Water-dilutable binder composition containing one or more water-dilutable hydroxy-functional polyurethane urea paste resins having a urea group content (calculated as xe2x80x94NHCONHxe2x80x94) of from 10 to 300 mmol, a urethane group content (calculated as xe2x80x94NHCOOxe2x80x94) of from 20 to 300 mmol, in each case in 100 g of solid resin, an OH number of from 20 to 250, an acid number of from 15 to 80 and a molar mass Mn of from 1000 to 20,000, obtainable by

The invention relates to water-dilutable binder compositions which can advantageously be used as a paste resin for the milling of pigments. The resulting pigment pastes are suitable for incorporation into aqueous coating compositions, especially for incorporation into water-based lacquers and water-based finishing lacquers. The water-dilutable binder compositions can be used in automotive and industrial lacquering for coating plastics and metal substrates.
In the preparation of stable pigmented water lacquers it is necessary to wet the pigments thoroughly, grind them finely in suitable dispersing units and disperse them stably in order to prevent agglomeration or sedimentation of the pigments. When low-solvent water-dilutable dispersions or emulsions are used, the action of the shearing forces may be inadequate owing to the very low viscosities. In addition, it must be taken into account that water-dilutable high molecular weight dispersions or emulsions are not always stable to shear in dispersing units. In those cases it is therefore necessary to replace a portion of the binder that is to be used by a paste resin in which the pigments are milled. The pigment or ground pastes so obtained are subsequently mixed (xe2x80x9clacquered upxe2x80x9d or made up) with the main binder.
The mentioned paste resins must meet a number of requirements. For example, the paste binders are to be compatible with the main binder(s) and are not to impair the properties of the lacquer in the required added amount. They are to exhibit a good wetting ability for the pigments in question, are to be stable to storage over a prolonged period and are not to bring about colour changes in the lacquer. For the preparation of repair lacquers from standardised mixed lacquers in particular, it is very important to use lacquer concentrates which are highly reproducible in terms of colouristic and technological properties, in order to produce desired shades of colour economically and without unreasonable outlay in terms of shade.
Various binders which are suitable as a paste resin have already been described, which binders can be used in water-based lacquers or water-based finishing lacquers having various binder compositions. For example, in EP-A-0 260 447, polyester resins, acrylate resins and/or amine-formaldehyde condensation resins are used as the milling resin for the preparation of water-based lacquers. The water-based lacquers contain acrylated polyesters and polyurethane resins as the main binder. The milling resins described therein are not always fully compatible with the main binders, which can lead inter alia to an impairment of the metallic effect in the formulation of metallic lacquers.
EP-A-0 299 148 describes pigment pastes based on water-dilutable polyurethane paste resins, the polyurethane resins being prepared from polyester polyols, the acid component of which contains at least 50 wt. % long-chained carboxylic acids having from 18 to 60 carbon atoms in the molecule.
EP-A-438 090 describes milling resins based on water-dilutable polyester urethanes, which are obtained by reacting carboxyl-group-free polyester polyols and low molecular weight diols, at least some of the low molecular weight diols containing an acid group capable of anion formation, with diisocyanates.
A disadvantage of the mentioned milling pastes is that pigment pastes formulated therefrom, especially white pastes, produce lacquers having an inadequate covering power. It is also very difficult using the known paste formulations to produce a deep black. The formulated pigment pastes are often highly thixotropic, so that the metering ability and pumpability of the pastes are greatly impaired. Furthermore, both the known paste resins and the pigment pastes formulated therewith are not stable to frost, and the resistance to chemicals of the water lacquers prepared using those paste resins or of coatings obtained therefrom is in need of improvement. Occasionally, inadequate solids contents are achieved in the preparation of paste resin dispersions, which inter alia can impair the processability and render it less economical.
Furthermore, EP-A-0 469 389 discloses aqueous two-component polyurethane coating compositions which contain water-dilutable hydroxy-functional polyurethane resins having a total urethane and urea group content of from 9 to 20 wt. %, based on the weight of the polyurethane, and water-dispersible polyisocyanates. The coating compositions may additionally contain as a 3rd component up to 20 wt. % of a polyol having a molar mass of from 62 to 1000, preferably from 62 to 250, which may optionally contain polyether groups. The use of the mentioned polyurethane resins as a paste resin is not mentioned.
Accordingly, the object of the invention was to make available water-dilutable binder compositions which are suitable as a paste resin and which can be used as a pigment paste formulation for incorporation into aqueous coating compositions. Pigment pastes formulated from the binder compositions are to exhibit very good compatibility with a large number of different binder systems as well as a very good pigmenting and wetting ability, and consequently are to enable pigmented lacquers to be prepared in an energy- and time-saving manner. It is to be possible to process and meter, and especially also pump, the pigment pastes readily. The pigment pastes are to yield lacquers having a very good covering power and enable the production of a deep black. The pigment pastes and the aqueous lacquers prepared therefrom are also to be stable to storage and to frost. Coatings having a high gloss, a good metallic effect and also very good hardness and resistance to chemicals are to be obtained.
The object is achieved by a water-dilutable binder composition containing
A) one or more water-dilutable hydroxy-functional polyurethane urea resins having a urea group content (calculated as xe2x80x94NHCONHxe2x80x94) of from 10 to 300, preferably from 20 to 250, mmol in 100 g of solid resin, a urethane group content (calculated as xe2x80x94NHCOOxe2x80x94) of from 20 to 300, preferably from 80 to 250, mmol in 100 g of solid resin, an OH number of from 20 to 250, preferably from 40 to 200, especially from 60 to 150, an acid number of from 15 to 80, preferably from 18 to 65, especially from 19 to 45, and a number-average molar mass Mn of from 1000 to 20,000 g/mol, preferably from 1500 to 15,000 g/mol, which are obtained by
I) preparing an NCO-group-containing polyurethane prepolymer by reacting
a1) one or more hydroxy-functional compounds having a number-average molar mass Mn of from 360 to 8000 g/mol, preferably from 500 to 5000 g/mol, with
a2) one or more polyisocyanates and
a3) at least one compound having at least one group that is able to react with isocyanate and at least one group that is ionic or capable of ion formation,
II) subsequently reacting the NCO-group-containing polyurethane prepolymer with
a4) one or more hydroxy-functional monoamines and optionally with one or more polyols, in such relative amounts that the resulting polyurethane has the desired hydroxyl numbers and urea and urethane group contents,
III) neutralising at least some of the ionic groups of the resulting polyurethane before or after the reaction in step II, and converting the resulting reaction product into the aqueous phase,
xe2x80x83and
B) from 2.0 to 25 wt. %, based on the solids content of polyurethane urea resin used, of one or more polyether polyols having a molar mass of from 400 to 5000 g/mol, preferably from 500 to 3000 g/mol.
The binder composition according to the invention contains as component A) one or more water-dilutable hydroxy-functional polyurethane urea resins.
The water-dilutable hydroxy-functional polyurethane urea resins and their preparation will be described hereinbelow.
For the preparation of the water-dilutable polyurethane urea resins, an NCO-functional polyurethane prepolymer is first prepared in a first step (I). The polyurethane prepolymer is obtained by reacting components a1) to a3).
Component a1) for the preparation of the NCO-functional polyurethane prepolymer is hydroxy-functional linear or branched compounds which preferably have an OH-functionality of from 2 to 3, especially 2, an OH number of from 50 to 250 and a number-average molar mass (Mn) of from 360 to 8000 g/mol, preferably from 500 to 5000 g/mol.
There may be used as component a1) polyester polyols, polycarbonate polyols, polyether polyols, polylactone polyols and/or poly(meth)acrylate polyols and the corresponding diols. The polyols and diols may each be used individually or in combination with one another.
Polyester polyols, for example polyester diols, are preferably used as component a1). They are especially linear polyester polyols, especially linear polyester diols.
The polyester polyols can be prepared in a conventional manner known to the person skilled in the art, for example by polycondensation from organic dicarboxylic acids or their anhydrides and organic polyols. The dicarboxylic acids and the polyols may be of aliphatic, cycloaliphatic or aromatic nature.
The acid component for the preparation of the polyester polyols is preferably low molecular weight dicarboxylic acids or their anhydrides having from 2 to 17, preferably less than 16, especially less than 14, carbon atoms in the molecule. Suitable dicarboxylic acids are, for example, phthalic acid, isophthalic acid, alkylisophthalic acid, terephthalic acid, hexahydrophthalic acid, adipic acid, trimethyladipic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, glutaric acid, succinic acid, itaconic acid and 1,4-cyclohexanedicarboxylic acid. Instead of the acids, the corresponding anhydrides, where they exist, can also be used. In order to achieve branching, amounts of carboxylic acids having a higher functionality may also be added, for example trifunctional carboxylic acids such as trimellitic acid, malic acid and dimethylolpropionic acid.
Polyols which can be used for the preparation of the polyester polyols are preferably diols, for example glycols, such as ethylene glycol, 1,2-propanediol, 1,2-, 1,3- and 1,4-butanediol, 2-ethylene-1,3-propanediol, 1,6-hexanediol, 1,2- and 1,4-cyclohexanediol, hydrogenated bisphenol A and neopentyl glycol.
The diols may optionally be modified by small amounts of higher-hydric alcohols.
Examples of higher-hydric alcohols which can be used concomitantly are trimethylolpropane, pentaerythritol, glycerol and hexanetriol. Chain-terminating monohydric alcohols, for example those having from 1 to 18 carbon atoms in the molecule, such as propanol, butanol, cyclohexanol, n-hexanol, benzyl alcohol, isodecanol, saturated and unsaturated fatty alcohols, can also be used proportionately.
The components are reacted in such relative amounts that the desired OH numbers of the polyester polyols are obtained.
