaction. As a consequence the first chain extension is a half acid ester with little polymerization or polyester formation.
Suitable anhydrides include, without limitation, anhydrides of dicarboxylic acids with carboxyl groups on adjacent carbons. The anhydrides can be aliphatic, cycloaliphatic, or aromatic. Examples include without limitation, maleic anhydride, succinic anhydride, phthlalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and trimellitic anhydride. Other anhydrides useful in the invention include, without limitation, adipic anhydride, glutaric anhydride, malonic anhydride, and the like.
The reaction of the polycarboxylic acid or anhydride with the core polyol results in formation of a first intermediate that has carboxyl functionality and may contain some primary or secondary hydroxyl groups that result from any unreacted hydroxyl groups on the core polyol.
The stoichiometry is chosen so that at least one primary hydroxyl group of the core polyol reacts with the polycarboxylic acid or anhydride. Preferably at least two hydroxyl groups on the core polyol will be reacted. In some embodiments the molar ratio of hydroxyl on the core polyol to carboxyl group on the polycarboxylic acid or anhydride will be approximately 1:1, so that essentially every hydroxyl group on the core polyol is esterified.
The first intermediate, which contains at least one carboxyl group and optionally has primary or secondary hydroxyl groups as noted above, is next reacted with a compound containing an epoxide group to form a second intermediate having a chain extension based on an epoxide-containing compound.
A wide variety of epoxide containing compounds may be used in the practice of the present invention. Epoxides are well-known in the art, and may be characterized by the general formula:
where R1, R2, R3 and R4 are each independently hydrogen (with the proviso that at least one of R1-R4 is other than hydrogen), an organic radical, which may be polymeric or non-polymeric and may contain unsaturation and/or heteroatoms, or one of R1 or R2 together with one of R3 or R4 may form a cyclic ring, which may contain unsaturation and/or heteroatoms.
Useful epoxides can be prepared from monofunctional alcohols, e.g., butanol and hexanol, by reaction with an epihalohydrin (e.g., epichlorohydrin) or by reaction of an allyl group with peroxide. For example, a monoepoxide can be prepared by reacting a mono-alcohol or mono-acid with an epihalohydrin or a monounsaturate with peroxide.
In one preferred embodiment, the epoxide is a monoepoxide preferably an epoxy ester, also known as a glycidyl ester. Glycidyl esters can be prepared by reacting a monofunctional carboxylic acid (e.g., octanoic acid, benzoic acid, benzylic acid, cyclohexane carboxylic acid) with an epihalohydrin (e.g., epichlorohydrin) under conditions well-known in the art. In a preferred embodiment, the monofunctional carboxylic used to produce the glycidyl esters is a branched neo-acid such as, without limitation, neodecanoic or neononanoic acid. Glycidyl esters are commercially available, e.g., as Cardura(copyright) E from Shell Oil Company, Glydexx(copyright) N-10 from Exxon, or Araldite(copyright) PT910 from Ciba-Geigy. Glycidyl esters may be described by the formula:
wherein R is a hydrocarbon group of from 1 to about 40 carbon atoms, preferably from about 1 to about 20 carbon atoms, and most preferably from about 1 to about 12 carbon atoms. This hydrocarbon group may be substituted, as is known in the art. In a preferred embodiment.
Another useful class of monoepoxides is glycidyl ethers. Glycidyl ethers can be prepared by the reaction of monofunctional alcohols (e.g., n-butanol, propanol, 2-ethylhexanol, dodecanol, phenol, cresol, cyclohexanol, benzyl alcohol) with an epihalohydrin (e.g., epichlorohydrin). Useful glycidyl ethers include the glycidyl ether of 2-ethylhexanol, the glycidyl ether of dodecanol, the glycidyl ether of phenol, and the like. These compounds are commercially available under the Erisys(copyright) product family from CVC Specialties.
The reaction of the epoxide compound with the first intermediate is preferably carried out without catalyst. In this case, the epoxide group of the epoxide-containing compound reacts faster with the carboxyl group than with any primary or secondary hydroxyl groups that may be present on the first intermediate. Therefore, a relatively clean chain extension is achieved to form a second intermediate that contains secondary hydroxyl groups resulting from ring opening of the epoxide, as well as any primary or secondary hydroxyl groups that remained unreacted in the formation of the first intermediate, above.
Preferably the epoxy containing compound is reacted in a molar ratio of about 1:1 with respect to carboxyl groups on the first intermediate. However, if carboxyl groups are desired in the final product (for example for salting with amines to provide a water dispersible coating), an excess of carboxyl functional first intermediate may be used.
The next step in preparing the resin of the invention is to add carbamate groups to the second intermediate. As discussed above, the second intermediate contains at least secondary hydroxyl groups resulting from the ring opening of the epoxy containing compound. It may also contain primary or secondary hydroxyl groups on the core, if less than a molecular equivalent of polycarboxylic compound was used to react with the core polyol.
Techniques for adding carbamate groups to the second intermediate are known in the art and are described, for example, in P. Adams and F. Barren xe2x80x9cEsters of Carbamate Acidxe2x80x9d, Chemical Review, Vol. 65 (1965). For example, a carbamate group may be added to the second intermediate by reacting the second intermediate with phosgene and then ammonia to form a compound having primary carbamate groups, or by reaction of the second intermediate with phosgene and then a primary amine to form a compound having secondary carbamate groups. Alternatively, the second intermediate may be reacted with one or more ureas to form a compound with secondary carbamate groups (i.e., N-alkyl carbamates). This reaction is accomplished by heating a mixture of the second intermediate and urea. Another technique is the reaction of the second intermediate with a monoisocyanate, for example methylisocyanate, to form a compound with secondary carbamate groups.
The second intermediate can be reacted with a carbamate compound to form the carbamate-functional second intermediate. In one embodiment, the carbamate compound is cyanic acid, which may be formed by the well-known reaction of the thermal decomposition of urea or by other methods, such as described in the U.S. Pat. Nos. 4,389,386 or 4,364,913. In another embodiment, the carbamate compound is a compound comprising a carbamate group. In this embodiment, the reaction between the second intermediate and the carbamate compound is believed to be a transesterification between the hydroxyl groups on the second intermediate and the carbamate ester on the carbamate compound. The carbamate compound can be any compound having a carbamate group capable of undergoing a transesterification with the hydroxyl groups on the second intermediate. These include, without limitation, methyl carbamate, butyl carbamate, propyl carbamate, 2-ethylhexyl carbamate, cyclohexyl carbamate, phenyl carbamate, hydroxypropyl carbamate, hydroxyethyl carbamate, and the like. Useful carbamate compounds can be characterized by the formula:
