Multicomponent coating materials, adhesives and sealing compounds comprising a (meth)acrylate (A) containing, based on (A), up to 90% by weight of hydroxyl-containing monomers in copolymerized form, of which (a1) from 20-90% by weight, based on (A), are 4-hydroxybutyl (meth)acrylate and/or 2-alkylpropane-1,3-diol mono(meth)acrylate, and (a2) from 0-40% by weight based on (A), are other hydroxyl-containing monomers; and (B) an adduct preparable from (b1) a diisocyanate, and (b2) a compound of the general formula I having an isocyanate-reactive group:

This application is a National Phase of Patent Application PCT/EP01/04700 filed Apr. 26, 2001.
The present invention relates to novel multicomponent coating materials, adhesives and sealing compounds. The present invention further relates to the use of the novel multicomponent coating materials for producing novel clearcoat systems or color- and effect-imparting solid-color topcoat, basecoat and multicoat systems in the OEM finishing and refinishing of motor vehicles, in the interior and exterior coating of constructions, in furniture, window and door coating and in industrial coating, including coil coating, container coating, and the impregnation of electrical engineering components. The present invention relates additionally to the use of the novel multicomponent adhesives and sealing compounds for producing novel adhesive films and seals, especially in the fields of use recited above.
Two-component coating materials comprisingxe2x80x94in very general termsxe2x80x94reactive components having isocyanate-reactive functional groups, customary and known polyisocyanates, and adducts of diisocyanates and dioxolanes, dioxanes or oxazolidines which have an isocyanate-reactive functional group, in a molar ratio of 1:1, are known from German Patent Application DE 196 09 617 A1.
According to page 3, line 68 to page 4, line 10, said reactive components comprise, inter alia, hydroxy-functional polymers having a hydroxyl group content of from 0.1 to 20% by weight (corresponding to from 33 to 660 mg KOH/g). The number-average molecular weight of the polymers is preferably from 1000 to 100,000. The polymers contain preferably more than 50% by weight of C1-C20 alkyl (meth)acrylate, vinyl aromatics having up to 20 carbon atoms, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl halides, nonaromatic hydrocarbons having 4 to 8 carbon atoms and 1 or 2 double bonds, unsaturated nitrites, and mixtures thereof. Preference is given to polymers containing up to 60% by weight of C1-C10 alkyl (meth)acrylates, styrene, or mixtures thereof.
Furthermore, the polymers include hydroxy-functional monomers, corresponding to the above hydroxyl group content, and also other monomers, which are not specified in any greater detail, such as unsaturated acids, especially carboxylic acids, acid anhydrides, or acid amides.
According to page 9, lines 30 to 45, xe2x80x9cPreparation and testing of the clearcoats with the compounds Axe2x80x94two-component systemxe2x80x9d, the hydroxy-functional vinyl polymer Lumitol(copyright) H 136 from BASF Aktiengesellschaft, having an OH number of 136 mg KOH/g, is used as the reactive component. These known clearcoats have a high solids content of up to 76% by weight. The clearcoat finishes produced from them possess good mechanical properties, in particular a high level of hardness and flexibility, and also high chemical resistance.
The two-component coating materials known from DE 196 09 617 A1 are, however, not so broadly applicable as would in fact be desirable. Moreover, there is a need to extend their pot life, that is to say the time within which, after the two components have been mixed, the coating materials can be processed without problems and give flawless coatings.
German Patent DE 197 09 467 C 2 or German Laid-Open Specification DE 197 09 465 A 1 disclose heat-curable coating materials based on hydroxyl-containing binders and crosslinking agents which comprise hydoxyl-reactive functional groups. After their curing they have a storage modulus Exe2x80x2 in the rubber-elastic range of at least 107.6 Pa and a loss factor tan xcex4 at 20xc2x0 C. of not more than 0.10, the storage modulus Exe2x80x2 and the loss factor having been measured by means of dynamic mechanical thermoanalysis on free films having a thickness of 40xc2x110 xcexcm. Binders used include, inter alia, (meth)acrylate copolymers containing 4-hydroxybutyl methacrylate in a copolymerized form. The coatings produced from the known coating materials are scratch-resistant and chemical-stable. Nevertheless, it is necessary to improve further on the level of scratch resistance already obtained, for particularly demanding end uses: for example, in the OEM finishing and refinishing of particularly high-value, top-class automobiles. Furthermore, the known coatings ought to have even better polishability.
Methylpropane-1,3-diol mono(meth)acrylate and its polymers of low molecular weight are known from German Patent Application DE 32 34 045 A 1. The polymers are used to prepare light-sensitive compositions which are used for imagewise exposure. It is unknown whether they are also suitable for the production of multicomponent coating materials, adhesives or sealing compounds.
German Patent Application DE 198 50 210.9, unpublished at the priority date of the present specification, describes the use of 2-methyl-propane-1,3-diol mono(meth)acrylate to prepare (meth)acrylate copolymers. The (meth)acrylate copolymers in question are used to prepare multicomponent coating materials, adhesives and sealing compounds. The multicomponent coating materials give scratch-resistant coatings, especially clearcoats.
It is an object of the present invention to further develop the known multicomponent coating materials while losing nothing of the profile of properties already achieved so as to give new, advantageous multicomponent coating materials which have a high solids content at low viscosity and have a long pot life and which give coatings, especially clearcoat systems and color- and/or effect-imparting solid-color topcoat, basecoat and multicoat systems, which in addition to a high level of hardness, flexibility and chemical resistance also possess outstanding flowout, very good intercoat adhesion, an outstanding overall visual impression, very good weathering stability, very high scratch resistance, and very good polishability. It is also an object of the present invention to further develop the existing two-component adhesives and sealing compounds to give new multicomponent adhesives and sealing compounds having a high solids content and low viscosity and a long pot life which give adhesive films of especially high bond strength and seals having a particularly high sealing capacity even to chemically aggressive substances.
Accordingly we have found the novel multicomponent coating materials, adhesives and sealing compounds comprising
(A) at least one (meth)acrylate copolymer having an OH number from 130 to 200, a glass transition temperature of from xe2x88x9235 to +60xc2x0 C., a number-average molecular weight of from 1000 to 5000 daltons and a mass-molecular weight of from 2000 to 20,000 daltons, which contains, based on the (meth)acrylate copolymer (A), up to 90% by weight of hydroxyl-containing, olefinically unsaturated monomers (a) in copolymerized form, of which
(a1) from 20 to 90% by weight, based on the (meth) acrylate copolymer (A), are hydroxybutyl (meth)acrylate and/or 2-alkylpropane-1,3-diol mono(meth)acrylate, and
(a2) 0 to 40% by weight based on the (meth)acrylate copolymer (A), are other hydroxyl-containing, olefinically unsaturated monomers;
and
(B) at least one adduct preparable from
(b1) at least one diisocyanate and
(b2) at least one compound of the general formula I having an isocyanate-reactive functional group:
in which the variables have the following definitions:
R1 and R2 independently of one another are hydrogen atoms or alkyl radicals having 1 to 10 carbon atoms;
X and Y independently of one another are oxygen atom, sulfur atom or a radical  greater than Nxe2x80x94R6, in which R6 is an aliphatic radical having 1 to 30 carbon atoms, whose carbon chain may be interrupted by one or more oxygen atoms, or is an aromatic group having 6 to 30 carbon atoms;
R3 is an alkylene radical having 1 to 5 carbon atoms; and
R4 and R5 independently of one another are hydrogen atoms, isocyanate-reactive functional groups or radicals R6;
with the proviso that one radical R4, R5 or R6 contains an isocyanate-reactive functional group or one radical R4 or R5 is an isocyanate-reactive functional group, in which case the other radicals R41 R5 or R6xe2x80x94where presentxe2x80x94contain no isocyanate-reactive functional groups;
the molar ratio of isocyanate groups in the diisocyanates (b1) to the isocyanate-reactive functional groups in the compound I being from 0.8:1.2 to 1.2:0.8.
In the text below, the novel multicomponent coating materials, adhesives and sealing compounds are referred to for brevity as xe2x80x9ccoating materials, adhesives and sealing compounds of the inventionxe2x80x9d.
Furthermore, the novel process for producing a clearcoat system by applying a clearcoat to a primed or unprimed substrate or a coating system present thereon has been found in which the coating material of the invention is used as the clearcoat.
Furthermore, the novel process for producing a color and/or effect coating system by applying a pigmented solid-color topcoat to a primed or unprimed substrate has been found in which the coating material of the invention is used as the solid-color topcoat.