The polyester polyols are preferably substantially free of carboxyl groups. They may have, for example, acid numbers of  less than 3, preferably  less than 1. It is, however, also possible for the polyester polyols to contain carboxyl groups; for example, they may then have acid numbers of from 5 to 50 mg of KOH/g. The carboxyl groups may be introduced, for example, via di- or tri-functional carboxylic acids, such as, for example, trimellitic acid, malic acid, and dihydroxymonocarboxylic acids, such as, for example, dimethylolpropionic acid.
The polyester polyols may be used individually or in combination with one another.
Also preferred as component a1) are polycarbonate polyols and especially polycarbonate diols.
The polycarbonate polyols are esters of carbonic acid, which are obtained by reacting carbonic acid derivatives, for example diphenyl carbonate or phosgene, with polyols, preferably diols. Suitable diols are, for example, ethylene glycol, 1,2- and 1,3-propanediol, 1,4- and 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol and 1,4-bishydroxymethylcyclohexane.
The polycarbonate polyols may be used individually or in combination with one another.
Also suitable as component a1) are polyether polyols and/or polylactone polyols.
Suitable polyether polyols are, for example, polyether polyols having the following general formula:
H[Oxe2x80x94(CHR4)n]mOH
in which R4 represents hydrogen or a lower alkyl radical (for example C1 to C6), optionally having various substituents, n=from 2 to 6 and m=from 10 to 50. The radicals R4 may be identical or different. Examples of polyether polyols are poly(oxytetramethylene) glycols, poly(oxyethylene) glycols and poly(oxypropylene) glycols or mixed block copolymers which contain different oxytetramethylene, oxyethylene and/or oxypropylene units.
The polyether polyols may be used individually or in combination with one another.
The polylactone polyols are polyols, preferably diols, which are derived from lactones, preferably caprolactones. Those products are obtained, for example, by reacting an epsilon-caprolactone with a diol. The polylactone polyols are distinguished by repeating polyester components, which are derived from the lactone. Those repeating molecule components may correspond, for example, to the following general formula:
wherein n is preferably from 4 to 6 and R5 is hydrogen, an alkyl radical, a cycloalkyl radical or an alkoxy radical, and the total number of carbon atoms in the substituents of the lactone ring does not exceed 12. Lactones that are preferably used are the epsilon-caprolactones in which n has the value 4. Special preference is given to the unsubstituted epsilon-caprolactone. The lactones may be used individually or in combination.
Diols suitable for the reaction with the lactones are, for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol and dimethylolcyclohexane.
The polylactone polyols may be used individually or in combination with one another.
Poly(meth)acrylate polyols may also be used as component a1). The poly(meth)acrylate polyols are polymers of hydroxy-functional (meth)acrylic acid esters and further radically polymerisable unsaturated monomers prepared by means of free-radical polymerisation. There may preferably be used poly(meth)acrylate polyols which, owing to the specific preparation process, have a selective structure with terminal OH groups. The poly(meth)acrylate polyols may likewise be used individually or in combination with one another.
There may additionally be used in component a1) optionally one or more low molecular weight polyhydric alcohols, preferably difunctional alcohols, having a molar mass of from 62 to 356 g/mol. Examples thereof are ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,2- and 1,4-cyclohexanediol, dimethylolpropane, neopentyl glycol, cyclohexanedimethanol and hydroxyethylated or hydroxypropylated bisphenol A or bisphenol F.
There may be used as component a2) for the preparation of the NCO-functional prepolymers any organic polyisocyanates, preferably diisocyanates, individually or in combination. The polyisocyanates may be, for example, of aromatic, aliphatic and/or cycloaliphatic nature. They may also be diisocyanates containing ether or ester groups. Examples of suitable diisocyanates are trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylene diisocyanate, 2,3-dimethylethylene diisocyanate, 1-methyltrimethylene diisocyanate, 1,3-cyclopentylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,2-cyclohexylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, 1-isocyanatomethyl-5-isocyanato-1,3,3-trimethylcyclohexane, bis-(4-isocyanato-phenyl)-methane, norbornene diisocyanate, 4,4-diisocyanato-diphenyl ether, 1,5-dibutylpentamethylene diisocyanate, 2,3-bis-(8-isocyanatooctyl)-4-octyl-5-hexylcyclohexane, 3-isocyanatomethyl-1-methylcyclohexyl isocyanate and/or 2,6-diisocyanatomethyl capronate.
It is also possible to use non-yellowing and/or sterically hindered isocyanates which have from 4 to 25, preferably from 6 to 16, carbon atoms and contain as substituent on the basic structure, in the alpha-position with respect to the NCO group, one or two linear, branched or cyclic alkyl groups having from 1 to 12, preferably from 1 to 4, carbon atoms. The basic structure may consist of an aromatic or alicyclic ring or of an aliphatic linear or branched carbon chain having from 1 to 12 carbon atoms. Examples thereof are isophorone diisocyanate, bis-(4-isocyanatocyclohexyl)methane, 1,1,6,6-tetramethyl-hexamethylene diisocyanate, 1,5-dibutyl-pentamethylene diisocyanate, 3-isocyanatomethyl-1-methyl-cyclohexyl isocyanate, p- and m-tetramethylxylylene diisocyanate and/or the corresponding hydrogenated homologues.
Component a3) for the preparation of the NCO-functional prepolymer is preferably low molecular weight compounds which have at least one, preferably more than one, especially two, groups that are able to react with isocyanate groups and at least one group that is ionic or capable of ion formation. Carboxyl, phosphoric acid and sulfonic acid groups, for example, come into consideration as groups capable of anion formation. Preferred anionic groups are carboxyl groups. There come into consideration as groups capable of cation formation, for example, primary, secondary and tertiary amino groups or onium groups, such as quaternary ammonium, phosphonium and/or tertiary sulfonium groups. Groups that are anionic or capable of anion formation are preferred. Suitable groups that are able to react with isocyanate are especially hydroxyl groups as well as primary and/or secondary amino groups.
Preferred compounds that are suitable as component a3) are those which contain carboxyl and hydroxyl groups. Examples of such compounds are hydroxyalkanecarboxylic acids of the following general formula:
xe2x80x83(HO)xQ(COOH)y
wherein
Q represents a straight or branched hydrocarbon radical having from 1 to 12 carbon atoms and x and y each represent from 1 to 3. Examples thereof are citric acid and tartaric acid. Preference is given to carboxylic acids wherein x=2 and y=1.
A preferred group of dihydroxyalkanoic acids is alpha,alpha-dimethylolalkanoic acids.
Preference is given to alpha,alpha-dimethylolpropionic acid and alpha,alpha-dimethylolbutyric acid.
Further examples of dihydroxyalkanoic acids that can be used are dihydroxypropionic acid, dimethylolacetic acid, dihydroxysuccinic acid or dihydroxybenzoic acid.
Further compounds that can be used as component a3) are amino-group-containing acids, for example alpha,alpha-diamino-valeric acid, 3,4-diaminobenzoic acid, 2,4-diamino-toluene-sulfonic acid and 4,4-diamino-diphenyl ether sulfonic acid, as well as dihydroxy compounds which contain a tertiary and/or quaternary amino group, such as, for example, N-methyldiethanolamine, N-methyl diisocyanate and 2-N,N-dimethylamino-2-ethyl-1,3-propanediol.
The reaction of components a1), a2) and a3) together is carried out in a conventional manner known to the person skilled in the art, for example at temperatures of from 50 to 120xc2x0 C., preferably from 70 to 100xc2x0 C., optionally with the addition of catalysts.
Components a1), a2) and a3) are reacted in such amounts that a reaction product having free isocyanate groups is formed, that is to say an excess of polyisocyanate is used. For example, a ratio of equivalents of NCO groups:OH groups of from 1.1:1 to 2.0:1, preferably from 1.2:1 to 1.9:1, can be used.
The NCO-group-containing polyurethane prepolymer obtained in step I is then reacted in a further step II) with component a4) and thus converted into a urea-group-containing and hydroxy-functional polyurethane. Component a4) is one or more hydroxy-functional monoamines each having a primary or secondary amino group. The hydroxy-functional monoamines may optionally be used together with one or more polyols. The reaction is carried out with complete consumption of the amino groups. The monoamines that can be used may contain one or preferably more than one hydroxyl group. They may be, for example, alkanolamines, dialkanolamines, alkylalkanolamines and/or arylalkanolamines having at least 2 and not more than 18 carbon atoms in the alkanol, alkyl and aryl radical. Examples of monoamines having one hydroxyl group that can be used are monoethanolamine, N-methylethanolamine, 3-amino-1-propanol, 2-amino-2-methylpropanol, N-phenylmethanolamine and N-cyclohexylethanolamine. Examples of monoamines having two or more hydroxyl groups are diethanolamine, diisopropanolamine, 2-amino-2-ethyl-1,3-propanediol and 2-amino-2-hydroxymethylpropane-1,3-diol.
The hydroxyamines and the polyols that are optionally present (component a4) are used in such an amount that OH numbers of from 20 to 250, preferably from 40 to 200, especially from 60 to 150, and urea group contents of from 10 to 300, preferably from 20 to 250, mmol in 100 g of solid resin are achieved in the resulting reaction product. Complete conversion is desired with a virtually equivalent molar ratio between the reactive amino group and the isocyanate group. Optionally, a very small NCO excess can be used. The ratio of equivalents of NCO groups to amino groups is to be less than 1.05:1, but it is preferably 1:1.
The polyols which are optionally present together with the hydroxyamines can serve to introduce hydroxyl groups into the polyurethane. They are preferably low molecular weight alcohols having two or more hydroxyl groups. Examples thereof are neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and glycerol, hydroxypivalic acid neopentyl glycol ester, 2-ethyl-2-methyl-1,3-propanediol, 1,6-hexanediol, cyclohexanedimethanol and ditrimethylolpropane.
It is, however, also possible to introduce an amount of cationic groups into the polyurethane urea resin in addition to the anionic groups. In terms of equivalents, the cationic groups are to be present only as a fraction, based on the anionic groups. The cationic groups are preferably tertiary and/or quaternary amino groups. For example, from 0.05 to 25%, preferably from 0.1 to 10%, of cationic groups, based on equivalents of anionic groups, may be present. The introduction of additional cationic groups can be effected, for example, by reacting the NCO prepolymer with compounds having at least one hydroxyl group and one tertiary or quaternary amino group. The procedure may, for example, be such that the mentioned compounds having tertiary and/or quaternary amino groups are reacted with the NCO prepolymer together with the amino alcohols. Examples of compounds having at least one hydroxyl group and one tertiary or quaternary amino group are N-methyldiethanolamine, N-methyl-diisopropanol and 2-N,N-dimethylamino-2-ethyl-1,3-propanediol.