wherein R1 is substituted or unsubstituted alkyl (preferably of 1-8 carbon atoms) and R2 is H, substituted or unsubstituted alkyl (preferably of 1-8 carbon atoms, substituted or unsubstituted cycloalkyl (preferably of 6-10 carbon atoms), or substituted or unsubstituted aryl (preferably of 6-10 carbon atoms). Preferably, R2 is H.
The transesterification reaction between the second intermediate and the carbamate compound can be conducted under typical transesterification conditions, e.g., temperatures from room temperature to 150xc2x0 C. with transesterification catalysts such as calcium octoate, metal hydroxides (e.g., KOH), Group I or II metals (e.g., Na, Li), or metal carbonates (e.g., K2CO3). These may be enhanced by use in combination with crown ethers, metal oxides (e.g., dibutyltin oxide), metal alkoxides (e.g., NaOCH3, Al(OC3H7)3), metal carboxylic acid salts (e.g., stannous octoate, calcium octoate), protic acids (e.g., H2SO4), MgCO3, or Ph4SbI. The reaction may also be conducted at room temperature with a polymer-supported catalyst such as Amberlyst-15(copyright) (Rohm and Haas) as described by R. Anand, Synthetic Communications, 24(19), 2743-47 (1994), the disclosure of which is incorporated herein by reference.
In another embodiment, the carbamate compound comprises a molecule with an isocyanate group and a carbamate group. Such a molecule can be prepared for example by reacting an organic diisocyanate with a difunctional compound that contains, in addition to a carbamate group, a reactive hydroxyl or amino group. The difunctional molecule can be, for example, a hydroxycarbamate that is the reaction product of ammonia or a primary amine with an alkylene carbonate, which is well known in the art.
Diisocyanates suitable for reaction with the difunctional compound to form the carbamate compound include aliphatic or cycloaliphatic diisocyanates, such as 1,11-diisocyanatoundecane, 1,12-diisocyanatododecane, 2,2,4- and 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,3-diisocyanatocyclobutane, 4,4xe2x80x2-bis-(isocyanatocyclohexyl)methane, hexamethylene diisocyanate (HMDI), 1,2-bis-(isocyanatomethyl)cyclobutane, 1,3- and 1,4-bis-(isocyanatomethyl)cyclohexane, hexahydro-2,4- and/or -2,6-diisocyanatotoluene, 1-isocyanato-2-isocyanatomethyl cyclopentane, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, 2,4xe2x80x2-dicyclohexylmethane diisocyanate, and 1-isocyanato-4(3)-isocyanatomethyl-1-methyl cyclohexane.
Other suitable diisocyanates include aromatic diisocyanates, such as, without limitation, tetramethyl-1,3- and/or -1,4-xylylene diisocyanate, 1,3- and/or 1,4-phenylene diisocyanate, 2,4- and/or 2,6-toluene diisocyanate, 2,4- and/or 4,4xe2x80x2-diphenyl-methane diisocyanate, 1,5-diisocyanato naphthalene, p-xylylene diisocyanate and mixtures thereof.
Suitable diisocyanates are also understood to include those containing modification groups such as biuret, uretdione, isocyanurate, allophanate and/or carbodiimide groups, as long as they contain two isocyanate groups.
The carbamate compound can be prepared by converting one of the isocyanate groups of the diisocyanate to a carbamate group by reacting the diisocyanate with the difunctional compound. To make it easier to convert just one isocyanate group, it is preferred to use a diisocyanate compound that has isocyanate groups of different reactivity. In this situation, one of the isocyanates will react preferentially with the difunctional compound.
Examples of diisocyanates having isocyanate groups of different reactivity include, without limitation, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (also known as isophorone diisocyanate), 1-isocyanato-2-isocyanatomethylcyclopentane, 1-isocyanato-1-methyl-4(3)-isocyanatomethylcyclohexane, 2,3-toluenediisocyanate, and 2,4-toluenediisocyanate. In a preferred embodiment, isophorone diisocyanate is used.
The product of such a reaction is a compound with an isocyanate group and a carbamate group. As an illustration, when the diisocyanate is isophorone diisocyanate, and the difunctional molecule is a reaction product of ammonia and propylene carbonate, one isomer of the carbamate compound can be represented by the idealized structure
The idealized structure illustrates the preferential reaction of the difunctional compound with the primary isocyanate on isophorone diisocyanate. The actual product of such a reaction statistically will include some product substituted on the secondary isocyanate, as well as disubstitued diisocyanate and some unreacted diisocyanate. The product can then be reacted with the second intermediate to provide the resin of the invention.
The resin of the invention can contain carbamate groups on the core, on the second chain extension, or both. It follows from the discussion above that any carbamate groups on the core will be attached to primary or secondary hydroxyl carbamate groups, while any carbamate groups on the second chain extension will be attached to secondary hydroxyl groups.
In one embodiment, the presence of at least some free hydroxyl groups on the carbamate-functional resin is preferred to increase intercoat adhesion by allowing for hydrogen bonding. For example, all or a portion of the primary hydroxyl groups on the second intermediate may be selectively carbamoylated, leaving unsubstituted secondary hydroxyl groups on the resin of the invention. The reaction rate of a primary hydroxyl group with the carbamate compound is greater than that of a secondary hydroxyl group. Selective carbamoylation of the primary groups is straightforward because the carbamate compound reacts preferentially with the primary hydroxyl group.
On the other hand, in another embodiment, all of the available hydroxyl groups on the second intermediate are converted to carbamate groups. This is desirable when greater crosslinking density is desired in the resin.
In another embodiment, the carbamate-functional resin of the invention can be prepared by direct carbamoylation of the core polyol itself. The primary hydroxyl groups of the core may be converted to carbamate functionality by any of the techniques noted above. To make the resin soluble in organic solvents, it is preferred that at least one of the primary hydroxyl groups on the core polyol be converted by reaction with a second compound having an isocyanate group and a carbamate group. Such compounds are prepared from organic diisocyanates as discussed above. Preferably, most or all of the primary or secondary hydroxyl groups on the core polyol are reacted with the second molecule to form a highly carbamate-functional resin.
In a non-limiting example, a hyperbranched core polyol is made by reacting trimethylolpropane and dimethylol propionic acid in a 1:3 molar ratio such that there are equal equivalents of hydroxyl groups on the trimethylolpropane to carboxyl groups on the dimethylolpropionic acid. A core polyol results that has six primary hydroxyl groups. The core polyol is reacted with a carbamate-functional isocyanate molecule, which is in turn prepared by the reaction of isophorone diisocyanate with a hydroxy carbamate.
High solids coating compositions can be prepared by combining the carbamate-functional resin (A) of the invention with a compound (B) containing a plurality of functional groups that are reactive with the carbamate groups on the carbamate-functional resin. Such reactive groups include siloxane, silane, and anhydride groups, as well as active alkylol or alkoxyalkyl groups on aminoplast crosslinking agents or on other compounds such as phenol/formaldehyde adducts.