Not least, the novel process for producing a multicoat color and/or effect coating system on a primed or unprimed substrate by
(1) applying a basecoat to the substrate,
(2) drying and/or partially curing or completely curing the basecoat film,
(3) applying a clearcoat to the dried and/or partially cured basecoat film or to the cured basecoat, and
(4) curing the clearcoat film together with the basecoat film, or separately curing the clearcoat film,
has been found in which
(a) a conventional basecoat and the coating material of the invention as the clearcoat,
(b) a conventional clearcoat and the coating material of the invention as basecoat, or
(c) a pigmented and an unpigmented coating material of the invention, as basecoat and as clearcoat, are used.
Not least, the novel process for producing novel adhesive films and/or seals on and in primed and unprimed substrates has been found in which adhesives and/or sealing compounds of the invention are applied onto and/or into the substrates and cured.
In the text below, the novel processes are referred to collectively as xe2x80x9cprocesses of the inventionxe2x80x9d.
Further subjects of the invention will emerge from the description.
In the light of the prior art, it was surprising and unforeseeable for the skilled worker that the object on which the present invention is based could be achieved by the specific combination of a selected (meth)acrylate copolymer (A) and of an adduct (B) which gives rise to the preferential profile of properties of the novel coating materials, adhesives and sealing compounds of the invention and of the coatings, adhesive films and seals produced from them. A further surprise was the extraordinarily broad applicability of the specific combination. Yet a further surprise was the good reflow behavior of the coatings of the invention.
The coating materials, adhesives and sealing compounds of the invention are multicomponent systems. This means that their highly reactive constituents are present in a form in which they are divided between a plurality of components which, viewed individually, are stable on storage, and said constituents are not combined until a comparatively short time before use. In the context of the present invention, xe2x80x9ccomparatively shortxe2x80x9d means a period of from 1 min to 24 h and xe2x80x9cstable on storagexe2x80x9d means that the component in question can be stored for at least 24 h, preferably for at least one week, without decomposition and/or premature crosslinking. The constituents are preferably divided between two components, the binders and, if present, the reactive diluents being present in one component and the crosslinking agents in the other.
The first component of the coating materials, adhesives and sealing compounds of the invention comprises the component containing binder.
The essential constituent of the binder-containing component for use in accordance with the invention is at least one binder. In accordance with the invention, this comprises at least one (meth)acrylate copolymer (A) having specific properties and a specific composition.
Thus the (meth)acrylate copolymer (A) for use in accordance with the invention has
an OH number of from 130 to 200, preferably from 135 to 190, preferably from 140 to 185, and in particular from 145 to 180 mg KOH/g,
a glass transition temperature of from xe2x88x9235 to +60, in particular from xe2x88x9220 to +40, xc2x0 C.,
a number-average molecular weight of from 1000 to 5000 daltons, in particular from 2000 to 4500 daltons, and
a mass-average molecular weight of from 2000 to 20,000 daltons, in particular from 4000 to 16,000 daltons.
The (meth)acrylate copolymer (A) contains, based in each case on (A), up to 90, preferably up to 88, more preferably up to 86, with particular preference up to 84, with very particular preference up to 82, and in particular up to 80, % by weight of hydroxyl-containing, olefinically unsaturated monomers (a) in copolymerized form, of which
(a1) from 20 to 90, preferably from 22 to 88, more preferably from 24 to 86, with particular preference from 26 to 84, with very particular preference from 28 to 82, and in particular from 30 to 80, % by weight, based in each case on the (meth)acrylate copolymer (A), are 4-hydroxybutyl (meth)acrylate and/or 2-alkylpropane-1,3-diol mono(meth)acrylate, and
(a2) from 0 to 40, preferably from 1 to 38, more preferably from 2 to 36, with particular preference from 3 to 34, with very particular preference from 4 to 32, and in particular from 6 to 30, % by weight, based in each case on the (meth)acrylate copolymer (A), are other hydroxyl-containing, olefinically unsaturated monomers.
Examples of suitable 2-alkylpropane-1,3-diol mono(meth)acrylates (a1) are 2-methyl-, 2-ethyl-, 2-propyl-, 2-isopropyl- or 2-n-butyl-propane-1,3-diol mono(meth)acrylate, of which 2-methylpropane-1,3-diol mono(meth)acrylate is particularly advantageous and, is used preferably in accordance with the invention.
Examples of suitable other hydroxyl-containing, olefinically unsaturated monomers (a2) are hydroxyalkyl esters of acrylic acid, methacrylic acid or another hydroxyalkyl esters of acrylic acid, methacrylic acid or another alpha, beta-ethylenically unsaturated carb-oxylic acid (i) derived from an alkylene glycol which is esterified with the acid, or (ii) obtainable by reacting the acid with an alkylene oxide such as ethylene oxide or propylene oxide; especially hydroxyalkyl esters of acrylic acid, methacrylic acid, crotonic acid or ethacrylic acid in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 3-hydroxypropyl, 3-hydroxybutyl methacrylate, ethacrylate or crotonate; 1,4-bis(hydroxymethyl)cyclohexane or octahydro-4,7-methano-1H-indene-dimethanol monoacrylate, monomethacrylate, monoethacrylate or monocrotonate; or reaction products of cyclic esters, such as epsilon-caprolactone, for example, and these hydroxyalkyl esters; or olefinically unsaturated alcohols such as allyl alcohol; or polyols such as trimethylolpropane monoallyl or diallyl ether or pentaerythritol monoallyl, diallyl or triallyl ether. These higher-functional monomers (a2) are used generally only in minor amounts. In the context of the present invention, minor amounts of higher-functional monomers (a2) are amounts which do not lead to crosslinking or gelling of the (meth)acrylate copolymers (A) unless the intention is that the copolymers should be present in the form of crosslinked microgel particles.
Also suitable as monomers (a2) are ethoxylated and/or propoxylated allyl alcohol, which is sold by Arco Chemicals, or 2-hydroxyalkyl allyl ethers, especially 2-hydroxyethyl allyl ether. If used, they are used preferably not as sole monomers (a2) but in an amount of from 0.1 to 10% by weight, based on the (meth)acrylate copolymer (A).
Also suitable are reaction products of acrylic acid and/or methacrylic acid with the glycidyl ester of an alpha-branched monocarboxylic acid having 5 to 18 carbon atoms per molecule, especially a Versatic(copyright) acid, or, instead of the reaction products, an equivalent amount of acrylic and/or methacrylic acid which is then reacted, during or after the polymerization reaction, with the glycidyl ester of an alpha-branched monocarboxylic acid having 5 to 18 carbon atoms per molecule, in particular a Versatic(copyright) acid (cf. Rxc3x6mpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, N.Y., 1998, xe2x80x9cVersatic(copyright) acidsxe2x80x9d, pages 605 and 606).
Furthermore, the (meth)acrylate copolymers (A) comprise further olefinically unsaturated monomers (a3), whose proportion in (A) is at least 10, preferably at least 12, more preferably at least 14, with particular preference at least 16, with very particular preference at least 18, and in particular at least 20, % by weight.
Examples of Suitable Monomers (a3) are
Monomers (a31)
(Meth)acrylic esters which are essentially free from acid groups, such as (meth)acrylic alkyl or cycloalkyl esters having up to 20 carbon atoms in the alkyl radical, especially methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate or methacrylate; cycloaliphatic (meth)acrylic esters, especially cyclohexyl, isobornyl, dicyclopentadienyl, octahydro-4,7-methano-1H-indene-methanol or tert-butylcyclohexyl (meth)acrylate; (meth)acrylic oxaalkyl or oxacycloalkyl esters such as ethoxytriglycol (meth)acrylate and methoxyoligoglycol (meth)acrylate having a molecular weight Mn of preferably 550 daltons or other ethoxylated and/or propoxylated, hydroxyl-free (meth)acrylic acid derivatives (further examples of suitable monomers (a2) of this kind are known from the laid-open specification DE 196 25 773 A1, column 3, line 65 to column 4, line 20). In minor amounts they may contain higher-functional (meth)acrylic alkyl or cycloalkyl esters such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,5-pentanediol, 1,6-hexanediol, octahydro-4,7-methano-1H-indenedimethanol or cyclohexane-1,2-, -1,3- or -1,4-diol di(meth)acrylate; trimethylolpropane-di- or -tri(meth)acrylate; or pentaerythritol di-, tri- or tetra(meth)acrylate. As far as the amounts of higher-functional monomers (a31) are concerned, the comments made above with respect to the monomers (a2) apply.