In order to achieve adequate water dilutability, at least some of the groups in the polyurethane urea resin that are ionic or can be converted into ionic groups are neutralised in a further step III. The neutralisation may take place either before or after the reaction with the hydroxyamines. The polyurethane resins preferably contain anionic groups. The anionic groups are neutralised using bases. Preferred examples of basic neutralising agents are tertiary amines, such as trimethylamine, triethylamine, dimethylethylamine, dimethylbutylamine, N-methylmorpholine, dimethylethanolamine and dimethylisopropanolamine. Isocyanate-group-free polyurethane urea resins can also be neutralised using amines containing groups that are able to react with isocyanate groups, for example using primary or secondary amines or amino alcohols.
After the neutralisation, the polyurethane urea resin is converted into the aqueous phase. Neutralisation and conversion into the aqueous phase may also be carried out simultaneously, however.
The polyurethane urea resin is in a colloidal state in the aqueous phase and exhibits intrinsically viscous behaviour. That means that the viscosity falls as the shear rate increases. The viscosity of the polyurethane urea dispersion, measured at a shear rate of 231 sxe2x88x921 and a solids content of 35 wt. %, is from 0.5 to 10 Pas. The degree of neutralisation is preferably from 60 to 120%, especially from 70 to 100%. The aqueous resin dispersion has a solids content of preferably from 25 to 50 wt. %, especially from 28 to 42 wt. %.
The particle size of the polyurethane urea resin in the aqueous phase is preferably in the range of from 25 to 200 nm, preferably from 30 to 100 nm.
The aqueous polyurethane urea dispersion may preferably have, for example, the following composition:
The binder composition according to the invention contains as component B) from 2.0 to 25 wt. %, based on the solids content of the polyurethane urea resin used, of one or more polyether polyols having a molar mass of from 400 to 5000, preferably from 500 to 3000, g/mol.
Examples of suitable polyether polyols are poly(oxytetramethylene) glycols, poly(oxyethylene) glycols and poly(oxypropylene) glycols or mixed block copolymers which contain different oxytetramethylene, oxyethylene and/or oxypropylene units. Preference is given to polyether polyols that are obtained without the concomitant use of ethylene oxide, that is to say especially using only propylene oxide or tetrahydrofuran. Special preference is given to the use of polyoxypropylene glycols having molar masses of from 500 to 3000 g/mol. Different polyether polyols can be combined with one another.
The binder composition according to the invention can be prepared by mixing components A) and B). That can be effected in various ways. For example, it is possible to add the polyether polyols (component B) to the water-dilutable polyurethane resin (component A) before, during or after formation of the emulsion, that is to say before, during or after the conversion of the water-dilutable polyurethane resin into the aqueous phase. The procedure can preferably be carried out in such a manner that the polyether polyols (component B) are added to the water-dilutable polyurethane resin (component A) before it is converted into the aqueous phase. If the polyether polyols are added before the conversion into the aqueous phase, it is also possible to add the polyether polyols to the NCO prepolymer together with the hydroxy-functional monoamines. The reaction conditions for the reaction of the NCO prepolymer with the hydroxy-functional monoamines are chosen in a manner known to the person skilled in the art so that the NCO groups react only with the amino groups.
The above-described water-dilutable polyurethane resins (component A) may optionally be used in combination with amounts of further water-dilutable OH-functional resins. There are suitable as further water-dilutable OH-functional resins, for example, conventional water-dilutable OH-functional (meth)acrylic copolymers, polyester resins, and optionally modified polyurethane resins other than the above-described water-dilutable polyurethane resins. The further water-dilutable OH-functional resins can be formulated as a binder composition together with the water-dilutable polyurethane resins (component A) and with component B) by mixing. However, they may also be added separately to the binder composition of component A) and component B).
Pigment pastes can advantageously be prepared from the binder composition according to the invention. Suitable pigments for the preparation of the pigment pastes are virtually all colouring and/or effect pigments. Suitable colouring pigments are all pigments of organic or inorganic nature customary in lacquers. Examples of inorganic or organic colouring pigments are titanium dioxide, micronised titanium dioxide, iron oxide pigments, carbon black, azo pigments, phthalocyanine pigments, quinacridone or pyrrolopyrrole pigments. Examples of effect pigments are metal pigments, for example of aluminium, copper or other metals; interference pigments, such as, for example, metal-oxide-coated metal pigments, for example titanium-dioxide-coated or mixed-oxide-coated aluminium, coated mica, such as, for example, titanium-dioxide-coated mica, and graphite effect pigments.
The pigment pastes prepared from the binder composition according to the invention may also contain water and small amounts of organic solvents as well as additives customary in lacquers.
The organic solvents optionally present in the pigment paste are solvents conventionally employed in lacquer technology. They may come from the preparation of the paste binder or are added separately. They are preferably water-miscible solvents. Examples of suitable solvents are mono- or poly-hydric alcohols, for example propanol, butanol, hexanol; glycol ethers or esters, for example diethylene glycol dialkyl ethers, dipropylene glycol dialkyl ethers, in each case with C1- to C6-alkyl, ethoxypropanol, butoxyethanol, glycols, for example ethylene glycol, propylene glycol, N-methylpyrrolidone as well as ketones, for example methyl ethyl ketone, acetone, cyclohexanone. The solvents may contain amounts of aromatic or aliphatic hydrocarbons, such as, for example, toluene, xylene or linear or branched aliphatic C6-C12-hydrocarbons. The organic solvents are present in an amount of up to, for example, a maximum of 10 to 15 wt. %, based on the total pigment paste.
Various lacquer additives may be incorporated into the pigment pastes prepared from the binder composition according to the invention. The additives are conventional additives which can be used in the lacquers sector and are known to the person skilled in the art. Examples of additives which may advantageously already be contained in the pigment paste are dispersing agents, wetting agents, antifoams, catalysts and substances for adjusting the pH value.
The ratio by weight of pigment to binder in the pigment paste can vary within relatively wide limits. It may be, for example, from 0.3:1 to 20:1, preferably from 0.5:1 to 15:1. The pigment:binder ratio to be set is dependent, for example, on the nature and particle size of the pigments used. In the case of formulations containing finely divided transparent pigments and containing carbon black, a pigment:binder ratio of from 0.8:1 to 2.0:1 can be used, for example, and in the case of formulations containing coarsely divided opacifying pigments, for example containing titanium dioxide, a pigment:binder ratio of from 4:1 to 8:1 can be used. In formulations containing metal effect pigments, for example aluminium pigments, a pigment:binder ratio of from 1.5:1 to 2.5:1 can be set, for example.
The pigment pastes containing the binder compositions according to the invention can be prepared in a conventional manner. For example, the individual constituents of the pigment paste can be mixed together and then ground in known dispersing units, for example in stirrer disk devices, three-roller mills, ball mills, sand or bead mills. That procedure is employed especially when colouring pigments are used. Units, dispersing times and other dispersing conditions depend essentially on the pigments used. If pigment pastes containing effect pigments, for example aluminium pigments or interference pigments, are to be prepared, then it is sufficient simply to stir or mix the pigments with the paste binder and optionally the further constituents of the pigment paste. Solids contents in the pigment paste of, for example, from 25 to 85 wt. % are obtained, depending on the pigment used.
The pigment paste can preferably contain, for example, from 5 to 90 parts by weight of pigment and from 10 to 95 parts by weight of the aqueous binder composition according to the invention. In addition, there may preferably be added, for example, from 0 to 40 parts by weight of water, from 0 to 10 parts by weight of organic solvents, from 0 to 5 parts by weight of neutralising agent and from 0 to 5 parts by weight of auxiliary substances. The above-mentioned parts by weight are to add up to 100 parts by weight.
It is also possible to combine the binder compositions according to the invention with amounts of further paste resins, which may likewise be OH-functional, in the pigment paste. The further paste resins which can optionally be used may be, for example, melamine resins, polyester resins, poly(meth)acrylates and/or optionally modified polyurethane resins other than the binder compositions according to the invention.
The invention relates also to aqueous coating compositions which contain the binder compositions according to the invention. The aqueous coating compositions may contain the binder compositions according to the invention as paste resin in the form of a pigment paste. It is, however, also possible for the aqueous coating compositions to contain the binder compositions according to the invention as paste resin and/or as the main binder (lacquering-up binder).
For the preparation of the aqueous coating compositions, the pigment pastes containing the binder compositions according to the invention are made up or lacquered up with a further binder, the actual main binder. There are suitable as lacquering-up binders all water-dilutable binders which are compatible with the paste resin and which are conventionally used for the preparation of water-based lacquers and water-based finishing lacquers for automotive and industrial lacquering. Examples of water-dilutable resins which can be used are polyurethane resins, polyester urethane resins, fatty-acid-modified polyester urethane resins, acrylated polyurethane resins and/or acrylated polyester resins, as well as poly(meth)acrylate resins. The lacquering-up binders may be used individually or in combination. Polyurethane resins and modified polyurethane resins are preferably used. Special preference is given to the use of mixtures of different polyurethane resins. It is, however, also possible to use the polyurethane resins in combination with other water-dilutable resins, for example with water-dilutable polyacrylate and/or polyester resins. Suitable polyurethane resins and suitable mixtures of polyurethane resins are described, for example, in DE-A-43 39 085, DE-A-39 36 794, DE-A-43 44 063, DE-A-41 15 042, DE-A-41 15 015, DE-A-43 23 896, DE-A-41 22 265, DE-A-42 28 510, DE-A-196 43 802, EP-A-089 497, EP-A-297 576.