Examples of compounds (B) include, without limitation, melamine formaldehyde resin including monomeric or polymeric melamine resin and partially or fully alkylated melamine resin, urea resins (e.g., methylol ureas such as urea formaldehyde resin and alkoxy ureas such as butylated urea formaldehyde resin), N-methylol acrylamide emulsions, isobutoxy methacrylamide emulsions, polyanhydrides (e.g., polysuccinic anhydride), and siloxanes or silanes (e.g., dimethyldimethoxy silane). Aminoplast resins such as melamine formaldehyde resin or urea formaldehyde resin are especially preferred. Also useful are aminoplast resins where one or more of the amino nitrogens is substituted with a carbamate group for use in a process with a curing temperature below 150xc2x0 C., as described in U.S. Pat. No. 5,300,328.
Aminoplast resins useful as compound B in the coating compositions of the invention can be highly alkylated or partially alkylated amino resins formed by the reaction of an amine with an aldehyde. Preferred amino resins include those which are reaction products of amines such as urea or melamine with an aldehyde such as formaldehyde. Such aminoplast resins are characterized by a degree of alkylation, degree of self crosslinking or a degree of polymerization, alkylol content, and imino content. Imino groups and amino groups on an aminoplast resin arise from the incomplete reaction of the aldehyde with the amine. Aminoplast resins are characterized as low-imino if the imino content is less than about 10%, that is, if less than about 10% of the functional groups on the resin consist of imino or amino groups. Commonly, low-imino aminoplast resins contain less than 5% imino content. On the other hand, if the imino content of an aminoplast resin is greater than about 10%, it can be characterized as high-imino. More commonly, the imino content of a high imino resin is 15% or higher. Commercial high imino melamine resins, for example, are available with up to about 35% imino content.
In another embodiment, the coating compositions of the invention can further comprise a carbamate-functional acrylic resin. Carbamate-functional resins are known in the art to be useful in clearcoat compositions. They include a plurality of carbamate functional groups on an acrylic backbone. The carbamate groups are introduced into the resin by transcarbamation of a hydroxyl-functional resin following polymerization of acrylic monomers, and can also be prepared from acrylic monomers containing carbamate functional groups. Such carbamate-functional acrylic resins are described, for example, in U.S. Pat. No. 5,605,965 to Rehfuss et al., the disclosure of which is hereby expressly incorporated by reference.
In this embodiment, the coating compositions of the invention comprise two carbamate-functional resins and at least one compound containing a plurality of functional groups reactive with the carbamate groups. The carbamate-functional acrylic resin, if present, makes up from between about 5 and about 95% by weight of the total carbamate resin in the composition.
A solvent may optionally be utilized in the coating composition used in the practice of the present invention. The coating composition according to the present invention can be applied without solvent. However, in many cases, it is desirable to use a solvent in the coating composition as well. This solvent should act as a solvent with respect to both the carbamate-functional resin or resins as well as the component (B). In general, depending on the solubility characteristics of components (A) and (B), the solvent can be any organic solvent and/or water. In one preferred embodiment, the solvent is a polar organic solvent. More preferably, the solvent is a polar aliphatic solvent or polar aromatic solvent. Still more preferably, the solvent includes a ketone, ester, acetate, aprotic amide, aprotic sulfoxide, or aprotic amine. Examples of useful solvents include, without limitation, methyl ethyl ketone, methyl isobutyl ketone, amyl acetate, ethylene glycol butyl ether-acetate, propylene glycol monomethyl ether acetate, xylene, N-methylpyrrolidone, or blends of aromatic hydrocarbons. In another embodiment, the solvent can be water or a mixture of water with co-solvents.
The coating composition used in the practice of the invention may include a catalyst to enhance the cure reaction. For example, when aminoplast compounds, especially monomeric melamines, are used as component (B), a strong acid catalyst may be utilized to enhance the cure reaction. Such catalysts are well-known in the art and include, for example, p-toluenesulfonic acid, dinonylnaphthalene disulfonic acid, dodecylbenzenesulfonic acid, phenyl acid phosphate, monobutyl maleate, butyl phosphate, and hydroxy phosphate ester. Other catalysts that may be useful in the composition of the invention include Lewis acids, zinc salts, and tin salts.
Additional agents, for example surfactants, fillers, stabilizers, wetting agents, dispersing agents, adhesion promoters, UV absorbers, HALS, etc., may be incorporated into the coating composition. While the agents are well-known in the prior art, the amount used must be controlled to avoid adversely affecting the coating characteristics.
Coating compositions can be coated on the article by any of a number of techniques well-known in the art. These include, for example, spray coating, dip coating, roll coating, curtain coating, and the like. The coatings can be cured at about 200xc2x0 F. to 350xc2x0 F. for a period of about 10 to 60 minutes.
In one preferred embodiment, the coating composition according to the invention is preferably utilized in a high-gloss coating and/or as the clearcoat of a composite color-plus-clear coating. High-gloss coatings as used herein are coatings having a 20xc2x0 gloss (ASTM D523-89) or a DOI (ASTM E430-91) of at least 80. In other preferred embodiments, the coating composition may be utilized to prepare high-gloss or low-gloss primer or enamel coatings.
When the coating composition according to the invention is used as the clearcoat of a composite color-plus-clear coating, the pigmented basecoat composition may be any of a number of types well-known in the art, and does not require explanation in detail herein. Polymers known in the art to be useful in basecoat compositions include acrylics, vinyls, polyurethances, polycarbonates, polysters, alkyds, and siloxanes. Preferred polymers include acrylics and polyurethanes. In one preferred embodiment of the invention, the basecoat composition also utilizes a carbamate-functional acrylic polymer. Basecoat polymers are preferably crosslinkable, and thus comprise one or more type of crosslinkable, functional groups. Such groups include, for example, hydroxy, isocyanate, amine, epoxy, acrylate, vinyl, silane, and acetoacetate groups. These groups may be masked or blocked in such a way so that they are unblocked and available for the cross-linking reaction under the desired curing conditions, generally elevated temperatures. Useful cross-linkable functional groups include hydroxy, epoxy, acid, anhydride, silane, and acetoacetate groups. Preferred cross-linkable functional groups include hydroxy functional groups and amino functions groups.
Basecoat polymers may be self cross-linkable, or may require a separate cross-linking agent that is reactive with the functional groups of the polymer. When the polymer comprises hydroxy functional groups, for example, the crosslinking agent may be an aminoplast resin, isocyanate and blocked isocyanates (including isocyanurates), and acid or anhydride functional cross-linking agents.
The carbamate functional resins and coating compositions of the invention have been described above with respect to preferred embodiments. The following examples give further non-limiting descriptions of the use of the carbamate-functional resins in the coatings of the invention.