Monomers (a32)
Ethylenically unsaturated monomers carrying at least one acid group, preferably a carboxyl group, per molecule, or a mixture of such monomers. As component (a32) it is particularly preferred to use acrylic acid and/or methacrylic acid. However, it is also possible to use other ethylenically unsaturated carboxylic acids having up to 6 carbon atoms in the molecule. Examples of such acids are ethacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid. It is also possible to use ethylenically unsaturated sulfonic or phosphonic acids, or their partial esters, as component (a32). Further suitable monomers (a32) are maleic acid mono(meth)acryloyloxyethyl ester, succinic acid mono(meth)acryloyloxyethyl ester and phthalic acid mono(meth)acryloyloxyethyl ester, and also vinylbenzoic acid (all isomers), alpha-methylvinylbenzoic acid (all isomers) or vinylbenzenesulfonic acid (all isomers). Further examples of acid-group-containing monomers (a32) are known from the laid-open specification DE 196 25 773 A1, column 2, line 58 to column 3, line 8, or from International Patent Application WO 98/49205, page 3, lines 23 to 34.
Monomers (a33)
Vinyl esters of alpha-branched monocarboxylic acids having 5 to 18 carbon atoms in the molecule. The branched monocarboxylic acids may be obtained by reacting formic acid or carbon monoxide and water with olefins in the presence of a liquid, strongly acidic catalyst; the olefins may be cracking products of paraffinic hydrocarbons, such as mineral oil fractions, and may comprise branched and straight-chain acyclic and/or cycloaliphatic olefins. The reaction of such olefins with formic acid or with carbon monoxide and water produces a mixture of carboxylic acids in which the carboxyl groups are located predominantly on a quaternary carbon atom. Other olefinic starting materials are, for example, propylene trimer, propylene tetramer and diisobutylene. Alternatively, the vinyl esters may be prepared in a conventional manner from the acids; for example, by reacting the acid with acetylene. Particular preference, owing to their ready availability, is given to the use of vinyl esters of saturated aliphatic monocarboxylic acids having 9 to 11 carbon atoms which are branched on the alpha carbon atom.
Monomers (a34)
N,N-Diethylamino-alpha-methylstyrene (all isomers), N,N-diethylaminostyrene (all isomers), alkylamine, crotylamine, 2-N,N-dimethyl-, 2-N-ethyl-, 2-N,N-diethyl-, 2-amino- or 2-N-methyl-, 2-N-propyl-, 2-N,N-dipropyl-, 2-N-butyl-, 2-N-N-dibutyl-, 2-N-cyclohexyl or 2-N,N-cyclohexyl-methyl-amino or 2-N,N,N,N-tetramethylammonium- or 2-N,N-dimethyl-N,N-diethy-ammonium-, 2-tetramethylphosphonium or 2-triethylsul-fonium-ethyl acrylate, -ethyl methacrylate, -propyl acrylate or -propyl methacrylate, or 3-amino- or 3-N,N-dimethyl-, 3-N-methyl-, 3-N-ethyl-, 3-N,N-diethyl-, 3-N-propyl-, 3-N,N-dipropyl-, 3-N-butyl-, 3-N,N-dibutyl-, 3-N-cyclohexyl- or 3-N,N-cyclohexylmethylamino or 3-N,N,N,N-tetramethylammonium- or 3-N,N-dimethyl-N,N-diethylammonium-, 3-tetramethylphosphonium- or 3-triethylsulfoniumpropyl acrylate or -propyl methacrylate.
Monomers (a35)
Diarylethylenes, especially those of the general formula V:
R7R8Cxe2x95x90CR9R10xe2x80x83xe2x80x83(V),
in which the radicals R7, R8, R9 and R10 in each case independently of one another are hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals, with the proviso that at least two of the variables R1, R2, R3 and R4 are substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, especially substituted or unsubstituted aryl radicals. Examples of suitable alkyl radicals are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, amyl, hexyl or 2-ethylhexyl. Examples of suitable cycloalkyl radicals are cyclobutyl, cyclopentyl or cyclohexyl. Examples of suitable alkylcycloalkyl radicals are methylenecyclohexane, ethylenecyclohexane or propane-1,3-diylcyclohexane. Examples of suitable cyclo-alkylalkyl radicals are 2-, 3- or 4-methyl-, -ethyl-, -propyl- or -butylcyclohex-1-yl. Examples of suitable aryl radicals are phenyl, naphthyl or biphenylyl, preferably phenyl and naphthyl and especially phenyl. Examples of suitable alkyl aryl radicals are benzyl or ethylene- or propane-1,3-diylbenzene. Examples of suitable cycloalkylaryl radicals are 2-, 3- or 4-phenylcyclohex-1-yl. Examples of suitable arylalkyl radicals are 2-, 3- or 4-methyl-, -ethyl-, -propyl- or -butylphen-1-yl. Examples of suitable arylcycloalkyl radicals are 2-, 3- or 4-cyclohexylphen-1-yl. The aryl radicals R7, R8, R9 and/or R10 are preferably phenyl or naphthyl radicals, especially phenyl radicals. The substituents that may be present in the radicals R7, R8, R9 and/or R10 are electron withdrawing or electron donating atoms or organic radicals, especially halogen atoms, nitrile, nitro, partially or fully halogenated alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and arylcycloalkyl radicals; aryloxy, alkyloxy and cycloalkyloxy radicals; arylthio, alkylthio and cycloalkylthio radicals and/or primary, secondary and/or tertiary amino groups. Diphenylethylene, dinaphthaleneethylene, cis- or trans-stilbene, vinylidene-bis(4-N,N-dimethylaminobenzene), vinylidene-bis(4-aminobenzene)-or vinylidene-bis(4-nitrobenzene), especially diphenylethylene (DPE), are particularly advantageous and so are used with preference. In the context of the present invention, the monomers (a35) are used in order to regulate the copolymerization advantageously such that batchwise free-radical copolymerization is also possible.
Monomers (a36)
Cyclic and/or acyclic olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclo-hexene, cyclopentene, norbornene, butadiene, isoprene, cyclopentadiene and/or dicyclopentadiene.
Monomers (a37)
Amido-containing monomers such as (meth)acrylamides such as (meth)acrylamide, N-methyl-, N,N-dimethyl-, N-ethyl-, N,N-diethyl-, N-propyl-, N,N-dipropyl-, N-butyl-, N,N-dibutyl-, N-cyclohexyl-, N,N-cyclo-hexylmethyl- and/or N-methylol-, N,N-dimethylol-, N-methoxymethyl-, N,N-di(methoxymethyl)-, N-ethoxy-methyl- and/or N,N-di(ethoxyethyl)-(meth)acrylamide; monomers containing carbamate groups, such as (meth)acryloyloxyethyl carbamate or (meth)acryloyl-oxypropyl carbamate; or monomers containing urea groups, such as ureidoacrylate or ureidomethacrylate;
Monomers (a38)
Monomers containing epoxide groups, such as the glycidyl ester of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid and/or itaconic acid.
Monomers (a39)
Vinylaromatic hydrocarbons such as styrene, vinyl toluene, diphenylethylene or alpha-alkylstyrenes, especially alpha-methylstyrene;
Monomers (a310)
Nitriles such as acrylonitrile and/or methacrylonitrile;
Monomers (a311)
Vinyl compounds, especially vinyl halides and/or vinylidene dihalides, such as vinyl chloride, vinyl fluoride, vinylidene dichloride or vinylidene difluoride; N-vinyl amides such as vinyl-N-methylformamide, N-vinylcaprolactam or N-vinyl pyrrolidone; 1-vinylimidazole; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and/or vinyl cyclohexyl ether; and/or vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate and/or the vinyl ester of 2-methyl-2-ethylheptanoic acid.
Monomers (a312)
Allyl compounds, especially allyl ethers and allyl esters such as allyl methyl, ethyl, propyl or butyl ether or allyl acetate, propionate or butyrate.
Monomers (a313)
Polysiloxane macromonomers having a number-average molecular weight Mn of from 1000 to 40,000 and having on average from 0.5 to 2.5 ethylenically unsaturated double bonds per molecule; especially polysiloxane macromonomers having a number-average molecular weight Mn of from 2000 to 20,000, with particular preference from 2500 to 10,000, and in particular from 3000 to 7000 and having on average from 0.5 to 2.5, preferably from 0.5 to 1.5, ethylenically unsaturated double bonds per molecule, as are described in DE 38 07 571 A1 on pages 5 to 7, in DE 37 06 095 A1 in columns 3 to 7, in EP 0 358 153 B1 on pages 3 to 6, in U.S. Pat. No. 4,754,014 A1 in columns 5 to 9, in DE 44 21 823 A1 or in International Patent Application WO 92/22615 on page 12, line 18 to page 18, line 10.