It is also possible to use the binder composition according to the invention as the lacquering-up binder.
The aqueous coating compositions prepared with the binder compositions according to the invention may optionally also contain crosslinking agents. The crosslinking agents may be, for example, formaldehyde condensation resins, such as phenol-formaldehyde and amine-formaldehyde condensation resins, as well as blocked and unblocked polyisocyanates. Amine resins suitable as crosslinking agents are, for example, alkylated condensates which are prepared by reaction of aminotriazines and amidotriazines with aldehydes. To that end, amines or amino-group-carrying compounds, such as melamine, guanamine, benzoguanamine or urea, are condensed according to known processes with aldehydes, especially formaldehyde, in the presence of alcohols, such as methanol, ethanol, propanol, butanol or hexanol.
Polyisocyanates suitable as crosslinking agents are, for example, any organic polyisocyanates having aliphatically, cycloaliphatically, araliphatically and/or aromatically bonded free isocyanate groups. They are liquid at room temperature or liquefied by the addition of organic solvents. The polyisocyanates generally have a viscosity at 23xc2x0 C. of from 1 to 6000 mPas, preferably greater than 5 and less than 3000 mPas. Such polyisocyanates are generally known and are described, for example, in DE-A 38 29 587 or DE-A 42 26 243.
The polyisocyanates are preferably polyisocyanates or polyisocyanate mixtures having solely aliphatically and/or cycloaliphatically bonded isocyanate groups having a mean NCO functionality of from 1.5 to 5, preferably from 2 to 3.
Especially suitable, for example, are xe2x80x9clacquer polyisocyanatesxe2x80x9d based on hexamethylene diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (IPDI) and/or bis(isocyanatocyclohexyl)-methane and the derivatives, known per se, of those diisocyanates containing biuret, allophanate, urethane and/or isocyanurate groups. Triisocyanates, such as nonane triisocyanate, may also be used. Sterically hindered polyisocyanates are also highly suitable. Examples thereof are 1,1,6,6-tetramethyl-hexamethylene diisocyanate, 1,5-dibutyl-pentamethyl diisocyanate, p- or m-tetramethylxylylene diisocyanate and the corresponding hydrogenated homologues. Those diisocyanates can also be converted in a suitable manner into compounds having a higher functionality, for example by trimerisation or by reaction with water or trimethylolpropane.
Blocked polyisocyanates may also be used as crosslinking agents. They are, for example, the polyisocyanates already mentioned above, which have been blocked with conventional volatile monovalent blocking agents. There are used as blocking agents, for example, alkyl monoalcohols, phenols, oximes, amines, phthalimide or beta-keto compounds.
However, further crosslinking agents known in the lacquers industry can also be used, providing the appropriate reactive groups are available in the binders that are used.
The crosslinking agents may be used individually or in admixture.
They are the crosslinking agents customary in the lacquers industry, which are comprehensively described in the literature and are obtainable as commercial products.
If crosslinking agents are to be used in the coating compositions, the choice of crosslinking agents is dependent on the crosslinkable functional groups in the lacquering-up binder(s) and/or in the paste binder. Especially advantageous binder systems are those containing crosslinking agents that react with hydroxyl groups, since the paste binder with its hydroxyl groups can then be included in the crosslinking reaction. It is not absolutely necessary for the lacquering-up binder also to contain crosslinkable functional groups. The lacquering-up binders may also be, for example, physically drying binders, so that a crosslinking reaction takes place only between the paste resin and the crosslinking agent.
The aqueous coating compositions prepared with the binder compositions according to the invention may also contain water, small amounts of organic solvents, and additives customary in lacquers. Examples of additives customary in lacquers are flow agents, agents affecting rheology, such as highly disperse silica or polymeric urea compounds, thickeners, such as crosslinked polycarboxylic acid or polyurethanes, antifoams, wetting agents, anti-pitting agents and hardening accelerators. The additives are used in conventional amounts known to the person skilled in the art. The aqueous coating compositions may also contain crosslinked polymer microparticles.
There may be added to the aqueous coating compositions effect pigments, such as, for example, the aluminium and/or interference pigments mentioned above, also in a conventional manner, for example in the form of a solvent paste, and not as a pigment paste containing paste resin.
Amounts of organic solvents may be present in the coating compositions, preferably not more than 20 wt. %, especially not more than 15 wt. %. The organic solvents are preferably water-miscible. They are conventional solvents customary in lacquering technology. They may come from the preparation of the binders or are added separately. Examples of such solvents are the solvents already mentioned above which can be used for the preparation of the pigment pastes.
For the preparation of the coating compositions, the pigment paste and/or the lacquering-up binder(s) and the further constituents are thoroughly mixed together and homogenised in a conventional manner. Owing to the good wetting properties of the paste binder, lacquering up takes place while the state of dispersion is maintained, that is to say flocculation of the pigments is prevented.
If lacquers containing both colouring and effect pigments are to be prepared, it is advantageous to prepare pigment pastes containing the colouring pigments and pigment pastes containing the effect pigments separately and then combine the two pigment pastes during formulation of the lacquer.
The coating compositions containing the binder compositions according to the invention can be formulated on the basis of physically drying or chemically crosslinking binders. If, for example, they are two-component coating compositions, the binder components that react together must be stored separately and cannot be mixed together until shortly before application.
In general, the coating compositions can, if required, be adjusted to the spraying viscosity before application, using water or organic solvents.
The hardening conditions are dependent on the choice of binders and the possible crosslinking agents. With appropriate selection of the crosslinking agents, for example in the case of polyisocyanate crosslinking agents, the coating compositions do not require baking and can be hardened at room temperature or forced at higher temperatures, for example up to 80xc2x0 C., preferably up to 60xc2x0 C. However, it is also possible to harden them at higher temperatures of, for example, from 80 to 150xc2x0 C., for example when they contain melamine resins and/or blocked polyisocyanates.
The aqueous coating compositions containing the binder compositions according to the invention are especially suitable for the preparation of colouring and/or effect base layers as well as pigmented finishing lacquer layers in the case of multi-layer lacquering. The preferred field of application is the lacquering of motor vehicles and motor vehicle parts. The binder compositions according to the invention and the coating compositions containing them can be used, according to the hardening conditions, both for vehicle repair lacquering (hardening temperatures of, for example, from 20 to 80xc2x0 C.) and for the series lacquering of motor vehicles (hardening temperatures of, for example, from 100 to 140xc2x0 C.).
Other industrial applications are also possible, however.
Accordingly, the invention relates also to the use of the coating compositions containing the binder compositions according to the invention in a process for multi-layer lacquering, in which a filler layer is applied to an optionally pre-coated substrate, for example to a substrate pre-coated with a primer, and a finishing lacquer layer is applied to the filler layer, wherein the finishing lacquer layer can be applied in the form of a pigmented single-layer finishing lacquer or in the form of a colouring and/or effect base lacquer layer and a clear lacquer layer applied thereto, and wherein the single-layer finishing lacquer and the base lacquer contain the binder compositions according to the invention. The clear lacquer can be applied to the base lacquer either after drying or hardening or wet-in-wet, optionally after exposure to air for a short time. Suitable clear lacquers are in principle all known unpigmented or transparently pigmented coating compositions, such as are customary, for example, in the lacquering of motor vehicles. They may be solvent- or water-based single- or two-component clear lacquers or powdered clear lacquers.
The coating compositions are applied by conventional methods, preferably by means of spray application.
Suitable substrates are metal and plastics substrates, especially the substrates known in the automotive industry, such as, for example, iron, zinc, aluminium, magnesium, stainless steel or alloys thereof, as well as polyurethanes, polycarbonates or polyolefins.
Pigment pastes and/or water lacquers prepared from the binder compositions according to the invention are stable to frost and storage. They exhibit no settling of the pigments even after prolonged storage. High-gloss coatings having a high degree of resistance to chemicals and very good hardness are obtained. If pigment pastes containing metal pigments, especially aluminium pigments, are prepared and incorporated into corresponding coating compositions, the coating compositions have a considerably lower solvent content than metal effect lacquers prepared in the conventional manner using a solvent paste of the aluminium pigments. The coatings exhibit a very good metallic effect. In contrast to high molecular weight dispersions or emulsions, the binder compositions according to the invention are stable to shear, so that they are especially suitable for the milling of pigments. On account of their very good wettability, especially highly concentrated pigment pastes can be prepared.
Pigment pastes prepared from the binder compositions according to the invention, especially white pigmented pastes, produce coating compositions having a very good covering power. With the paste binders according to the invention, a deep black can also be formulated as a shade of colour.