Carbamate-functional resins and their use in high solids coating compositions


An apparatus for inspecting a disk-like object comprising at least one first module for inspecting a surface of the disk-like object and at least one second module insertable in the apparatus. The at least one second module is arranged to inspect a different element of the disk-like object than the surface of the disk-like object.

With the optical detection of defects in a semiconductor wafer, it is also essential to take the systematic defects into account which occur due to thickness variations when photoresist is applied to the wafer. Optical devices are particularly suited to inspect the surface of wafers. As disclosed in EP 455 857 the inspection of the surface can be done, for example, by evaluating light beams reflected from the surface of the wafer.
To find macroscopic defects on semiconductor wafers, dies on the same wafer are compared in a so-called die-to-die method. Due to the use of high-precision processes, extremely uniform structures are formed on the wafer. This is why the images taken from the dies will also be identical if there are no process malfunctions which would negatively affect the formation of the dies. Any differences between two images could therefore be interpreted as a defect. A method of this type has been described, for example, in US 2004/0105578 A1. However, the comparison can only be made for such areas on the wafer which have the same sort of dies. As a result this approach is only suitable for areas with so-called productive dies. Other areas on the wafer comprising, for example, test fields or areas without structure or situated near the edge of the wafer cannot be inspected in this way. It has been found, however, that important information can be derived from these areas which can enable or facilitate an early detection of defects. Problems with the application of photoresist in particular near the edge of the wafer can be detected at an early stage because it is here that such problems appear first, and theses problems propagate from the edge towards the center as the production continues. If these areas are not inspected, the defects cannot be detected. As a result, these defects will later also occur on the productive dies which may lead to the wafer being useless.
An apparatus for inspecting a defective wafer edge with diffracted light is disclosed, for example, in JP 09269298 A. An elliptical reflector is provided having its first focus coincide with the wafer edge, and a detector in its second focus. The wafer edge is illuminated by means of a light source producing parallel coherent light directed towards the edge in the same vertical orientation as the wafer and vertical to a virtual tangent on the wafer edge. The 0-th order of the diffracted light is filtered out by an absorber plate. The diffracted light is focused by the elliptical reflector in the second focus and received there by means of a detector. However, the apparatus is realized as a separate device and cannot be integrated into an apparatus for the integral inspection of a disk-like object.
Further, JP 11351850 discloses an apparatus based on the same principle as JP 09269298 A. It is only characterized by additional sensors mounted in the vicinity of the wafer edge, and by differentiating between defects having a random orientation and defects parallel to the surface of the wafer, i.e., transverse to the rotation direction.
U.S. Pat. No. 6,587,193 further discloses inspecting the surface of a wafer wherein an illumination is selected which scans the wafer in the form of a line. The illumination line is guided across the surface of the wafer in such a way that a two-dimensional image can be created.
From U.S. Patent Application 2003/0202178 A1 a method and apparatus for inspecting a wafer are known. Herein an illumination is radiated onto the wafer in such a way that an edge of the wafer is irradiated. This serves to scan the edge of the wafer, the result of which can then be processed by an image processing unit. Defects of the wafer can be detected by comparing the acquired edge image with a stored comparison image.
U.S. Pat. No. 5,359,407 discloses an apparatus wherein the top and bottom surfaces of a flat disk are alternately partially scanned by a light beam. In contrast to the case where the top and bottom surfaces are scanned simultaneously, diffracted light from one side is prevented from getting into the detector of the other side. Each detector is always uniquely associated with one side. To scan the two sides, either two laser beams are used, or one laser beam is subdivided into two partial beams. These partial beams are moved by one or more rotary mirrors within an angular area and redirected by deflection mirrors to each of the surfaces in such a way that the area of the wafer to be inspected is crossed by the light dot of the laser beam.
U.S. Patent Application 2004/086171 discloses an apparatus and method for inspecting a substrate. The automatic apparatus comprises a first stage for carrying the substrate and a first imaging device records an image of the circumferential area of the substrate. Further, a second stage for carrying the substrate is provided, wherein a second imaging device is provided to record an image of the substrate. A plurality of individual systems is combined in one unit, which leads, however, to an effective increase in the footprint of the entire system.
U.S. Patent Application 2004/095575 discloses an apparatus for inspecting a wafer. With the aid of a first imaging device an image can be recorded of the wafer surface. A second imaging device is provided to image the top of the edge area, the wafer edge, and the bottom of the edge area. The second imaging device is mounted on a corresponding support structure of the apparatus.
U.S. Patent Application 2005/036671 discloses an apparatus for edge inspection. The wafer is placed on a stage, and a plurality of cameras is arranged in the area of the wafer edge, from which one camera images the top of the wafer edge and the other camera images the wafer edge.
No single prior art apparatus is able to perform a full inspection of a disk-like object.