Monomers (a314)
Acryloxysilane-containing vinyl monomers, preparable by reacting hydroxy-functional silanes with epichloro-hydrin and subsequently reacting the reaction product with (meth)acrylic acid and/or hydroxyalkyl esters and/or hydroxycycloalkyl esters of (meth)acrylic acid and/or further hydroxyl-containing monomers (a2).
The monomers (a1) and (a3) and, if appropriate, (a2) are selected so as to give the abovementioned OH numbers and glass transition temperatures. Moreover, the nature and amount of the monomers (a3), which contain reactive functional groups, are selected so as not to inhibit or prevent completely the crosslinking reactions of the hydroxyl groups with the below-described adducts (B) and/or crosslinking agents (C) in the second component.
The selection of the monomers (a) for adjusting the glass transition temperatures can be undertaken by the skilled worker with the aid of the following formula of Fox, by means of which the glass transition temperatures of poly(meth)acrylates can be calculated approximately:
            1      /      Tg        =                  ∑                  n          =          1                          n          =          x                                  Wn        /                  Tg          n                      ;      xe2x80x83                        ∑        n                          W        n              =    1
where
Tg=glass transition temperature of the poly(meth)acrylate;
Wn=Weight fraction of the nth monomer;
Tgn=glass transition temperature of the homopolymer of the nth monomer; and
x=number of different monomers.
The preparation of the (meth)acrylate copolymers (A) for use in accordance with the invention also has no special features as to method but takes place with the aid of the method of continuous or batchwise free-radically initiated copolymerization, which are known and customary in the field of plastics, in bulk, solution, emulsion, miniemulsion or microemulsion under atmospheric pressure or superatmospheric pressure in stirred vessels, autoclaves, tubular reactors, loop reactors or Taylor reactors at temperatures from 50 to 200xc2x0 C.
Examples of suitable copolymerization methods are described in patent applications DE 197 09 465 A1, DE 197 09 476 A1, DE 28 48 906 A1, DE 195 24 182 A1, DE 198 28 742 A1, DE 196 28 143 A1, DE 196 28 142 A1, EP 0 554 783 A1, WO 95/27742, WO 82/02387 or WO 98/02466.
Examples of suitable free-radical initiators are dialkyl peroxides, such as di-tert-butyl peroxide or dicumyl peroxide; hydroperoxides, such as cumene hydroperoxide or tert-butyl hydroperoxide; peresters, such as tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl per-3,5,5-trimethylhexanoate or tert-butyl per-2-ethylhexanoate; peroxodicarbonates; potassium, sodium or ammonium peroxodisulfate; azo initiators, examples being azodinitriles such as azobisiso-butyronitrile; Cxe2x80x94C-cleaving initiators such as benzopinacol silyl ether; or a combination of a nonoxidizing initiator with hydrogen peroxide. It is also possible to use combinations of the above-described initiators.
Further examples of suitable initiators are described in German Patent Application DE 196 28 142 A1, page 3, line 49 to page 4, line 6.
It is preferred to add comparatively large amounts of free-radical initiator, with the proportion of the initiator in the reaction mixture, based in each case on the total amount of the monomers (a) and of the initiator, being with particular preference from 0.2 to 20% by weight, with very particular preference from 0.5 to 15% by weight, and in particular from 1.0 to 10% by weight.
Furthermore, thiocarbonylthio compounds or mercaptans such as dodecyl mercaptan may be used as chain transfer agents or molecular weight regulators.
Preferably, the nature and amount of the (meth)acrylate copolymers (A) are selected such that the coating materials, adhesives and sealing compounds of the invention possess after curing a storage modulus Exe2x80x2 in the rubber-elastic range of at least 107.6 Pa and a loss factor tan xcex4 at 20xc2x0 C. of not more than 0.10, the storage modulus Exe2x80x2 and the loss factor having been measured by means of dynamic mechanical thermoanalysis on free films having a thickness of 40xc2x110 xcexcm (cf. German Patent DE 197 09 467 C2).
The amount of the above-described (meth)acrylate copolymers (A) in the coating materials, adhesives and sealing compounds of the invention may vary widely. The amount is dependent in particular on the functionality of the binders on the one hand and on the functionality of the below-described adducts (B) and of the crosslinking agents (D), on the other. Preferably, the amount is from 5.0 to 80, more preferably from 6.0 to 75, with particular preference from 7.0 to 70, with very particular preference from 8.0 to 65, and in particular from 9.0 to 60% by weight, based in each case on the solids content of the coating materials, adhesives and sealing compounds of the invention.
The binder component for use in accordance with the invention may contain customary and known additives (C) in effective amounts. The essential factor is that they do not inhibit or completely prevent the crosslinking reactions.
Examples of suitable additives (C) are color and/or effect pigments, organic and inorganic, transparent or opaque fillers, nanoparticles, reactive diluents curable thermally and/or with actinic radiation, low-boiling organic solvents and high-boiling organic solvents (xe2x80x9clong solventsxe2x80x9d), water, UV absorbers, light stabilizers, free-radical scavengers, thermally unstable free-radical initiators, photoinitiators and photocoinitiators, other, additional binders, crosslinking agents as used in one-component systems, catalysts for thermal crosslinking, devolatilizing agents, slip additives, polymerization inhibitors, defoamers, emulsifiers, wetting agents and dispersants, adhesion promoters, flow control agents, film-forming auxiliaries, sag control agents (SCAs), rheology control additives (thickeners), flame retardants, siccatives, dryers, antiskinning agents, corrosion inhibitors, waxes, flatting agents, precursors of organically modified ceramic materials, or additional binders.
The nature and amount of the additives (C) depend on the intended use of the coatings produced with the aid of the coating materials of the invention.
If, for example, a coating material of the invention is used to produce solid-color topcoats or basecoats, it normally comprises color and/or effect pigments (C) and also, if desired, opaque fillers. If a coating material of the invention is used, for example, to produce clearcoats or sealersxe2x80x94which is the preferred end usexe2x80x94these additives (C) are of course not present in the coating material in question.
Examples of suitable effect pigments (C) are metal flake pigments such as commercial aluminum bronzes, aluminum bronzes chromated in accordance with DE 36 36 183 A1, and commercial stainless steel bronzes and also nonmetallic effect pigments, such as pearlescent and interference pigments, for example. For further details, reference is made to Rxc3x6mpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, page 176, xe2x80x9cEffect pigmentsxe2x80x9d and pages 380 and 381, xe2x80x9cMetal oxide-mica pigmentsxe2x80x9d to xe2x80x9cMetal pigmentsxe2x80x9d.
Examples of suitable inorganic color pigments (C) are titanium dioxide, iron oxides, Sicotrans yellow, and carbon black. Examples of suitable organic color pigments (C) are thioindigo pigments, indanthrene blue, Cromophthal red, Irgazine orange and Heliogen green. For further details, reference is made to Rxc3x6mpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 180 and 181, xe2x80x9cIron blue pigmentsxe2x80x9d to xe2x80x9cBlack iron oxidexe2x80x9d, pages 451 to 453 xe2x80x9cPigmentsxe2x80x9d to xe2x80x9cPigment volume concentrationxe2x80x9d, page 563, xe2x80x9cThioindigo pigmentsxe2x80x9d, and page 567, xe2x80x9cTitanium dioxide pigmentsxe2x80x9d.
Examples of suitable organic and inorganic fillers (C) are chalk, calcium sulfates, barium sulfate, silicates such as talc or kaolin, silicas, oxides such as aluminum hydroxide or magnesium hydroxide, or organic fillers such as textile fibers, cellulose fibers, polyethylene fibers or wood flour. For further details, reference is made to Rxc3x6mpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 250 ff., xe2x80x9cFillersxe2x80x9d.
Examples of suitable thermally curable reactive diluents (C) are positionally isomeric diethyl-octanediols or hydroxyl-containing hyperbranched compounds or dendrimers, as are described for example in German Patent Application DE 198 50 243, unpublished at the priority date of the present specification.
Examples of suitable reactive diluents (C) curable with actinic radiation are those described in Rxc3x6mpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, N.Y., 1998, on page 491 under the key word xe2x80x9cReactive diluentsxe2x80x9d.
Examples of suitable low-boiling organic solvents (C) and high-boiling organic solvents (C) (xe2x80x9clong solventsxe2x80x9d) are ketones such as methyl ethyl ketone or methyl isobutyl ketone, esters such as ethyl acetate or butyl acetate, ethers such as dibutyl ether or ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol or dibutylene glycol, dimethyl, diethyl or dibutyl ether, N-methylpyrrolidone or xylenes, or mixtures of aromatic hydrocarbons such as Solventnaphtha(copyright) or Solvesso(copyright).