Water-dilutable binder agent composition

Abstract: a1) hydroxy-functional compounds having a molar mass (Mn) of from 360 to 8000 with

Abstract: a2) polyisocyanates and

Abstract: a3) compounds having at least one group that is able to react with isocyanates and at least one ionic group,

Abstract: II) subsequently reacting the polyurethane prepolymer with

Abstract: a4) hydroxy-functional monoamines and, optionally, polyols, and

Abstract: III) neutralising groups that can be converted into ionic groups, and from 2.0 to 25 wt. %, based on the solids content of polyurethane urea resin, of one or more polyether polyols having a molar mass of from 400 to 5000.


Visual task feedback for workstations in a materials handling facility may be implemented. Image data of a workstation surface may be obtained from image sensors. The image data may be evaluated with regard to the performance of an item-handling task at the workstation. The evaluation of the image data may identify items located on the workstation surface, determine a current state of the item-handling task, or recognize an agent gesture at the workstation. Based, at least in part on the evaluation, one or more visual task cues may be selected to project onto the workstation surface. The projection of the selected visual task cues onto the workstation surface may then be directed.

The efficient movement, storage, and control of items is more important than ever. Advances in communicating orders for items have led to increased expectations as to the promptness in which these orders are fulfilled. Various suppliers, merchants, distributors, or other conveyors of goods, may operate materials handling facilities to store and move items to satisfy received orders as part of a fulfillment network. For example, electronic marketplaces, such as those accessible via the Internet, may include a catalog of items or products available for purchase. These items may be offered as the basis for commerce (e.g., sale or trade). Customers may utilize a web browser to visit a merchant's website, select an item for purchase from the catalog, and engage in a checkout process to finalize an order for the item. The merchant may operate a fulfillment network including various materials handling facilities in order to process such orders, such as a facility that maintains an inventory of items, picks the ordered item from inventory, and prepares shipments of the purchased item. A shipment carrier may acquire such shipments from the merchant and deliver the shipments to the respective purchasing customers.
Improvements to materials handling systems have increased the throughput in which items may be processed at materials handling facilities. For instance, automation techniques for processes such as storing and retrieving items from inventory, as well as conveying items within a materials handling facility, may improve the performance of these processes. Some processes, however, are less susceptible to existing techniques for automation.
While embodiments are described herein by way of example for several embodiments and illustrative drawings, those skilled in the art will recognize that the embodiments are not limited to the embodiments or drawings described. It should be understood, that the drawings and detailed description thereto are not intended to limit embodiments to the particular form disclosed, but on the contrary, the intention is to cover all modifications, equivalents and alternatives falling within the spirit and scope as defined by the appended claims. The headings used herein are for organizational purposes only and are not meant to be used to limit the scope of the description or the claims. As used throughout this application, the word "may" is used in a permissive sense (i.e., meaning having the potential to), rather than the mandatory sense (i.e., meaning must). Similarly, the words "include", "including", and "includes" mean including, but not limited to.

Visual task feedback for workstations in materials handling facilities


Disclosed in an ink jet recording apparatus capable of providing high quality images in a stable manner for image signals of different transfer rates. A detector detects the receiving rate of an image signal supplied to the ink jet recording apparatus, and at least one of driving voltage, driving current, pulse duration, driving frequency and driving signal wave form is modified according to the detected receiving rate of the image signal.

1. Field of the Invention
The present invention relates to an ink jet recording apparatus having a function as facsimile, a copying machine or a printer, a composite apparatus having these functions, or an ink jet recording apparatus utilized as output equipment for example of a work station.
2. Related Background Art
Ink jet recording apparatuses have been developed and commercialized actively in recent years because of various advantages, and are known in various types such as based on ink discharge utilizing a piezoelectric element or utilizing ink bubbles generated by an electrothermal converting element such as a heat-generating resistor.
In an ink jet recording apparatus of the recording method utilizing the electrothermal converting element, a voltage or current pulse is supplied, in response to the image signal, to said converting element to generate thermal energy, thereby inducing a state change in the ink such as membrane boiling. A bubble is generated by said state change, and ink is discharged toward the recording material by the force of said bubble. The characteristics of bubble generation and discharge of the ink are dependent on the physical properties, for example, viscosity, of the ink, and therefore vary, in general, with the temperature thereof. For this reason, there is provided temperature control means as disclosed for instance in U.S. Pat. No. 4,719,472, for controlling the ink temperature within a certain range.
Also, the state of bubble generation is dependent on the voltage, current and duration of the pulse applied to the electrothermal converting element, so that these parameters are selected at optimum values according to the resistance or the surface characteristics of said electrothermal converting element.
A high image quality can be obtained in a stable manner by controlling the driving conditions in an optimum range as explained above.
However, with the progress of system integration, there is often encountered a situation where the same ink jet recording apparatus is used not only as a printer but also is output equipment of a facsimile apparatus or a copying machine, with respectively different transfer rates of the image signal. For example, an ink jet recording apparatus may have a printer mode in which the image signal is received at every 500 .mu.sec. and a facsimile mode in which the image signal is received at every 10 msec.
Such different receiving rates of the image signal varies the recording speed, thereby also causing a change in the aforementioned optimum driving conditions, so that the conventional recording apparatus is unable to provide stable recorded images.
Also, in the compressed image transmission as in the facsimile apparatus, the above-mentioned difficulty is encountered even for the same receiving rate, as the effective image signal receiving rate varies if the image compression rate is different.

Ink jet recording apparatus and method with drive control dependent on an image signal receiving frequency


The window of a holding electrode is a rectangular opening and an insulating plate is securely fitted in this window. The insulating plate has a rectangular flange shape having a rectangular opening. A glass substrate is securely fitted in the opening of the insulating plate. While the insulating plate may be a low-cost glass plate or quartz plate, the glass plate made of the same material as the glass substrate is used. A predetermined raw gas is supplied into a reaction chamber to set the pressure therein to a predetermined level, and high-frequency power is applied between the glass substrate and the electrode. Because the peripheral portion of the glass substrate is surrounded by the insulating plate, it is possible to avoid the influence of the disturbance of the electric field which would otherwise occur at the interface between the substrate surface and the surface of the holding electrode due to the surface of the glass substrate being charged up when growing a film. This allows a film with a uniform thickness to be grown on the glass substrate.