Apparatus for inspecting a disk-like object


The purified strain of Lactobacillus acidophilus CNCM/I-1492 (L.a. 1492) when administered alone or in combination with another Lactobacillus acidophilus (L.a.) strain and Lactobacillus casei (L.c.) strain, has a beneficial effect on the cholesterol blood level in mammals. It also strenghtens the immune system, facilitates the absorption of nutrients and stimulates the intestinal flora. Such strains also neutralize side effects caused by antibiotics. The invention concerns the specific strain L.a. I-1492, a ferment comprising L.a. I-1492, L.a. and L.c. strains, a dairy product obtained by this ferment and a method of manufacturing the dairy product.

The present invention concerns a purified strain Lactobacillus acidophilus identified as CNCM/I-1492 (hereinafter called L.a. I-1492), the microorganism from this strain, a lactic ferment comprising this strain, a process for making dairy products using this ferment, and the dairy products obtained by this process and containing at least 500 million per gram of Lactobacillus acidophilus (including the L.a. I-1492 strain) or 380 million/gram of L.a. I-1492.
The invention also concerns the use of a ferment comprising the strain Lactobacillus acidophilus CNCM/I-1492 and of a dairy product containing the same in the pharmaceutical field for reducing the level of cholesterol in the blood of a mammal.
Yogurts are fermented dairy products obtained by fermentation of different lactic bacterias with milk. The most widely used milk is cow""s milk. These lactic bacterias (mainly Streptococcus thermophilus and Lactobacillus bulgaricus) are foreign bodies to the human intestinal flora and are not implanted in the digestive system during consumption of these dairy products.
Other lactic bacterias are present in their natural state in the human digestive system. It seems that the presence of such bacterias are beneficial and helpful in particular to improve the absorption of food while maintaining the equilibrium in the intestinal flora. Such other bacterias in particular are Lactobacillus casei and Lactobacillus acidophilus.
The dairy products containing such bacterias are of particular interest inasmuch as they allow better digestion and provide an easier absorption of calcium when the latter is in the presence of moderate amounts of lactose. Indeed, during fermentation, milk protein and sugar are hydrolyzed, thereby facilitating hydrolisation of minerals such as calcium, iron essential to their absorption.
It has also been demonstrated that the ingestion of a fermented milk containing Lb Acidophilus alone increase the phagocytes activities thereby stimulating non specific defense of the host.
Furthermore, the consumption of fermented milk Lb casei and milk Lb acidophilus has been found effective to rapidly reduce acute diarrhea in humans. Lb acidophilus has also been found to have a healing effect on other gastric-intestinal related problems such as diverticulitis, food poisoning, abnormal fermentation.
However, perfecting such products is extremely difficult inasmuch as these bacterias naturally present in humans are not easily given to rapid production of dairy products having a pleasant taste and texture.
Furthermore, it is known that the performance of combined strains in a same ferment is unpredictable because of the interactions between the strains. Hence the performance and properties of a ferment can be significantly different from the performance and properties of the pure strains of which the ferment is composed.
It has now been, surprisingly, discovered that the Lactobacillus acidophilus I-1492 strain, or L.a. I-1492, has not only a beneficial effect on digestion and the equilibrium of the intestinal tract, but also has a major pharmaceutical effect allowing the reduction of the cholesterol level in the blood of mammals, and more particularly humans.
This effect is particularly remarkable when the strain L.a. I-1492 is combined with some lactic bacterias in a lactic ferment. A thorough study of these products has revealed, in a totally surprising and unexpected way, that fermented dairy products obtained from such ferment display therapeutic properties which reduce the amount of cholesterol in the blood. The main factor seems to evidently be due to the presence of a high concentration of the strain L.a. I-1492 since such an effect has not been established for other yogurts and/or lactic bacterias. The combination of lactic bacterias which compose the ferment according to the invention, allows an increase and acceleration of the development of the strain L.a. I-1492 during production of the fermented dairy product. Furthermore, it is very likely that this ferment creates a synergy and thereby achieves the production of a fermented dairy product having improved therapeutic results as compared to the dairy products obtained with the L.a. I-1492 strain alone.
The present Invention concerns a purified strain Lactobacillus acidophilus I-1492 (L.a. I-1492) and the microorganism from this strain.
This strain can used in a lactic ferment, which is also an object of the invention, comprising a mixture of the following lactic strains:
L.a. I-1492
at least one other Lactobacillus acidophilus strain; and
at least one Lactobacillus casei strain.
The latter two strains may be of commercial origin and can be purchased from manufacturers of lactic ferments. For example, the commercial Lactobacillus acidophilus strain that is used in the ferment of the present invention may be the one sold under the trademark RP Texel by Rhxc3x4ne-Poulenc or the one sold under the trademark L.a. RO-52 by Rosell. The commercial Lactobacillus casei strain may be the one sold under the trademark E2AL by Rhxc3x4ne-Poulenc.
Another object of the invention is a fermented lactic product of the yogurt type obtained by fermentation of the strain or of the lactic ferment according to the invention, with a dairy compound.
A further object of the invention is a method of manufacturing a fermented dairy product by the fermentation of the ferment according to the invention, said product having the texture of a yogurt.
A further object of the invention is the use of such fermented dairy product in the stimulation of the immune system for curing sore throat, flu, sinusitis and urinary infection. This same fermented dairy product has also been found to be useful in treating gastric-intestinal related diseases and infections.
Still a further object of the invention is the use of the above dairy products to reduce the cholesterol blood level in mammals, especially humans, and a method of medical treatment comprising the ingestion of a dairy product according to the invention.
The invention as well as its advantages will be better understood upon reading the following non-restrictive description, and by referring to the enclosed drawings.
The purified Lactobacillus acidophilus strain I-1492 according to the invention was filed on Nov. 15, 1994 in the National Collection of Microorganism Cultures (25, Rue du Dr. ROUX, F-75724 Paris Cedex 15) according to the provisions of the Budapest Treaty.
The physiological, chemical and biochemical characteristics of the acidophilus strains that may be used in the ferment according to the invention are shown in tables 1 and 2. It has been found that the L.a. I-1492 strain present chemical, biochemical and physiological characteristics similar to those of the other L.a. strains. As a matter of fact, the L.a. I-1492 strain differs from the others only in that it degrades cholesterol more efficiently.
The fermenting profile for the L.a. strains which include the L.a. I-1492 strain is shown in table 3.
The chemical, biochemical and physiological characteristics of the casei strain which can be used in the ferment according to the invention in combination with the L.a. I-1492 strain, are compiled in tables 4 and 5.
The fermenting profile of the casei strain is shown in table 6.
A dairy product according to the present invention can be obtained by fermenting the ferment of the invention in a milk-based medium. For this purpose, the following process may be used.
Firstly, the L.a. I-1492, acidophilus and casei strains are incubated in a MRS type fermentation medium under 10% of CO2 according to a standard program comprising several steps. The recombined lacteal base which is partially lactose-free and degassed is pasteurized for 1,5 minutes at 95xc2x0 C. and inoculated at 10%. Finally, it is incubated according to the following program:
1) the L.a. I-1492 strain: 2 hours at 37xc2x0 C. under 10% CO2;
2) the acidophilus strain: 2 hours at 37xc2x0 C.; and
3) the casei strain: 1 hour at 37xc2x0 C.
The product is then co-fermented in an anaerobic atmosphere and medium for 15 hours at 37xc2x0 C. (degassing under CO2).
In order to realize the invention, any acidophilus and casei strains may be used as long as they present no health risk. Preferably, the following acidophilus strain should be used: RP Texel(trademark) by Rhxc3x4ne-Poulenc and L.a. RO-52(trademark) by Rosell. The commercial casei E2AL(trademark) by Rhxc3x4ne-Poulenc is preferably used. The proportions of L.a. I-1492, acidophilus and casei cultured strains, are respectively about 70/20/10. These proportions may evidently be somewhat varied. Nevertheless, the total concentration of Lactobacilli acidophilus (including those obtained from L.a. I-1492 strains) which is present in the dairy product once fermented, must be at least equal to 500*106/g and the concentration of L.a. I-1492 must be at least 380*106/g.
Although total amino acid content is similar to milk, free amino acid are significantly higher. The level of peptides comprised in the fermented dairy product, having a molecular weight between 1000 and 5000 Da. is around 30% and the level of small peptides having less than 10 residues is approximately 15%. It is known that such levels of peptides fortify, in a surprising way, the immune and digestive systems.
In the fermented dairy product thus obtained, the dairy proteins are disintegrated into peptides whose size may be more or less large, allowing for an easier digestion of the product. Indeed, subject allergic to milk proteins were able to digest the fermented dairy product thus obtained. Once the fermented dairy product is manufactured, it is thereafter refrigerated and must be consumed before it deteriorates. Generally, the consumption of the same must take place within a period of 60 to 120 days.
A dairy product according to the invention has been commercialized by the applicant, Bio-K PLUS International Inc. (whose address is: 635 Victoria, Westmount, H3Y 2R9, CANADA) since Jun. 2, 1996, under the trade-mark Bio K+. However, the ferment of the present invention, which comprises the L.a. I-1492, acidophilus and casei strains has never been disclosed. Nor have the specific purified strain L.a. I-1492 and method of manufacturing the commercialized Bio K + product been disclosed. As it may be appreciated, a man skilled in the art would not , with the commercialized Bio K+ product at hand, be able to reproduce the same product.
The applicant has also suprisingly found that the fermented dairy product according to the invention has a stimulation effect on the immune system and is thereby effective for treating various inflammatory reactions and/or infectious diseases such as colds, sinusitis, urinary infections. The recommended treatment is a dose of 100 g per day of the fermented dairy product for a period of 10 to 60 days depending on the case. Furthermore the fermented dairy product neutralizes side effects caused by antibiotics.
The fermented dairy product of the invention has also been found to have significant effect in treating diseases and infections related to the intestinal tract such as diarrhea, diverticulitis, mega-colon, Crohn disease. Indeed, the applicant has found that daily consumption of the dairy product of the invention eliminates most cases of the above-mentioned diseases.
Furthermore, the fermented dairy product of the present invention contains a fair amount of folic acid and vitamin B12 which was produced during fermentation of the lactic culture. As a result, consumption of such product resulted in fast recuperation time in subjects whom regularly exercise. This observation is especially true for older individuals. As a matter of fact, 8 out of 10 people consuming the product on a daily basis said they felt better.
The fermented dairy product according to the invention may also be used for the treatment of high blood levels of cholesterol. The recommended treatment consists of a dose of 100 g per day for a period of 30 to 60 days.
The effect of this dairy product on the level of cholesterol in the blood was tested on a group of 14 patients to whom was prescribed a dose of 100 g per day for a period of, depending on the case, 30 to-60 days. The results of these tests are shown in the following charts where the total cholesterol blood level (CHO total) present in the blood is indicated. Hence, these tests reveal that upon regular intake during a period of 60 days, the total cholesterol level failed from between 7 to 22% and that the xe2x80x9clow density levelxe2x80x9d (LDL) failed from between 9 to 25%. Furthermore, the level of triglycerides (TRIGLY) drops from between 28 to 43%. It can be seen that after 60 days of treatment, certain individuals recover a normal level of CHO/HDL (High density level) ratio, that is, a level comprised between 3.2 to 4.4 or of LDL/HDL ratio (that is, inferior to 3.8 for people aged 30 and over).

Lactic ferment comprising a particular strain of lactobacillus acidophilus and use thereof


The present invention relates to the use of modafinil and isomers thereof for correcting psychosocial life disturbances due to vigilance disorders observed during the evolution of myopathies.