Examples of suitable thermally unstable free-radical initiators (C) are organic peroxides, organic azo compounds, or Cxe2x80x94C-cleaving initiators such as dialkyl peroxides, peroxocarboxylic acids, peroxodicarbonates, peroxide esters, hydroperoxides; ketone peroxides, azodinitriles or benzpinacol silyl ether.
Examples of suitable catalysts (C) for the crosslinking are dibutyltin dilaurate, lithium decanoate or zinc octoate.
Examples of suitable photoinitiators and coinitiators (C) are described in Rxc3x6mpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, 1998, pages 444 to 446.
Examples of suitable other, additional binders (C) are oligomeric and polymeric linear and/or branched and/or block, comb and/or random (co)polymers of ethylenically unsaturated monomers, curable thermally and/or with actinic radiation, or polyaddition resins and/or polycondensation resins, as described in Rxc3x6mpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, N.Y., 1998, page 457: xe2x80x9cPolyadditionxe2x80x9d and xe2x80x9cPolyaddition resins (polyadducts)xe2x80x9d, pages 463 and 464: xe2x80x9cPolycondensatesxe2x80x9d, xe2x80x9cPolycondensationxe2x80x9d and xe2x80x9cPolycondensation resinsxe2x80x9d, and pages 73 and 74: xe2x80x9cBindersxe2x80x9d. Further examples of suitable other, additional binders (C) are the poly(meth)acrylates or acrylate copolymers described in the patent DE 197 36 535 A1, polyesters, especially those described in the patents DE 40 09 858 A1 or DE 44 37 535 A1, alkyds, acrylated polyesters, polylactones, polycarbonanes, polyethers, epoxy resin-amine adducts, (meth)acrylatediols, partially hydrolyzed polyvinyl esters, polyurethanes and acrylated polyurethanes, such as those described in patents EP 0 521 928 A1, EP 0 522 420 A1, EP 0 522 419 A1, EP 0 730 613 A1 or DE 44 37 535 A1, or polyureas.
Examples of suitable additional crosslinking agents (C) are amino resins, as described, for example, in Rxc3x6mpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, page 29, xe2x80x9cAmino resinsxe2x80x9d, in the text book xe2x80x9cLackadditivexe2x80x9d [Coatings additives] by Johan Bieleman, Wiley-VCH, Weinheim, N.Y., 1998, pages 242 ff., in the book xe2x80x9cPaints, Coatings and Solventsxe2x80x9d, second, completely revised edition, Eds. D. Stoye and W. Freitag, Wiley-VCH, Weinheim, N.Y., 1998, pages 80 ff., in the patents U.S. Pat. No. 4,710,542 A1 or EP-B-0 245 700 A1, and in the article by B. Singh and coworkers, xe2x80x9cCarbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industryxe2x80x9d, in Advanced Organic Coatings Science and Technology Series, 1991, Volume 13, pages 193 to 207; carboxyl-containing compounds or resins, as described for example in the patent DE 196 52 813 A1, compounds or resins containing epoxide groups, as described for example in the patents EP 0 299 420 A1, DE 22 14 650 B1, DE 27 49 576 B1, U.S. Pat. No. 4,091,048 A1 or U.S. Pat. No. 3,781,379 A1, blocked polyisocyanates, as described for example in the patents U.S. Pat. No. 4,444,94 A1, DE 196 17 C86 A1, DE 196 31 269 A1, EP 0 004 571 A1 or EP 0 582 051 A1, and/or tris(alkoxycarbonylamino)triazines, as described in the patents U.S. Pat. Nos. 4,939,213 A1, 5,084,541 A1, 5,288,865 A1 or EP 0 604 922 A1.
Examples of suitable devolatilizers (C) are diazadi-cycloundecane or benzoin.
Examples of suitable emulsifiers (C) are nonionic emulsifiers, such as alkoxylated alkanols and polyols, phenols and alkylphenols, or anionic emulsifiers such as alkali metal salts or ammonium salts of alkanecarboxylic acids, alkanesulfonic acids, and sulfo acids of alkoxylated alkanols and polyols, phenols and alkylphenols.
Examples of suitable wetting agents (C) are siloxanes, compounds containing fluorine, carboxylic monoesters, phosphoric esters, polyacrylic acids and copolymers thereof, or polyurethanes.
An example of a suitable adhesion promoter (C) is tricyclodecanedimethanol.
Examples of suitable film-forming auxiliaries (C) are cellulose derivatives such as cellulose acetobutyrate (CAB).
Examples of suitable transparent fillers (C) are those based on silicon dioxide, aluminum oxide or zirconium oxide; for further details, reference is made to Rxc3x6mpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, 1998, pages 250 to 252.
Examples of suitable sag control agents (C) are ureas, modified ureas and/or silicas, as are described, for example, in the references EP 0 192 304 A1, DE 23 59 923 A1, DE 18 05 693 A1, WO 94/22968, DE 27 51 761 C1, WO 97/12945 or xe2x80x9cfarbe+lackxe2x80x9d, November 1992, pages 829 ff.
Examples of suitable rheology control additives (C) are those known from the patents WO 94/22968, EP 0 276 501 A1, EP 0 249 201 A1 or WO 97/12945; crosslinked polymeric microparticles, as disclosed for example in EP 0 008 127 A1; inorganic phyllosilicates such as aluminum-magnesium silicates, sodium-magnesium phyllosilicates and sodium-magnesium-fluorine-lithium phyllosilicates of the montmorillonite type; silicas such as Aerosils, or synthetic polymers having ionic and/or associative groups, such as polyvinyl alcohol, poly(meth)acrylamide, poly(meth)acrylic acid, poly-vinylpyrrolidone, styrene-maleic anhydride or ethylene-maleic anhydride copolymers and their derivatives, or hydrophobically modified ethoxylated urethanes or polyacrylates.
An example of suitable flatting agent (C) is magnesium stearate.
Examples of suitable precursors (C) for organically modified ceramic materials are hydrolyzable organometallic compounds, especially of silicon and aluminum.
Further examples of the additives (C) recited above, and examples of suitable UV absorbers, free-radical scavengers, flow control agents, flame retardants, siccatives, dryers, antiskinning agents, corrosion inhibitors and waxes (C) are described in detail in the textbook xe2x80x9cLackadditivexe2x80x9d by Johan Bieleman, Wiley-VCH, Weinheim, N.Y., 1998.
The preparation of the binder component for use in accordance with the invention has no special features, but instead takes place in a customary and known manner by mixing of the above-described components (A) and, if desired, (C) in suitable mixing equipment such as stirred vessels, dissolvers, stirred mills, or extruders.
The second component of the coating materials, adhesives and sealing compounds of the invention comprises at least one adduct (B).
The adduct (B) can be prepared from a diisoyanate (b1) and a compound I (b2).
Examples of suitable diisocyanates are isophorone diisocyanate (5-isocyanato-1-isocyanatomethyl-1,3,3-trimethylcyclohexane), 5-isocyanato-1-(2-isocyanatoeth-1-yl)-1,3,3-trimethylcyclohexane, 5-isocyanato-1-(3-isocyanatoprop-1-yl)-1,3,3-trimethylcyclohexane, 5-iso-cyanato-(4-isocyanatobut-1-yl)-1,3,3-trimethylcyclo-hexane, 1-isocyanato-2-(3-isocyanatoprop-1-yl)cyclo-hexane, 1-isocyanato-2-(3-isocyanatoeth-1-yl)cyclo-hexane, 1-isocyanato-2-(4-isocyanatobut-1-yl)-cyclo-hexane, 1,2-diisocyanatocyclobutane, 1,3-diisocyanato-cyclobutane, 1,2-diisocyanatocyclopentane, 1,3-diiso-cyanatocyclopentane, 1,2-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclo-hexane, dicyclohexylmethane 2,4xe2x80x2-diisocyanate, tri-methylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), ethylethylene diisocyanate, trimethylhexane diisocyanate, heptamethylene diisocyanate or diisocyanates derived from dimeric fatty acids, as sold under the commercial designation DDI 1410 by Henkel and described in patents WO 97/49745 and WO 97/49747, especially 2-heptyl-3,4-bis(9-isocyanatononyl)-1-pentylcyclohexane, or 1,2-, 1,4- or 1,3-bis(iso-cyanatomethyl)cyclohexane, 1,2-, 1,4- or 1,3-bis(2-iso-cyanatoeth-1-yl)cyclohexane, 1,3-bis(3-isocyanatoprop-1-yl)cyclohexane, 1,2-, 1,4- or 1,3-bis(4-iso-cyanatobut-1-y) or is4-iso-cyanatocyclohexyl)methane with a trans/trans content of up to 30% by weight, preferably 25% by weight and in particular 20% by weight, as described by patent applications DE 44 14 032 A1, GB 1220717 A1, DE 16 18 795 A1 or DE 17 93 785 A1, preferably isophorone diisocyanate, 5-isocyanato-1-(2-isocyanato-eth-1-yl)-1,3,3-trimethyl-cyclohexane, 5-isocyanato-1-(3-isocyanatoprop-1-yl)-1,3,3-trimethyl-cyclohexane, 5-isocyanato-(4-isocyanatobut-1-yl)-1,3,3-trimethyl-cyclohexane, 1-isocyanato-2-(3-isocyanatoprop-1-yl)-cyclohexane, 1-isocyanato-2-(3-isocyanatoeth-1-yl)-cyclohexane, 1-isocyanato-2-(4-isocyanatobut-1-yl)-cyclohexane or HDI, especially HDI.