1. Field of the Invention
The present invention relates to a parallel flat type plasma CVD apparatus.
2. Description of the Related Art
In the fabrication of thin-film semiconductor devices, a parallel flat type plasma CVD apparatus is used to form thin films. FIG. 1 presents a cross-sectional view of a conventional plasma CVD apparatus. Provided on the upper inner wall of a reaction chamber 5 is a heater panel 4 with its heating surface set horizontally. A metal holding electrode 2 is provided below the heater panel 4 in the reaction chamber 5. A glass substrate 1 is attached to this holding electrode 2.
The holding electrode 2 has an open center in which a window 2a for placing the glass substrate 1 is provided, as shown in FIG. 2. A small projection is provided at the lower portion of the window 2a to be used to mount the glass substrate 1 in the window 2a. A uniform heating plate 3 is placed on the glass substrate 1 and is secured to the holding electrode 2 by means of a fastener 9.
A gas guiding member 7 for guiding, for example, SiH.sub.4 and H.sub.2 into the reaction chamber 5 is mounted on the bottom wall of the reaction chamber 5 via an insulating member 5a. This gas guiding member 7, made of a conductive material, has a top end portion extending horizontally with multiple gas outlet holes 6a formed in the top of the top end portion. The portion where the gas outlet holes 6a are formed constitutes a high-frequency electrode 6. This high-frequency electrode 6 faces the holding electrode 2 under the holding electrode 2.
A high-frequency power supply 11 is connected to the gas guiding member 7 so that high-frequency power having an oscillation frequency of 13.56 MHz is applied via the gas guiding member 7 to the high-frequency electrode 6 from the high-frequency power supply 11.
A gas discharge port 8 is provided in the bottom wall of the reaction chamber 5, which is grounded.
According to the thus constituted conventional plasma CVD apparatus, when a raw gas is supplied into the reaction chamber via the gas guiding member 7 while the glass substrate 1 is heated by the heater panel 4, and high-frequency power is applied between the high-frequency electrode 6 and the holding electrode 2 and glass substrate 1 by the high-frequency power supply 11, an amorphous silicon film is grown on the glass substrate 1.
When a thin film is formed by this conventional plasma CVD apparatus, the peripheral portion of the glass substrate 1 is affected by the holding electrode 2 because of the difference between the surface potential of the glass substrate 1 and that of the holding electrode 2. As a result, the film thickness changes from the center portion of the substrate to its periphery, and the film thickness is not uniform.
As a solution to this problem, a technique has been proposed by which an insulating member is attached, by means of screws or the like, onto the surface of the electrode (holding electrode) located on the side where the insulator substrate is to be attached, thus ensuring a uniform electric field to provide improved uniformity of the film thickness (see Unexamined Japanese Patent Publication No. Sho 62-189725). Unexamined Japanese Patent Publication No. Sho 61-177374 proposes another technique, by which an insulating ring is attached to the peripheral portion of the electrode located opposite the substrate, for uniform plasma distribution in the discharge area and improved uniformity of the film thickness.
The former method that attaches an insulating member to the electrode surface in order to make the electric field of the entire substrate uniform at the time of forming the thin film, thus improving the film thickness distribution, also forms a film on this insulating member, which may produce particles. This method therefore requires regular cleaning of the insulating member. At the time the insulating member is cleaned, the film formed on the surface of the insulating member must be removed by a plastoprocess and etching or the like and the insulating member must then be secured again to the electrode surface by screws. It is apparent that this method requires complicated maintenance work.
Like the former method, the latter method of attaching the insulating ring to the peripheral portion of the electrode located on the side opposite the substrate also requires complicated maintenance work.

Plasma CVD apparatus for forming a thin film of uniform thickness


An apparatus for generating a depth map includes a communication interface configured to receive video; a processor configured to generate depth map of the video according to a predetermined instruction; and a memory configured to store the instruction, wherein the instruction comprises instructions configured to perform: receiving an input to set a start point and an end point; providing a reference figure corresponding to the start point and the end point; and generating a depth map corresponding to the reference figure.

1. Technical Field
The present invention relates to a technology for generating a depth map from a video and more particularly, to a technology for generating a depth map of video according to a user's input.
2. Description of the Related Art
There are various methods for generating and editing a depth map from 2D video but many parts are carried manually.
There is a 3D mesh method for obtaining a depth map manually from 2D video, but it requires time and effort for generating a model at the beginning and editing it. There is also a painting method for generating a depth map but it can cause flickering problem since it is difficult to generate and edit depth maps consistently between image frames for image sequence when the depth map is generated by the painting method.

Apparatus and method for generating a depth map

ELECTRONICS AND TELECOMMUNICATIONS RESEARCH INSTITUTE


In manufacturing a magnetic recording disk, a magnetic film for a recording layer is deposited on a substrate of the magnetic recording disk in a magnetic-film deposition chamber, and the substrate is transferred from the magnetic-film deposition chamber to a lubricant-layer preparation chamber without exposing the substrate to the atmosphere. Then, a lubricant layer is prepared on the substrate in the lubricant-layer preparation chamber.

This invention relates to manufacture of magnetic recoding disks. Especially, this invention relates to a step of removing protrusions on a substrate and a step of forming a lubricant film on the substrate.
The manufacture of a magnetic recording disk such as a hard disk is roughly divided into former steps and latter steps. The former steps include deposition of an underlying film, deposition of a magnetic film for a recording layer, and deposition of an overcoat. The latter steps include preparation of a lubricant layer and other required steps. The lubricant layer is prepared considering contact of a magnetic head onto the disk in read-out.
The preparation of the lubricant layer is carried out by a following procedure.
To begin with, a substrate is taken out to the atmosphere after deposition steps because thin-films such as the magnetic film for a recording layer are usually deposited in a vacuum chamber. Then, burnishing is carried out to remove contaminants adhering to the substrate and to remove protrusions formed on the substrate during the film depositions. The burnishing is the step of removing the protrusions and the contaminants from the substrate by rubbing it with a tape-shaped polishing member. xe2x80x9cContaminantxe2x80x9d in this specification means material that may contaminate a substrate in general, which is gas, ion, molecular, particle or another substance.
The lubricant layer is prepared after the burnishing. As lubricant, a fluorine lubricant such as perfluoropolyether (PFPE) is used. Such the lubricant is diluted with solvent for improving uniformity. The diluted lubricant is coated onto the substrate by such a method as the dipping method where the substrate is dipped into the stored lubricant, or the spin-coating method where the lubricant is dropped onto the substrate when it is spun.
xe2x80x9cSubstratexe2x80x9d means a board that consists a magnetic recording disk in this specification. xe2x80x9cSurface of substratexe2x80x9d may mean a surface of a film or layer when a film deposition or a layer preparation has already been carried out onto the substrate.
Recent improvement of recording density in magnetic recording disks is remarkable. For example, in hard disks it is becoming 20 gigabit/inch2 in the year 2000 and 40 gigabit/inch2 in the year 2001. One of factors that enable the improvement of the recording density is to reduce the spacing. FIG. 19 shows a view explaining the spacing.
In FIG. 19, the spacing in case of hard disks is explained as an example. As shown in FIG. 19, a hard disk has the structure where a recording layer 91 is prepared on a substrates 9, an overcoat 92 is deposited on the recording layer 91, and a lubricant layer 93 prepared on the overcoat 92. A magnetic head for write and readout of information is located at a position slightly apart from the surface of the hard disk. The spacing, which is designated by xe2x80x9cSxe2x80x9d in FIG. 19, means distance between the write-readout device element 900 of the magnetic head and the recording layer 91 of the hard disk. Distance between the write-readout device element 900 and the lubricant layer 93 is called xe2x80x9cflying heightxe2x80x9d, which is designated by xe2x80x9cFHxe2x80x9d in FIG. 19. It is important to make the spacing S small in improving the recording density.
As the spacing S becomes smaller, demands to the manufacturing process have been becoming severer by years. For reducing the spacing S, it is required not only to reduce the flying height FH, which is about 10 to 20 nm in a typical hard disk drive (HDD) currently on sale in the market, but also required to make thickness of the overcoat 92 and thickness of the lubricant layer 93 thinner. As thickness of the overcoat 92 is made thinner, it is required to deposit a more compact and harder film as the overcoat 92. As thickness of overcoat 92 is made thinner, demand for thickness uniformity of the lubricant layer 93 becomes severer as well as demand for enhancing adhesion strength of the lubricant layer 93 becomes severer.
With the above described points in the background, method for depositing the overcoat 9 has been shifting from the conventional sputtering method to the chemical vapor deposition (CVD) method. Usually a carbon film is deposited as the overcoat 92. By the CVD method, it is enabled to deposit a carbon film called xe2x80x9cdiamond-like carbonxe2x80x9d (DLC) film. DLC film is known as the hard, compact and stable carbon film even when its thickness is small. This is the reason why the method has been shifting to the CVD method.
However, contaminants of gases or ions may adhere to the overcoat 92 under influence of residual gases when it is deposited by the CVD method. In addition, minute protrusions are easily formed on the overcoat 92 in the CVD method, resulting from abnormal film growth. If the lubricant layer 93 is prepared over the overcoat 92 on which contaminants or protrusions exist, there easily arise problems such as adhesion strength of the lubricant layer 93 may decrease, and thickness of the lubricant layer 93 may lose uniformity.
Adhesion strength of the lubricant layer 93 is enhanced when terminal groups of macromolecules composing the lubricant are bonded sufficiently with a carbon of the overcoat 92. For making adhesion strength higher, it is preferable that the macromolecules are bonded with a carbon in the surface of the overcoat 92 at one of or both terminal groups. On the other hand, it is desirable that degree of freedom of the macromolecules is high at the portion adjacent to the surface of the lubricant layer 93, on purpose of prevention the write-readout device element 900 of the magnetic head from chucking with the disk. In short, both terminal groups are preferably not bonded.
Macromolecule bonded with a carbon at one of or both terminal groups is hereinafter called xe2x80x9cbonded lubxe2x80x9d. Macromolecule not bonded with a carbon at either of terminal groups is hereinafter called xe2x80x9cfree lubxe2x80x9d. Thickness ratio of the bonded lub layer against the whole lubricant layer 93 is hereinafter called xe2x80x9cbonded ratioxe2x80x9d. Though the optimum bonded ratio has been supposed about 20-30% so far, demand for accuracy of the bonded ratio tends to be severer as the lubricant layer 93 is made thinner.
For obtaining the demanded bonded ratio, it has been attempted to carry out treatment for controlling bonds of the terminal groups after the lubricant-layer preparation. In this treatment, thermal energy or light energy is applied to the lubricant layer 93, thereby controlling bonds of the terminal groups. This treatment is hereinafter called xe2x80x9cpost-preparation treatmentxe2x80x9d.
However, when the overcoat 92 is exposed to the atmosphere after the deposition, many contaminants of gases or ions in the atmosphere are adsorbed with the surface the overcoat 92 because the surface has been chemically activated. As a result, when the lubricant layer 93 is prepared, a contamination layer may be formed between the lubricant layer 93 and the overcoat 92. If the contamination layer is formed, it may become difficult to obtain an accurate bonded ratio by the post-preparation treatment. For preventing these problems, equipment that reduces contaminants is required. Including such the point, the current situation is that huge investment is inevitable for coordinating manufacture environment.
Object of the invention is to solve the described problems in the manufacturing process, which have been brought from the reduction of the sp acing.
To accomplish this object, the invention presents a method and an apparatus for manufacturing a magnetic recording disk, where steps from magnetic-film deposition to lubricant-layer preparation are carried out without vacuum breaking. The invention also presents a method and an apparatus for manufacturing a magnetic recording disk, where a substrate is cleaned prior to lubricant-layer preparation. The invention also presents a method and an apparatus for manufacturing a magnetic recording disk, where burnishing is carried out in vacuum after magnetic-film deposition. The invention also presents a method and an apparatus for manufacturing a magnetic recording disk, where post-preparation treatment to coordinate adhesive strength and surface lubricity of a lubricant layer is carried out in vacuum. The invention also presents an in-line type substrate processing apparatus comprising a plurality of vacuum chambers provided along each of a plurality of circumventive transfer paths, a connection transfer path connecting at least two of the circumventive transfer paths, and a transfer system that transfers a substrate to be processed along the circumventive transfer paths and the connection transfer path without exposing the substrate to the atmosphere.