The present invention relates to a novel therapeutic use of modafinil and derivatives thereof.
Modafinil, or benzhydrylsulphinylacetamide, is a compound of formula:
This compound and its therapeutic use as an active agent on the central nervous system have been described in patent application FR-A-2,385,693.
Modafinil is used therapeutically in the treatment of narcolepsies and idiopathic hypersomnias.
The laevorotatory and dextrotatory isomers of modafinil have also been described in EP-A-0 233 106, the laevorotatory isomer being presented as having better bioavailability.
It has now been discovered that modafinil and the isomers thereof have a beneficial effect on the vigilance disorders associated with myopathies and in particular with myotonic dystrophy.
Myotonic dystrophy, or Steinert""s disease, which is the most frequent of the adult dystrophies, is a hereditary disease whose prevalence is estimated to be about 5 to 8/100,000 (P. S. Harper, in xe2x80x9cMyotonic dystrophyxe2x80x9d, 2nd Ed., Saunders, Pa., USA, 1989). This disorder, which is transmitted according to a dominant autosomal method, is always associated with a genetic abnormality (located on chromosome 19) which is characterized by an abnormal amplification of a trinucleotide sequence belonging to a gene encoding a protein kinase.
Myotonic dystrophy is a multisystem pathology which can include an attack of the skeletal and respiratory muscles, of the heart, of the endocrine system, of the lens of the eye and of the central nervous system. It is often revealed by the musculo-skeletal attack which comprises a spontaneous or provoked myotony, an atrophy and a motor deficiency which essentially affects the muscles of the face, the muscles for chewing, the sterno-cleido-mastoid muscles and the distal musculature of the limbs. The neurological attack (objectified by MRI) comprises lesions such as ventricular dilation, atrophy and modification of the subcortical white matter, as well as hippocampal neurofibrillar degenerations and neuronal losses. This neurological attack is revealed, clinically speaking, by cognitive disorders which can range up to an overall picture of subcortical dementia, a lack of initiative and personality disorders (indifference, laziness, aggressiveness, etc.).
An effect on respiratory function and sleep disorders are common. For some patients, the principal discomfort expressed is severe diurnal hypersomnolence (P. S. Harper, R. Rxc3xcdel, in xe2x80x9cMyotonic Dystrophyxe2x80x9d, A. Engel and C. Franzini-Armstrong, eds. Myology 2nd Edition, 1994). The mechanisms of the diurnal hypersomnia of myotonic dystrophy are still unknown. It might be related to a carbonarcosis linked to an alveolar hyperventilation, or to a syndrome of sleep apnoea which are central and/or obstructive or of idiopathic origin. However, diurnal hypersomnia episodes can be observed in dystrophic patients who have a functional respiratory examination assessment which is normal and a polysomnography which is also normal. In this situation, Steinert""s myotonic dystrophy would result from an attack of the central nervous system, which is not evoked in the conventional overall pictures of Gxc3xa9lineau disease (narcolepsy), sleep apnoea or idiopathic hypersomnia (Van der Mechxc3xa9 et al., Neurol, Neurosurg Psychiatry, 57: 626-628, 1994; Ono et al., Neurology, 46: 228-231, 1986).
The diurnal hypersomnolence of patients suffering from Steinert""s disease (myotonic dystrophy) has already been the subject of a number of therapeutic attempts using medicinal products which have stimulatory properties on the central nervous system.
The medical literature available to date presents preliminary results obtained with two compounds which have different mechanisms of action and pharmacological profiles: methylphenidate (Van der Mechxc3xa9 et al., Muscle and Nerve 9: 341-344, 1986) and selegiline (Antonini et al., J. Neurol. Sciences 147; 167-169, 1997). In the first case, an improvement in the level of consciousness was observed, whereas the use of the monoamine oxidase MOA-B inhibitor proved to be ineffective at the dose of 20 mg/day.
This context of therapeutic attempts, which is relatively unfavourable, can perhaps be linked to the physiopathological specificity of myotonic dystrophy, especially when it is accompanied by CNS lesions which are found neither in Gxc3xa9lineau disease nor in idiopathic hypersomnias nor in sleep apnoea.
Modafinil differs considerably from the conventional psychostimulants (d-amphetamine, methylphenidate) with respect to neurochemlical activity. Specifically, within the. dose ranges which modify consciousness, modafinil, unlike d-amphetamine and methylphenidate, has no effect on dopamine, which is the principal target of the conventional psychostimulants. Modafinil also differs from amphetamine in terms of behavioural activity. In addictive substance discrimination tests, the generalization of the effects of modafinil with amphetamine is very weak; modafinil leads neither to self-administration nor to preference of place, which are two behaviours rapidly developed in the case of conventional psychostimulants. In addition, modafinil does not modify the self-administration of cocaine and does not influence the relapse of this behaviour. Finally, while modafinil can activate the expression of the c-fos proto-oncogene in cerebral tissue, it does so in zones which are entirely different from those with which the conventional psychostimulants are concerned. Thus, in a publication by J S. Lin et al. (PNAS, 1996), the c-fos proto-oncogene is not expressed in the central dopaminergic projection zones (including the cortex) after administration of awakening doses of modafinil in cats, whereas it is highly expressed in these regions after administration of equally-awakening doses (with respect to those of modafinil) of d-amphetamine and of methylphenidate.
With these trains of thought and these experimental data in mind, the inventors have discovered, unexpectedly, that modafinil administered to patients suffering from myotonic dystrophy makes it possible to restore a level of diurnal vigilance which is compatible with a satisfactory psychosocial life and relationships. These positive results appear to be all the more unexpected given the fact that patients suffering from Steinert""s disease have normal function or respiratory examinations and normal polysomnography assessments, which are situations which are a good argument for an original effect of modafinil which is independent of what has already been discovered and what has been the subject of patents for already adapted therapeutic use.
The inventors have discovered more generally that modafinil and the isomers thereof make it possible to correct the vigilance disorders which are observed during the evolution of myopathies.
A subject of the present invention is thus a method for correcting vigilance disorders observed during the evolution of myopathies in a patient, which comprises the administration to this patient of an effective dose of modafinil or of one of the isomers thereof.
A subject of the present invention is more particularly a method for correcting vigilance disorders associated with myotonic dystrophy, or Steinert""s disease, which comprises the administration to this patient of an effective dose of modafinil or of one of the isomers thereof.
In patients suffering from myopathies, and in particular from myotonic dystrophy, modafinil and the isomers thereof can be used to specifically combat diurnal hypersomnolence, in order to restore a sleep pattern which is comparable to that of normal sleep and to improve the quality of psychosocial life and relationships.
Modafinil and the isomers thereof can be administered in a form which is suitable for oral administration, and which contains modafinil or each of the isomers thereof in single doses of between 50 and 600 mg, preferably 100 to 400 mg.
The preferred pharmaceutical forms are pharmaceutical forms intended for repeated oral administration in the form of breakable or unbreakable tablets, gel capsules, wafer capsules or controlled-release microgranules.
Modafinil can, however, be administered via other routes, in particular transdermally, and can be provided in the form of ointments, salves, gels, solutions, lotions, liquid forms which form films on the skin for transdermal administration or forms of xe2x80x9cpatchxe2x80x9d type.
Thus, in a series of patients suffering from myotonic dystrophy, in whom validated methods for studying disturbances of the waking/sleeping cycle had demonstrated diurnal hypersomnias of frequency and duration which were considered to be pathological (with respect to clinical and therapeutic experience of sleep apnoeas and narcolepsy), [patients] were treated with oral doses of modafinil of between 100 and 400 mg/day. In the majority of these patients, the modafinil treatment proved to be subjectively effective; the patients report a clear regression of the vigilance disorders and diurnal somnolence and an improvement of their psychosocial life.

Method for correcting the vigilance disorders associated with myopathies


A compressor unloaded system for use in compressed air supply systems having reciprocating type air compressor means supplied with atmospheric or turbocharged air is shown. Means are provided to block off the air intake of such compressors, and to maintain back pressure against the exhaust valve of said air compressor during an unloading cycle, thereby preventing operation of the intake and exhaust valves of such compressor, and creating an "air spring" in the cylinder of such air compressor during an unloading cycle.