The compounds I have an isocyanate-reactive functional group. Examples of suitable isocyanate-reactive functional groups are hydroxyl groups, thiol groups and primary or secondary amino groups.
The compounds I have the general formula I:
in which general formula I R1 and R2 independently of one another are hydrogen atoms or alkyl radicals having 1 to 10 carbon atoms, preferably methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isoamyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl-hex-1-yl, n-nonyl or n-decyl, especially isopropyl;
X and Y independently of one another are oxygen atoms, sulfur atoms or radicals  greater than Nxe2x80x94R6, in which R6 is an aliphatic radical having 1 to 30 carbon atoms whose carbon chain may be interrupted by one or more oxygen atoms, such as the above-described radicals R1 and R2, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosanyl or oligo(ethylene glycol)-1-yl, oligo(propylene glycol)-1-yl or oligo(butylene glycol)-1-yl or the corresponding mixed oligomers having a degree of oligomerization of up to 15. Furthermore, R6 may be an aromatic radical having 6 to 30 carbon atoms, such as phenyl, naphthyl or biphenyl-1-yl.
R3 is an alkylene radical having 1 to 5 carbon atoms, such as methylene, eth-1-2-ylene, trimethylene, tetramethylene or pentamethylene.
R4 and R5 independently of one another are hydrogen atoms, isocyanate-reactive functional groups, or radicals R6.
It is essential for the compounds I that one radical R41, R5 or R6 contains an isocyanate-reactive functional group or one radical R4 or R5 is an isocyanate-reactive functional group, the other radicals R4, R5 or R6xe2x80x94if presentxe2x80x94containing no isocyanate-reactive functional groups.
Examples of highly suitable compounds I are
dioxolanes of the general formula II:
dioxanes of the general formula III:
oxazolidines of the general formula IV:
in which the radicals R1, R2, R4, R5 and R6 are as defined above, the radicals R4 or R6 containing an isocyanate-reactive functional group.
Examples of suitable dioxolanes (II), dioxanes (III) and oxazolidines (IV) and their preparation are described in detail in the examples of German Patent Application DE 196 09 617 A1, page 5, line 54 to page 9, line 27.
Of these, the oxazolidines (IV) have particular advantages, and so are used with particular preference in accordance with the invention. Examples of especially suitable oxazolidines (IV) are N-(2-hydroxy-ethyl)-1,3-oxazolidine or N-(2-hydroxyethyl)-2-iso-propyl-1,3-oxazolidine, as described on page 6, Table 1, No. 5a and No. 5b of German Patent Application DE 196 09 617 A1.
For the preparation of the adduct (B) it is essential that the molar ratio of isocyanate groups in the diisocyanates (b1) to the isocyanate-reactive functional groups in the compound I (b2) is from 0.8:1.2 to 1.2:0.8, preferably from 0.9:1.1 to 1.1:0.9, and in particular 1:1.
The amount of the above-described adducts (B) in the coating materials, adhesives and sealing compounds of the invention may vary very widely. It depends in particular on the functionality of the crosslinking agents (D) and of the (meth)acrylate copolymer (A) and on the intended viscosity of the coating materials, adhesives and sealing compounds of the invention. The amount is preferably from 20 to 90, more preferably from 22 to 85, with particular preference from 23 to 80, with very particular preference from 24 to 75, and in particular from 25 to 70% by weight, based in each case on the solids content of the coating materials, adhesives and sealing compounds of the invention, it being possible to choose the amount of (B) to be up to twice as high as the amount of (A).
The second component to be used in accordance with the invention further comprises at least one reactive crosslinking agent (D). This crosslinking agent (D) may, however, also be present in a third component for use in accordance with the invention.
In the context of the present invention, a reactive crosslinking agent (D) is a crosslinking agent which in contrast to the above-described crosslinking agents (C) for one-component systems already reacts below 90, preferably below 70, more preferably below 60, with particular preference below 50, with special preference below 40, with very particular preference below 30xc2x0 C., and in particular at room temperature W the above-described (meth)acrylate copolymers (A), the adducts (B) following the elimination of ketone, and with any reactive diluents (C) that may be present for the thermal curing.
Examples of suitable reactive crosslinking agents (D) are polyisocyanates which contain on average more than two isocyanate groups in the molecule and may have been hydrophilically or hydrophobically modified. The polyisocyanates (D) are preferably liquid and of low viscosity, so that they can easily be incorporated into the second component or into the mixture of first and second components. Particular preference is given to the use of polyisocyanates (D) having from 2 to 5 isocyanate groups per molecule and having viscosities at 23xc2x0 C. of from 100 to 2000 mpa.s. If desired, small amounts of organic solvents (C), preferably from 1 to 25% by weight, based-on pure polyisocyanate (D), may be added to the polyisocyanates (D) in order thus to increase the ease of incorporation of the polyisocyanate (D) and, if appropriate, to reduce its viscosity to a level within the abovementioned ranges.
Examples of suitable polyisocyanates (D) are polyurethane prepolymers containing isocyanate groups, which can be prepared by reacting polyols with an excess of the above-described diisocyanates (b1) and are preferably of low viscosity. It is also possible to use polyisocyanates (D) containing isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea and/or uretdione groups. Polyisocyanates containing urethane groups, for example, are prepared by reacting some of the isocyanate groups with polyols, such as trimethylolpropane and glycerol, for example. It is preferred to use aliphatic or cycloaliphatic diisocyanates (b1), especially hexamethylene diisocyanate, dimerized and trimerized hexamethylene diisocyanate, isophorone diisocyanate, 2-isocyanato-propylcyclohexyl isocyanate, dicyclohexylmethane 2,4xe2x80x2-diisocyanate or dicyclohexylmethane 4,4xe2x80x2-diiso-cyanate, or mixtures of these diisocyanates.
Very particular preference is given to the use of mixtures of polyisocyanates (D) which contain uretdione and/or isocyanurate groups and/or allophanate groups and are based on hexamethylene diisocyanate or isophorone diisocyanate, as formed by catalytic oligomerization of hexamethylene diisocyanate or isophorone diisocyanate using appropriate catalysts.
The amount of the above-described crosslinking agents (D) in the coating materials, adhesives and sealing compounds of the invention may also vary very widely. In particular, it depends on the functionality of the crosslinking agents (D) and of the (meth)acrylate copolymers (A) and on the amount of adduct (B). The amount is preferably from 20 to 70, more preferably from 22 to 65, with particular preference from 23 to 60, with very particular preference from 24 to 55, and in particular from 25 to 50% by weight, based in each case on the solids content of the coating materials, adhesives and sealing compounds of the invention.
In addition, the second component for use in accordance with the invention, orxe2x80x94if usedxe2x80x94additionally, or only, the third component for use in accordance with the invention may comprise at least one of the above-described additives (C), provided these do not undergo unwanted reactions with the adducts (B) and/or crosslinking agents (D), such as decomposition reactions or premature crosslinking reactions, for instance.
Otherwise, all or some of the above-described additives (C) employed in each case in the coating materials, adhesives and sealing compounds of the invention may be present in the form of an independent, separate, third or fourth component.
The preparation of the coating materials, adhesives and sealing compounds of the invention from the components described above has no particular methodological features but instead is carried out with the aid of the customary and known, above-described mixing apparatuses and methods, or by means of customary two-component or multicomponent metering and mixing units. Ideally, thorough mixing is carried out by hand.
The coating materials, adhesives and sealing compounds of the invention are used to produce coatings, adhesive films and seals on and/or in primed and unprimed substrates. In particular, the coating materials of the invention are used to produce solid-color topcoats, clearcoats, and also basecoats and clearcoats in multicoat color and/or effect coating systems.