Method for manufacturing a magnetic recording disk


Methods and devices for executing scripts written in a dynamic scripting language include parsing scripts in two stages, a pre-parse using a simplified grammar to generate script metadata regarding the high level structure of the script, and a full parse using the grammar and syntax of the dynamic scripting language and generated script metadata. The generated metadata may describe the high level structure that is present in the language of the script such as functions, object methods, and a top level call graph. The script metadata may be used during the full parse to determine the parts of the code to be fully parsed. The aspects minimize processing time spent in the parsing at run-time, and may eliminate processing required to interpret or compile sections of code that will not be executed. Script metadata as well as results of full parsing may also be cached to provide further processing efficiencies.

Dynamic scripting languages are presently a preferred development platform in computer programming and software development. In particular, JavaScript® is the main development language for web pages and web applications on the client side, while Python and Ruby are very popular languages for software development on the server side. Such programming languages are designed for interactive execution (scripting), and are thus, by necessity, dynamic (i.e., support dynamic types, reflection and introspection, and extensibility). Dynamic scripting languages typically execute via interpretation, in which, at runtime, the scripts are parsed and analyzed before they are executed.
Recently, just-in-time compilation has been introduced for a number of these languages, such as JavaScript, to address performance issues of dynamic languages. However, performance problems persist. This is particularly the case in constrained computing environments, such as a mobile device, where the performance and power efficiency of executing dynamic languages continue to be issues.

Execution of dynamic languages via metadata extraction


A scaffold system having modular components including interconnectable side walls or side trusses having extruded upper and lower truss members, decks and various section connectors which are interchangeable simplifying transportation, minimizing storage and reducing inventory requirements. Single person set-up and take-down is provided in a modular scaffolding system allowing assembly of a vast array of configurations that accommodate various architectural shapes. Drop-in assembly of aluminum side trusses of modular scaffold sections with steel modular scaffold section connectors provides strong construction. Spring loaded latched are used to maintain decks in place at modular scaffold section connectors.

This invention relates to modular scaffolding systems for the construction and maintenance industries.
One example of a modular scaffolding system, shown in U.S. Pat. No. 4,749,060 to Vandelinde entitled "Modular Stage Platform" issued Jun. 7, 1988 employs preassembled stage platforms which are interconnected at their ends with male and female connectors comprising vertical plates extending at opposite ends of such platforms. The connections may be maintained with fasteners including cylindrical rods or connecting pins. The patent discloses a platform in which its side trusses and deck are welded together to form a large box-like structure which cannot be easily transported in a flattened state. Some scaffolding systems have detachable side trusses and decks so that the scaffolding may be transported in a flat, knock down state.
Since scaffolding systems are intended as temporary structures, they are repeatedly assembled, disassembled and moved from place to place, and are exposed to wear and tear during their lifetimes. Additionally, scaffolding is often handled roughly such that components are subject to impact loads and stress concentrations when loaded onto and off of trucks. In such environments, protruding members for interconnecting stage platforms such as male and female connectors located at the ends of the platforms are often problematic because such connectors are often bent or otherwise damaged making interconnection of platforms difficult or impossible, and possibly reducing their strength.
It is desirable that a modular scaffolding system be simple to put together using relatively few parts and flexible assembly procedures with few or no tools. Of course, scaffolding systems also must exhibit uncompromising strength under adverse working conditions. Many presently available scaffolding systems are heavy, cumbersome and hard to move from place to place such as that disclosed in U.S. Pat. No. 4,749,060. Many preassembled stage platforms are modular only to the extent that they are interconnectable with other stage platforms. Such scaffolding systems do not employ exchangeable and interchangeable modular componentry such as detachable side trusses and decks that may be transported in a flat stack on a bed of a pick-up truck and readily erected and connected to one another to form a scaffolding. Moreover, some such stage platforms have welded joints which are subject to undesirably high shear and tensile stresses.


A composition and method for inhibiting corrosion of ferrous metals in contact with an aqueous solution comprising adding to the system from 0.1 to 500 ppm of an aminohydroxysuccinic acid compound selected from group consisting of compounds of the generalized formulas: ##STR1## wherein R is H or C.sub.1 to C.sub.6 alkyl, optionally substituted with --OH, --CO.sub.2 H, --SO.sub.3 H or phenyl, C.sub.4 C.sub.7 cycloalkyl, or phenyl which is optionally substituted with --OH, or --CO.sub.2 H, and R' is H, C.sub.1 to C.sub.6 alkyl, optionally substituted with --OH or CO.sub.2 H; and ##STR2## wherein R' is as above, and Z is selected from the group consisting of i) --(CH.sub.2).sub.n -- wherein n is an integer from 2 to 10, ii) --(CH.sub.2).sub.2 --X--(CH.sub.2).sub.2 -- wherein X is --O--, --S--, --NR"--; wherein R" is selected from the group consisting of H, C.sub.1 to C.sub.6 alkyl, hydroxyalkyl, carboxyallkyl, acyl, --C(O)OR"' wherein R"' is C.sub.1 C.sub.6 alkyl or benzyl and ##STR3## wherein R' is as above, ##STR4## wherein Y is H, C.sub.1 to C.sub.6 alkyl, alkoxy, halogen, --CO.sub.2 H, or --SO.sub.3 H, m is independently 0 or 1 and p is 1 or 2, and ##STR5## wherein R.sub.a and R.sub.b are independently H or C.sub.1 to C.sub.6 alkyl, Q is H or C.sub.1 to C.sub.6 alkyl and S is 0, 1 or 2; t is independently 0, 1, 2 or 3 and q is 0, 1, 2, or 3, and r is 1 or 2; or water soluble salts thereof.

Iron and iron-based metal alloys containing alloys such as mild steel are well-known materials used in constructing the apparatus of aqueous systems. In these systems water circulates, contacts the iron based metal surface, and may be concentrated, such as by evaporation of a portion of the water from the system. Even though such metals are readily subject to corrosion in such environments, they are used over other metals due to their strength and availability.
It is known that various materials which are naturally or synthetically occurring in the aqueous systems, especially systems using water derived from natural resources such as seawater, rivers, lakes and the like, attack ferrous-based metals. The term "ferrous-based metals", as used herein, shall mean any iron metal and/or metal alloys containing iron therein. Typical systems in which the iron metal parts are subject to corrosion include evaporators, single and multi-pass heat exchangers, cooling towers, and associated equipment and the like. As the water passes through or over the system, a portion of the system water evaporates thereby increasing the concentration of the dissolved materials contained in the system. These materials approach and reach a concentration at which they may cause severe pitting and corrosion which eventually requires replacement of the metal parts. Various corrosion inhibitors have been previously used to treat these systems.
For example, chromates, inorganic phosphates and/or polyphosphates have been used to inhibit the corrosion of metals which are in contact with water. The chromates, though effective, are highly toxic and consequently present handling and disposal problems. While phosphates are non-toxic, due to the limited solubility of calcium phosphate, it is difficult to maintain adequate concentrations of phosphates in many aqueous systems. Polyphosphates are also relatively non-toxic, but tend to hydrolyze to form orthophosphate which in turn, like phosphate itself, can create scale and sludge problems in aqueous systems (e.g. by combining with calcium in the system to form calcium phosphate). Moreover, where there is concern over eutrophication of receiving waters, excess phosphate compounds can serve as nutrient sources. Borates, nitrates, and nitrites have also been used for corrosion inhibition. These too can serve as nutrients in low concentrations, and/or represent potential health concerns at high concentrations.
Environmental considerations have also recently increased concerns over the discharge of other corrosion inhibiting metals such as zinc, which previously were considered acceptable for water treatment.
Much recent research has concerned development of organic corrosion inhibitors which can reduce reliance on the traditional inorganic inhibitors. Among the organic inhibitors successfully employed are numerous organic phosphonates. These compounds may generally be used without detrimentally interfering with other conventional water treatment additives. However, environmental concerns about the discharge of phosphorus in the form of organic phosphonates have begun to be heard. It is anticipated that in the future this will lead to limitations on the use of organic phosphonates in water treatment.
Another serious problem in industrial aqueous systems, especially in cooling water systems, evaporators, and boilers is the deposition onto heat transfer surfaces of scale, particularly scale-forming salts such as certain carbonates, hydroxides, silicates and sulfates of cations such as calcium and magnesium. Much of the water used in these systems contain various amounts of scale-forming salts. Because of the evaporation which takes place in these aqueous systems, the solids in the water become more concentrated; and, because of the inverse solubility of calcium carbonate, calcium sulfate and other hardness salts, the problem of the formation of water-insoluble scales on the heat transfer surfaces is intensified. In addition, many organic corrosion inhibitors (e.g. hydroxyethylidene diphosphonic acid) are very sensitive to calcium i.e., they have a high tendency to precipitate with calcium ions in solution.
Thus, there is a continuing need for safe and effective water treating agents which can be used to control corrosion, particularly when a substantial concentration of dissolved calcium is present in the system water. Water treating agents of this type are particularly advantageous when they are phosphorus-free.