I. Field of the Invention
The present invention relates generally to air supply systems using reciprocating type air compressors and, more particularly, to compressor unloading systems usable in such systems when they are used with and without an air dryer such as might be found in air supply systems for truck air brakes and the like. It is well known in the art that in such systems the air compressor operates in its pumping mode for only a short period of time, and that it is operated in what is known as an unloaded mode for approximately 70-90 percent of the time. How to unload the air compressor to save horsepower when the compressor is not pumping, without having other problems occur, has been a long standing problem in the art.
II. Description of the Prior Art
Air compressors used in medium and heavy duty vehicle air supply systems, such as those found in transport trucks, passenger buses, and the like, generally involve having an air compressor directly driven by the vehicle engine and supplied with inlet air at atmospheric pressure, or, in the case of many transport trucks today, turbocharged air from the engine turbocharger via the engine air intake manifold.
These air compressors generally are one, two or four cylinders in nature. The earliest attempts at internally unloading the air compressor in regard to two cylinder compressors was to simply hold the intake valves for both cylinders open and pump air back and forth between the cylinders, and this was relatively satisfactory when there was no concern with the fuel cost or the horsepower being lost.
With single cylinder air compressors, the earliest unloading method simply involved holding the intake valve open so that air was pumped in and out through the compressor intake opening.
In the European countries, the approach to the problem was somewhat different, and while the intake valve was left untouched, the compressor pumped all the time while the unloading function was performed external to the compressor via a separate diverted type system called an unloader valve. This method of unloading is now generally viewed as unsatisfactory because of the noise produced, and the horsepower losses incurred. Thus, design and development work focused on better ways to unload air compressors other than simply holding the intake valve open.
In many cases, when the intake valve was held open on a single cylinder and compressor and the compressor was supplied with naturally aspirated air, which was common at the time, since the compressor intake was supplied with a separate air cleaner, pumping back and forth through the air cleaner in many cases destroyed the air cleaner, or reduced its efficiency so it would not perform for the purpose for which it was intended.
This caused the truck manufacturers to switch to a system supplied with turbocharged inlet air from the engine turbocharger to avoid the air cleaner problems and assure a clean inlet air supply, but it was then found that when unloading in the conventional way, by holding the intake valve open, the faster the engine was running, the denser the air, and the more horsepower was lost due to the unloading. Thus, the search continued for a satisfactory solution to the problem.
A clutched compressor recently developed was not felt to be the answer to the horsepower loss problem because the compressor shaft normally runs through the compressor and often drives other accessories, such as the power steering, or engine fuel pump, and it was not satisfactory to have the power steering and other items nonfunctional for the time the compressor was unloaded. Also, the clutched compressor would substantially increase the cost of the air supply system, and this was not satisfactory. Thus, not much progress was made in developing a more efficient compressor unloading system, and until the present invention, the expedient of simply holding the intake valve open to allow unloading either to atmosphere, or the engine turbocharger, is the accepted way of unloading the air compressor.
This method of compressor unloading is known to be unsatisfactory when turbocharged inlet air is utilized for several reasons, including the loss of up to five (5) horsepower under certain operating conditions, the diversion of a significant amount of engine intake air through the compressor and air dryer out to the atmosphere when the compressor is in the unloading mode, and now with the advent of the air dryer in medium and heavy duty vehicle air brake systems, there is an inordinate loss of engine power, increased oil consumption, and waste of fuel in the unloading mode. Because of these new problems, past solutions were no longer acceptable by the engine and compressor makers, and much additional work and invention had to take place in the field of air compressor unloader systems before a satisfactory solution was arrived at. The inventions which have now been made, are disclosed and claimed in the present application, and in a copending application in which we are the inventors entitled RING VALVE TYPE AIR COMPRESSOR.


An insulated wire which comprises an aluminum conductor, having: an adhesion layer formed by directly baking, on the aluminum conductor, varnish containing a carboxy group; an insulation layer as an outer layer of the adhesion layer; and a reinforcement insulation layer as an outer layer of the insulation layer; and a method of producing the same.

Inverters have become installed in many types of electrical equipments, as efficient variable-speed control units. Inverters are switched at a frequency of several of kHz to several tens of kHz, to cause a surge voltage at every pulse thereof. Inverter surge is a phenomenon in which reflection occurs at a breakpoint of impedance, for example, at a starting end, a termination end, or the like of a connected wire in the propagation system, and consequently, to apply a voltage twice as high as the inverter output voltage at the maximum. In particular, an output pulse occurred due to a high-speed switching device, such as an IGBT (insulated gate bipolar transistor), is high in steep voltage rise. Accordingly, even if a connection cable is short, the surge voltage is high, and voltage decay due to the connection cable is also low. As a result, a voltage almost twice as high as the inverter output voltage occurs.
As coils for electrical equipments, such as inverter-related equipments, for example, high-speed switching devices, inverter motors, and transformers, use is made of insulated wires, which are mainly enameled wires, as magnet wires in the coils. Further, as described above, since a voltage almost twice as high as the inverter output voltage is applied to the in inverter-related equipments. Thus, it has become required to minimize the inverter surge deterioration of the enameled wire, which is one of the materials constituting the coils of those electrical equipments.
In general, partial discharge deterioration is a phenomenon in which an electrical-insulation material undergoes, in a complicated manner, for example, molecular chain breakage deterioration caused by collision with charged particles that have been generated by partial discharge of the insulating material, sputtering deterioration, thermal fusion or thermal decomposition deterioration caused by local temperature rise, and chemical deterioration caused by ozone generated due to discharge. For any of those, reduction in thickness of the electrical-insulation materials may be observed, which have been deteriorated as a result of the partial discharge.
It is believed that inverter surge deterioration of an insulated wire also proceeds by the same mechanism as in the case of general partial discharge deterioration. That is, inverter surge deterioration of an enameled layer is a phenomenon in which partial discharge occurs in the insulated wire due to the surge voltage with a high peak value, which is occurred at the inverter, and the coating of the insulated wire causes partial discharge deterioration as a result of the partial discharge, resulting in that the inverter surge deterioration of an enameled layer of the coating of the insulated wire is high-frequency partial discharge deterioration.
Such a deterioration of the enameled layer of the insulated wire can be prevented by the insulated wire having a high partial discharge inception voltage, and a method of using a resin having low relative permittivity in the enameled layer, and/or a method of increasing a thickness of the enameled layer, are considered.
However, in the former method, if other characteristics (heat resistance, solvent resistance, flexibility, and the like) required for the enameled layer are taken into consideration, it is difficult to select the resin having a particularly low in relative permittivity.
Moreover, in order to satisfy electrical properties, such as dielectric breakdown voltage and partial discharge inception voltage in the latter method, 60 μm or more is empirically required as the thickness of the enameled layer.
However, if a wire is passed through a high-temperature baking furnace a plurality of times in a production process in order to increase a thickness of an enameled layer composed of a thermosetting resin, a copper oxide coating grows on a surface of copper being a conductor, and adhesion force between the conductor and the enameled layer is lowered. As a result, there has existed a problem in which workability, such as flexibility, is significantly lowered.
Moreover, if the thickness to be applied in one-time baking is increased in order to reduce the number of times passing through the baking furnace, there has existed a disadvantage in which a solvent in varnish is not wholly evaporated and remains as gas bubbles in the enameled layer.
On the other hand, weight reduction is required for a motor, and development has been advanced on significant weight reduction of the coils by using an aluminum conductor. Not only the weight can be reduced by use of aluminum, but also ease of bending, namely flexibility being important for a winding wire for coils can also be improved.
Moreover, a passive state is formed on a surface of the aluminum conductor. Thus, lowering in the adhesion force between the conductor and the enameled layer as caused by growth of oxide coating, which has become the problem in the cupper conductor, can be prevented, and damage on an electrical wire coating in a coil working step, and lowering in electrical insulation performance can be prevented. In particular, the insulated wire having high mechanical strength, such as abrasion resistance, can be produced.
Where, it is understood that tensile stress applied to the conductor is increased by increasing the number of times of baking in baking of the enameled wire. Moreover, it is also known that physical strength of the conductor is significantly lowered by increase of a received heat quantity when aluminum is used for the conductor. Owing to these two phenomena, there has existed a problem in which reliability as the winding wire is reduced, such as lowering in accuracy of a conductor diameter or rupture strength (breaking strength) of the conductor by increasing the number of times of baking, in the case of the aluminum conductor enameled wire.
Hitherto, attempts have been made on improving characteristics, such as high heat resistance and high abrasion resistance, by a newly provided covering resin layer, in addition to enhance the partial discharge inception voltage by providing a covering resin outside the enameled wire. Proposals have been made on providing an extrusion covering layer on an enameled layer in, for example, Patent Literatures 1, 2, and the like. On the other hand, it is understood that, when extrusion covering is performed on the enameled wire of the Al conductor, adhesion force between the aluminum conductor and the enameled layer is readily lowered because a temperature of an extruded resin is high. However, no studies have been made on the adhesion force between the conductor and the enameled layer in the arts proposed in Patent Literatures 1 and 2. When coil winding on the motor or the transformer is performed in a state in which the adhesion force between the conductor and the enameled layer is low, damage is readily caused on the electrical wire coating in the coil working step, to cause a problem in which the electrical insulation performance is lowered and the reliability of a product is lowered.
It has become demanded to further improve various performances, such as heat resistance, mechanical properties, chemical properties, electrical properties, and reliability, in the electrical equipments developed in recent years, as compared to the conventional electrical equipments. Under the situations, excellent abrasion resistance, thermal aging resistance, and solvent resistance have become required for insulated wires, such as enameled wires, that are used as magnet wires for electrical equipments for aerospace use, electrical equipments for aircraft, electrical equipments for nuclear power, electrical equipments for energy, and electrical equipments for automobiles. For example, in recent electrical equipments, a capability of maintaining excellent thermal aging resistance for a further longer period of time is required in several cases.
Further, electrical equipments, which are represented by motors or transformers, have recently advanced in size reduction and performance improvement, and it becomes found that, in many applications, insulated wires to be used are pushed into a quite narrow space to pack. Specifically, it is not an exaggeration to say that the performance of a rotary electric machine, such as a motor, depends on how many electrical wires can be placed and packed in a stator slot.
As a result, as a means for increasing the ratio of the cross-sectional area of the conductor to the cross-sectional area of the stator slot (hereinafter, referred to a stacking factor or a space factor), it has been lately attempted to use a rectangular wire in which the conductor has a shape similar to a quadrilateral (square or rectangle). Use of a rectangular wire exhibits a dramatic effect in increasing the stacking factor. However, there are known that it is difficult to uniformly apply an insulation coating on a rectangular conductor, and that it is particularly difficult to control the thickness of the insulation coating in an insulated wire having a small cross-sectional area.