In methodological terms, the application of the coating materials of the invention has no special features but instead can be carried out by means of any customary application method, such as spraying, knifecoating, brushing, flowcoating, dipping, trickling or rolling, for example. It is preferred to employ spray application methods, such as, for example, compressed air spraying, airless spraying, high-speed rotation, electrostatic spray application (ESTA), alone or in conjunction with hot spray application such as hot air spraying, for example.
Suitable substrates are surfaces which are undamaged by curing of the coating materials, adhesives and/or sealing compounds present thereon using heat and, if appropriate, actinic radiation; examples include metals, plastics, wood, ceramic, stone, textile, fiber assemblies, leather, glass, glass fibers, glass wool and rock wool, mineral-bound and resin-bound building materials, such as plasterboards and cement boards or roofing tiles, and also combinations of these materials. Accordingly, the coating materials, adhesives and sealing compounds of the invention are also suitable for applications outside the automotive industry. Here they are particularly suitable for the coating, bonding and/or sealing of furniture, windows, doors, the interior and exterior of constructions, and for industrial coating, including coil coating, container coating, and the impregnation or coating of electrical engineering components. In the context of industrial coatings, they are suitable for the coating, bonding and/or sealing of virtually all parts for private or industrial use, such as radiators, domestic appliances, small metal parts such as nuts and bolts, wheel caps, rims, packaging, or electrical engineering components such as motor windings or transformer windings.
In the case of electrically conductive substrates it is possible to use primers which are prepared in a customary and known manner from electrodeposition coating (EDC) materials. For this purpose both anodic (AED) and cathodic (CED) electrodeposition coating materials are suitable, but especially CED coating materials.
The electrodeposition coating or electrodeposition coating film may be overcoated with a surfacer which is cured either alone or together with the electrodeposition coating film (wet-on-wet process). Overcoating with a surfacer is undertaken in particular in regions exposed to severe mechanical stress, such as by stonechipping, for example.
Examples of suitable cathodic electrodeposition coating materials and, where appropriate, of wet-on-wet processes are described in Japanese Patent Application 1975-142501 (Japanese laid-open specification JP 52-065534 A2, Chemical Abstracts No. 87: 137427) or in the patents and patent applications U.S. Pat. Nos. 4,375,498 A1, 4,537,926 A1, 4,761,212 A1, EP 0 529 335 A1, DE 41 25 459 A1, EP 0 595 186 A1, EP 0 074 634 A1, EP 0 505 445 A1, DE 42 35 778 A1, EP 0 646 420 A1, EP 0 639 660 A1, EP 0 817 648 A1, DE 195 12 017 C1, EP 0 192 113 A2, DE 41 26 476 A1 or WO 98/07794.
Similarly, appropriate surfacers, especially aqueous surfacers, which are also referred to as antistonechip primers or functional coats, are known from the patents and patent applications U.S. Pat. No. 4,537,926 A1, EP 0 529 335 A1, EP 0 595 186 A1, EP 0 639 660 A1, DE 44 38 504 A1, DE 43 37 961 A1, WO 89/10387, U.S. Pat. Nos. 4,450,200 A1, 4,614,683 A1 or WO 94/26827.
It is also possible to coat, bond or seal primed or unprimed plastics parts made, for example, of ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAT, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PC, PC/PBT, PC/PA, PET, PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM and UP (abbreviated codes in accordance with DIN 7728P1). In the case of unfunctionalized and/or apolar substrate surfaces, these may be subjected prior to coating in a known manner to a pretreatment, such as with a plasma or by flaming, or may be provided with an aqueous primer.
In accordance with the invention, the clearcoats and solid-color topcoats of the invention are produced by applying the coating materials of appropriate composition, according to the invention, to the substrates described above, after which the resulting clearcoat and solid-color topcoat films are cured.
In accordance with the invention, the adhesive films and seals of the invention are produced by applying the adhesives and sealing compounds of the invention onto and/or into the substrates described above. In the case of the adhesive bonding of substrates, the surfaces of two or more substrates to be bonded are preferably coated with the adhesive of the invention, after which the surfaces in question are brought into contact, under pressure if appropriate, and the resulting adhesive films are cured.
In accordance with the invention, a multicoat color and/or effect coating system according to the invention is produced on a primed or unprimed substrate by
(1) applying a basecoat to the substrate,
(2) drying and/or partial curing or full curing of the basecoat film,
(3) applying a clearcoat to the dried and/or partially cured basecoat film or the cured basecoat, and
(4) curing the clearcoat film together with the basecoat film, or separately curing the clearcoat film.
In a first preferred variant, a conventional basecoat and a clearcoat of the invention are used.
In a second preferred variant, a conventional clearcoat and a basecoat of the invention are used.
In a third preferred variant, a basecoat of the invention and a clearcoat of the invention are used.
Examples of conventional basecoats are known from patent applications EP 0 089 497 A1, EP 0 256 540 A1, EP 0 260 447 A1, EP 0 297 576 A1, WO 96/12747, EP 0 523 610 A1, EP 0 228 003 A1, EP 0 397 806 A1, EP 0 574 417 A1, EP 0 531 510 A1, EP 0 581 211 A1, EP 0 708 788 A1, EP 0 593 454 A1, DE-A-43 28 092 A1, EP 0 299 148 A1, EP 0 394 737 A1, EP 0 590 484 A1, EP 0 234 362 A1, EP 0 234 361 A1, EP 0 543 817 A1, WO 95/14721, EP 0 521 928 A1, EP 0 522 420 A1, EP 0 522 419 A1, EP 0 649 865 A1, EP 0 536 712 A1, EP 0 596 460 A1, EP 0 596 461 A1, EP 0 584 818 A1, EP 0 669 356 A1, EP 0 634 431 A1, EP 0 678 536 A1, EP 0 354 261 A1, EP 0 424 705 A1, WO 97/49745, WO 97/49747, EP 0 401 565 A1 or EP 0 817 684, column 5, lines 31 to 45.
Conventional clearcoats are one-component or multicomponent clearcoats, powder clearcoats, powder slurry clearcoats, UV-curable clearcoats or sealers, as known from the patent applications, patents and publications DE 42 04 518 A1, EP 0 594 068 A1, EP 0 594 071 A1, EP 0 594 142 A1, EP 0 604 992 A1, EP 0 596 460 A1, WO 94/10211, WO 94/10212, WO 94/10213, WO 94/22969 or WO 92/22615, U.S. Pat. Nos. 5,474,811 A1, 5,356,669 A1 or 5,605,965 A1, DE 42 22 194 A1, the product information bulletin from BASF Lacke+Farben AG, xe2x80x9cPulverlackexe2x80x9d [Powder coatings], 1990, the BASF Coatings AG brochure xe2x80x9cPulverlacke, Pulverlacke fxc3xcr industrielle Anwendungenxe2x80x9d [Powder coating materials, powder coatings for industrial applications], January 2000, U.S. Pat. No. 4,268,542 A1, DE 195 40 977 A1, DE 195 18 392 A1, DE 196 17 086 A1, DE-A-196 13 547, DE 196 52 813 A1, DE-A-198 14 471 A1, EP 0 928 800 A1, EP 0 636 669 A1, EP 0 410 242 A1, EP 0 783 534 A1, EP 0 650 978 A1, EP 0 650 979 A1, EP 0 650 985 A1, EP 0 540 884 A1, EP 0 568 967 A1, EP 0 054 505 A1, EP 0 002 866 A1, DE 197 09 467 A1, DE 42 03 278 A1, DE 33 16 593 A1, DE 38 36 370 A1, DE 24 36 186 A1, DE 20 03 579 B1, WO 97/46549, WO 99/14254, U.S. Pat. Nos. 5,824,373 A1, 4,675,234 A1, 4,634,602 A1, 4,424,252 A1, 4,208,313 A1, 4,163,810 A1, 4,129,488 A1, 4,064,161 A1, 3,974,303 A1, EP 0 844 286 A1, DE 43 03 570 A1, DE 34 07 087 A1, DE 40 11 045 A1, DE 40 25 215 A1, DE 38 28 098 A1, DE 40 20 316 A1 or DE 41 22 743 A1.
The curing of the applied coating materials, adhesive films and sealing compounds of the invention likewise has no special features as to method but instead takes place in general at room temperature over the course of 30 minutes to several days, for example, from 4 to 10 days. Curing can be assisted by the application of heat and/or actinic radiation. This is particularly the case when the coating materials, adhesive films and sealing compounds of the invention include constituents (C) which can be activated with actinic radiation, and/or comprise constituents (C) which are thermally curable, such as, for example, the crosslinking agents (C) for one-component systems. It is also the case, furthermore, when customary and known clearcoats or basecoats curable thermally and/or with actinic radiation are employed in the preparation of the multicoat color and/or effect coating systems of the invention. Curing with heat and actinic radiation is referred to in the art, inter alia, as xe2x80x9cdual curexe2x80x9d.