A system for cleaning a grain dryer screen includes a grain dryer screen supported within a grain bin and having a grain contacting surface opposing a grain debris contacting surface. A drying airflow path through the grain dryer screen is defined sequentially by the grain debris contacting surface and the grain contacting surface. A cleaning assembly includes a first cleaning arm mounted within the grain bin and disposed along the grain debris contacting surface. A cleaning assembly powering system is configured to move the first cleaning arm along a predetermined cleaning path relative to the grain debris contacting surface.

Grain bins are used for storing a variety of bulk materials, including grains, such as corn and wheat. At harvest, these grains typically contain excess moisture and, thus, need to be dried sufficiently and soon after harvest, to prevent insect infestation and quality deterioration. The purpose of storage, after the drying process, is to provide the dried grains with protection against insects, molds, rodents and birds, and to prevent moisture from re-entering the grains. Grains may be dried using traditional sun drying or may be dried mechanically. Mechanical drying systems may include heater systems located internally or externally relative to the grain bin. One exemplary in-bin drying system includes a top dry grain drying system. According to a top dry system, a layer of grain introduced into an overhead drying chamber within a grain bin is dried by a fan and heater and then dumped to a cooling area below. According to some designs, a smaller aeration fan captures heat from this previously dried grain received in the holding area, and pushes it upward to help dry the next layer of grain.
With regard to the top dry grain drying system, and other similar systems, there is a continuing need to improve efficiency and safety of the systems and methods employed to dry and store bulk materials. The present disclosure is directed to such an effort.

System and method for cleaning grain dryer screen


One of female and male connectors is installed on a mounting base in a waiting through a holder in a waiting condition, and can be freely coupled with the other connector in a projecting waiting direction of the one connector. The one connector is provided freely slidably in the holder and after the other connector is coupled with the one connector, both the connectors are freely slidable relative to the holder toward the mounting base while in a coupling condition. A clearance is provided between the holder and the one connector. A hood of the one connector is provided slidably in the holder. A flexible arm of the holder has an engaging portion at an end thereof. The one connector includes a flexible engaging piece having an engaging portion to be fit to/released from the engaging portion of the flexible arm; and the flexible engaging piece is freely contactable with a side wall in the vicinity of the flexible arm of the holder.

1. Field of the Invention
This invention relates to a connector coupling structure which is used in, for example, vehicle door and is preferable for coupling female and male connectors having multiple poles with each other or uncoupling them.
2. Description of the Relevant Art
In a vehicle door, a switch unit such as a power window switch unit is installed on a door trim by fitting a connector of wire harness placed on the door panel to a connector of switch unit to be installed on the door panel through a door trim.
FIG. 1 is a diagram for explaining an installation procedure of a conventional connector for vehicle door.
First, a wire harness 102 is placed on a door panel 101 and next waterproof sheet 103 is bonded to this door panel 101. A switch unit such as a power window switch unit is installed on a door trim 105 and a connector 107 of the switch unit 104 is fit to a connector 106 which is connected to an end of the wire harness 102 placed in the door panel 101 and finally the door trim 105 is installed on the door panel 101.
A connector coupling structure suitable for this kind of use has been disclosed in Japanese Patent Application Laid-Open Publication No. 9-55262.
FIGS. 2A to 2D are diagrams for explaining a conventional connector coupling structure.
In the conventional connector coupling structure, as shown in FIG. 2A, a female connector 205 provided on an electrical device 204 is fit to a male connector 201 which is inserted into an insertion hole 208a of a connector mounting plate 208 through a mounting opening 209a of an instrumental panel 209. This male connector 201 has a flexible engaging piece 202. Prior to fitting of the male connector 201, a protrusion 202a provided on the engaging piece 202 is engaged with a fitting hole 208a of the connector mounting plate 208. As shown in FIGS. 2B, 2C, the female connector 205 is inserted through the mounting opening 209a of the instrumental panel 209 and fit to the male connector 201. As a result, when the female connector 205 is normally fit to the male connector 201, the engaging piece 202 deflects downward so that a hook portion 203 on a front end of the engaging piece 202 is embedded into a recess hole 206 of the female connector 205. When the electrical device 204 is further pressed from this condition, as shown in FIG. 2D, the male connector 201 is forced up to an assembly position, so that the female connector 205 is locked within the mounting opening 209a of the instrumental panel 209 through a locking piece 204a of the electrical device 204.
According to the installation procedure of the conventional vehicle connectors, after the switch unit 104 is installed on the door trim 105, the connector 107 of the switch unit 104 is fit to the connector 106 connected to the end of the wire harness 102 placed in the door panel 101. Thus, the coupling of both the connectors 106, 107 is carried out by manual sensing method (the manual sensing work portion is indicated by symbol B in FIG. 1) so that work efficiency is poor. Further, because the connector 106 is located at an end of the long wire harness 102, when the door trim 105 is installed on the door panel 101 after the connector 107 of the switch unit 104 is fit to the connector connected to the end of the wire harness 102 placed in the door panel 101, catching of the wire harness 102 or the like occurs thereby leading to a connection failure of the wire harness 102, disconnection or the like.
In the above described conventional connector coupling structure, because there is formed a tapered face 202b on a rear portion of the protrusion 202a of the engaging piece 202 of the male connector 201, the male connector 201 is likely to retract on halfway of coupling of both the connectors 201, 205, so that it is difficult to install both the connectors 201, 205 at a normal position with both the connectors being coupled with each other completely. For example, if both the connectors 201, 205 are uncoupled for maintenance and inspection, the male connector 201 remains drooping behind the connector mounting plate 208, so that it is impossible to couple both the connectors 201, 205 with each other again when the maintenance and inspection is completed. If the wire harness connected to the male connector 201 is pulled for some reason after both the connectors 201, 205 are fit to each other, there is a fear that the connectors 201, 205 may be uncoupled because there is no locking means provided between both the connectors 201 and 205. Further, because both the connectors 201, 205 are fit to each other by only a holding force between a female terminal (not shown) of the male connector 201 and a male terminal 207 of the female connector 205, the fitting force between both the connectors 201 and 205 is insufficient so that it is weak against a vibration, thereby often producing looseness, abnormal noise and the like.


A computer system includes a chassis having a slot in a side panel. An expansion card carrier is removably mounted in the chassis by being inserted into and removed from the slot. The carrier includes a jumper board which has a first connector and a second connector. An expansion card is mounted on the jumper board. The expansion card has a connector which engages the first connector of the jumper board. The second connector is coupled to the first connector and is positioned at an end of the carrier for being plugged into a connector within the chassis.

The disclosures herein relate generally to a computer chassis and more particularly to the insertion and removal of expansion cards in a alive chassis.
The use of PCI expansion cards in computer chassis is well known. It often becomes necessary or desirable to add or replace these cards in a live chassis, i.e. a chassis that is in an operating mode. Typically, expansion cards include a plug which extends from one edge thereof. The cards are mounted in the chassis in a vertical orientation with the plug edge connected into a horizontal motherboard. This arrangement requires vertical insertion and removal of the card.
However, in order to vertically insert or remove a card, the chassis top cover must be removed. This requires removal of fastening devices which hold the cover in place. As a result, the cover removal is time consuming. Removal of the cover of a live chassis and insertion or removal of a card therein presents additional problems. In some instances, the chassis may be mounted in a component rack. Component racks are used to store components of computer systems in a centralized location. The racks are tall metal cabinets with trays for supporting components including a chassis. If a chassis is mounted in a component rack, and an expansion card is to be added or removed, the chassis must first be removed from the rack after which the chassis cover can be removed to permit access to insert and/or remove expansion cards.
Other problems associated with inserting the expansion cards on the board. The include alignment of the card plug with the plug on the mother board, the card edge connector insertion/extraction force is quite large, and strain relief of the expansion card and the mother board requires consideration.
Therefore, what is needed is a device which protects and aligns an expansion card during insertion and removal of the card from a live chassis so that chassis covers do not have to be removed and the chassis does not have to be removed from a rack or cabinet.

Expansion card carrier and method for a computer system