Insulated wire and method of producing the same


A cordless modem system where a mobile station unit (MSU) is located in the computer and a base station unit (BSU) is connected to the telephone line. A radio frequency (RF) link is developed between the two units to allow a cordless connection. A series of commands are used between the two units to allow the MSU to request a channel, the BSU to grant a channel, the BSU to notify of a ring, and the MSU to request the BSU to go off hook. In addition, there is preferably a command sequence to allow authorization of a particular MSU or BSU. There are two full duplex channels in each MSU and BSU. This allows multiple BSUs and MSUs to be utilized in a small area. Communications between the two units are secure based on address values for each unit contained in the various commands. The communications software utilized in the computer is not even aware of the presence of the cordless connection. Two embodiments of the MSU are provided, one configured as an external data access arrangement (DAA) to be connected with laptop modems configured to utilize external DAAs, and in a second embodiment the MSU is incorporated with the modem hardware to provide a single, fully integrated unit. The BSU is a single preferably relatively small box which simply plugs into the telephone line.

1. Field of the Invention
The invention relates to a system having a cordless connection between a modem in a computer and a telephone land line, and more particularly to allowing multiple units and yet maintaining security of each connection.
2. Description of the Related Art
Mobile computers, particularly laptop computers and notebook computers have become increasingly popular. They have performance and capabilities near that of a desktop unit, and if color active matrix liquid crystal displays are utilized, the display is as good as a desktop unit. When combined with the mobility, the popularity is quite understandable. However, one problem with using portable computers is that often they need to be connected to various equipment. For example, when located in a office, it is desirable to connect to various office wide items or non-portable items. For example, a network interface is often necessary, as is a SCSI port for use with various external devices such as CD-ROMs. This situation has conventionally been handled using expansion bases, which contain expansion cards for network and SCSI use and connections for a video monitor, a printer and a full size keyboard, or port replicator strips, which are used to simply provide the connections to the monitor, printer and keyboard without the need for expansion cards.
One of the computer applications which is becoming prevalent is electronic mail or E-mail. The modern business often has a local area network (LAN), with E-mail and appointment calendar applications. A remote user, such as the laptop user away from the office needs to check periodically to maintain in full contact. Thus, a very common addition to a portable computer is a modem to allow remote access to the LAN or other dial up services. Typically this modem is installed in the laptop computer, not directly in any expansion base. So while an expansion base or port replicator may alleviate certain wiring problems, as the various cables need not be disconnected or connected when removing or installing the portable computer, it does not resolve the wiring concerns in the case of a modem, where a separate telephone line is still required to be plugged and unplugged into the modem in the computer. This results in aggravation for the user. Further, this phone line is yet another of the tangled mass of cables utilized with the modern computer. While the monitor, keyboard and SCSI cables are generally located right next to the computer to interconnect the various components, the telephone line often has to be strung across an office and thus is either unsightly or very difficult to route. This is a further drawback to standard conventional modem communications where the modem is contained in the personal computer, be it a laptop or a desktop unit.
Thus the use of a modem in a laptop computer results in aggravations for the user and additionally requires unsightly and cumbersome cabling. Therefore it is clearly desirable to simplify both the laptop portability concerns and the unsightly wiring problem.
The present invention relates to a cordless modem system where a mobile station unit (MSU) is located in the computer or connected to the computer and a base station unit (BSU) which is connected to the telephone line. A radio frequency (RF) link is developed between the two units to allow a cordless connection between the computer and the telephone line. The BSU is completely powered from the telephone line, while the MSU is powered from the computer system. A software protocol is utilized between the two units to open a channel when a call is received or the computer wishes to go off hook. Each MSU and BSU have a personalized identification. The BSU is allowed to perform communications only with authorized and identified MSUs, while the MSU can perform communications only with BSUs with which it has previously communicated. A series of commands are present between the two units to allow the MSU to request a channel, the BSU to grant a channel, the BSU to notify of a ring, and the MSU to request the BSU to go off hook. In addition, there is preferably a command sequence to allow authorization of a particular MSU for use with the BSU.
Preferably, there are two channels in each MSU and BSU, each channel being full duplex. This presence of two channels allows multiple BSUs and MSUs to be utilized in a small area if desired. Once a particular BSU is receiving input or has made a connection with a particular MSU, the BSU is then dedicated to that MSU for the duration of the call. By having two channels, two BSUs can be present in the same environment. Communications between the two units are secure in that the BSUs and MSUs include collision detection logic to determine if both channels are already active. If so, the MSUs and BSUs do not start communication. If a channel is available, an MSU requests that channel, with the request command including the address or identification number of the MSU. The BSU receives the authorization request, checks its list of authorized MSUs and if present and the channel is available, provides a grant command to the MSU. When the BSU receives a call and a ring from the telephone line, after checking for an open channel, the BSU transmits a designated MSU identification along with a ring indication command so that only the specified MSU will answer the call. Further, the grant and ring indication commands include the BSU identification number so that the MSU will communicate only with that particular BSU while the call is on-going. In this manner, one MSU will not intercept the calls for another MSU after the link has been established and a BSU will not provide calls to unauthorized MSUS. This allows data transfer to be secure even though multiple MSUs are present and can generally share a single BSU.
Further, the development of the protocol is such that the communications software utilized in the computer is not even aware of the presence of the cordless connection. Both the MSUs and BSUs contain microcomputers and proper signaling to sense what action is requested from the modem or telephone line and perform the cordless or radio transmission function seamlessly. Thus conventional communication software can be utilized without any particular special commands or structure. This allows the user to continue to use his preferred communication software package.
Two embodiments of the MSU are provided, one configured as an external data access arrangement (DAA) to be connected with laptop modems configured to utilize external DAAs, while in the second embodiment the MSU is incorporated with the modem hardware to provide a single, fully integrated unit. The BSU is a single, preferably relatively small, box which simply plugs into the telephone line.
Thus by having this transparent cordless link, the laptop user does not have to disconnect or connect a telephone line each time he moves his laptop and further the telephone line need not be routed across open areas or through difficult passages.

Cordless modem system having multiple base and remote stations which are interusable and secure