For thermal curing, the customary and known equipment, such as infrared and near-infrared lamps, hot air blowers, or circulating-air ovens are suitable.
In the context of the present invention, actinic radiation is electromagnetic radiation such as near infrared, visible light, UV light or x-rays, but especially UV light, and corpuscular radiation, especially electron beams. For curing, the corresponding radiation sources, such as UV lamps, for instance, are employed.
The coating materials, adhesives and sealing compounds of the invention have a high solids content with low viscosity and a long pot life.
The resulting coatings of the invention, especially the solid-color topcoats, clearcoats and multicoat color and/or effect coating systems, possess high hardness, flexibility and chemical resistance, excellent flowout, very good intercoat adhesion, an outstanding overall visual impression, very good weathering stability, very high scratch resistance, and very good polishability.
The adhesive films of the invention are of high and long-term bond strength even under extreme and/or very sharply and rapidly changing climatic conditions.
The seals of the invention provide complete and long-term sealing against chemically aggressive substances.
Therefore, the primed and unprimed substrates of the invention that are coated with at least one coating of the invention, bonded with at least one adhesive film of the invention and/or sealed with at least one seal of the invention possess not only the advantages set out above but also a particularly long service life, which makes them particularly valuable from an economic standpoint.

Multi-component coatings, adhesives and sealants and the use thereof

Abstract: wherein R1 and R2 are hydrogen or alkyl radicals, X and Y are oxygen, sulfur or  greater than Nxe2x80x94R6 where R6 is alkyl radical or aryl radical, R3 is alkylene radical and R4 and R5 are hydrogen, isocyanate-reactive groups or radicals R6; where R4, R5 or R6 contains an isocyanate-reactive group or R4 or R5 is an isocyanate-reactive functional group, and where R4, R5 or R6, where present, contain no isocyanate-reactive groups and the molar ratio of isocyanate groups in (b1) to the isocyanate-reactive groups in the compound I is 1.0.


An energy storage device that stores hot and/or cold energy includes an evaporating part and a condensing part. According to one aspect, the evaporating part includes a heat tube in a U shape or a thimble shape and further includes one or more power cycle tubes. A working substance within the evaporating part evaporates after absorbing heat and condenses in the condensing part after releasing heat.

Most of the current refrigerating and energy storing apparatuses and air conditioners utilize a compressor for cycle refrigerating the working substance through compression-expansion. It has the drawbacks of high product energy consumption, high operating cost, unstable operation, complicated maintenance, use of harmful medium, direct and indirect discharge of greenhouse gases and other contamination, noise pollution, strong dependence on electric power, and strong influence on electric power peak load.
The published specification of the Chinese a patent application for invention No. 91101569.8 discloses a refrigerating device composed of air conduit, coolant, transfusion box and cold storing body, wherein the air conduit exchanges heat with the coolant through the transfusion box for coolant, and the transfusion box for coolant exchanges heat with the cold storing body by communicating the coolant in steel tubes. In winter, it automatically introduce the amount of cold in the atmosphere by utilizing the static pressure difference generated by the hot and cold air and wind velocity in the air conduit, and store it in the cold storing body by using latent heat of phase change of water. When refrigerating in summer, the cold energy can be released through the heat exchange by the cold water supplying tube and the circulating of coolant with the cold storing body.
Said energy storage apparatus utilizes natural cold energy to achieve the object of energy saving and preventing the discharge of greenhouse gases and other contamination. But it has the following defects: (1) the input and output of cold energy is carried out by a large amount of commercial coolant, thus forced circulation is required at least for the output of cold energy, resulting in the low efficiency of the natural convection; (2) the input and output of cold energy both go through a secondary heat exchange, which will lower the efficiency of heat exchange and increase the loss of cold energy; (3) the air conduit can not eliminate loss of cold energy during conduction and convection; (4) the air conduit would be clogged; (5) the air and the steel tube wall have low efficiency of heat exchange, and a large amount of tubing and supports are required in real engineering; (6) the natural cold energy storage device satisfying the requirement of heat preservation, anti-expansion, anti-infiltration, and high efficiency of heat exchange is expensive, which is difficult to be put into practice.
Some of the current cold storing devices also use a single heat tube shown in FIG. 1 as the cold conducting element, but such storage apparatus with single heat tube still has the following defects: (1) the ascending vapor and descending coolant are in the same tube with circulation resistance occurred therebetween, causing an effect of heat exchange between each other, thus affecting the conducting power. Therefore the single heat tube has small cold conducting power; (2) relatively higher manufacturing cost under the condition of same conducting power; (3) the assembling is limited by angle; (4) it can not achieve ordered freezing by switching on and off or adjusting the magnitude of power.

Heat tube device utilizing cold energy and application thereof


An apparatus for radiometric measurement of thin fluid films includes a housing (1) enclosing means of radiation, a radiation guide, a reflector (4) and one or more detectors (5). The means of radiation is normally an IR radiator (2). The radiation guide is either a radiation tube (3) or a radiation cone (7). The reflector (4) is of the type non-imagining optics. If there is more than one detector (5) normally at least one detector is a reference detector.

It is known that different substrates absorb different, specific bands of IR (infrared) radiation. Thus, by directing IR radiation towards a thin film of the substrate it is possible to determine the thickness of the film. By a radiometric analysis it is further possible to determine the proportion of ingredients in the substrate and by continuous monitoring it is possible to establish changes of said proportion. Radiometric analysis is based on the change of energy or absorption of radiation, which in this case has wave-lengths within the IR area.
In many applications it is important to be able to control the thickness of a fluid film and the amount of different ingredients of the fluid film. This control could be used to optimize the desired effect, reduce the amount of used fluid and thereby save costs. In many instances it is normal to use superfluous amounts of a fluid, to be on the safe side. Controlling and monitoring the actual amount of fluid and its ingredients may diminish such superfluous amounts.


An earth probing system uses deep penetration of electromagnetic waves into soil and other media. Advantage is taken of the lower attenuation of radar waves in soil by frequencies of about three megahertz or less. Bursts of electromagnetic energy of various frequencies in this range are consecutively transmitted. The transmitting antenna is continuously tuned, so as to maintain resonance during each burst, allowing large circulating currents and high power output. In a receiving antenna system, a dual antenna arrangement is providing for obtaining improved reception. A corresponding dual antenna circuit employs "spatial notch filtering", automatic adjustment of antenna gain-frequency variations, as well as compensation for transmitter gain variation. The system may be implemented in a totally analog, totally digital, or hybrid manner. Preferably, a signal processing method detects and digitally samples signals reflected from subsurface layers and buried objects. The invention provides means for removing system distortions and interfering signals, for compensating for aliasing errors and frequency-dependent antenna gain and phase variations, and for avoiding masking errors introduced by strong reflections.

1. Field of the Invention
The present invention relates to earth probing systems. More specifically, the invention relates to earth probing systems using low frequency electromagnetic energy to provide detailed information regarding subsurface formations, especially such systems involving system distortion compensation, noise separation, interference removal, and recording, display and mapping of subsurface formations.
2. Related Art
Historically, seismic (sound) waves have been radiated into the earth to detect and map subsurface layers and buried objects. In the recent past, electromagnetic waves have been employed to produce similar detections and mapping. However, results have been limited to shallow ground penetration depths because of the extreme attenuation of the electromagnetic waves as they propagate through the earth. The attenuation of the electromagnetic wave varies drastically with frequency, as seen in TABLE 1.
TABLE 1 ______________________________________ ATTENUATION OF RADAR ENERGY BY A LAYER OF BITUMINOUS COAL AS A FUNCTION OF RADAR FREQUENCY ONE WAY ATTENUATION FREQUENCY (dB per Meter) ______________________________________ 250 KiloHertz 0.005 500 KiloHertz 0.01 1.0 MegaHertz 0.02 5.0 MegaHertz 0.10 25.0 MegaHertz 0.50 100.0 MegaHertz 2.00 500.0 MegaHertz 10.00 1.0 GigaHertz 20.00 ______________________________________
An early example of an attempt to use radio frequency mapping is that of Deardorf (U.S. Pat. No. 1,838,371), who used relatively low power to identify subsurface anomalies in the earth. Potapenko (U.S. Pat. No. 2,139,460) calculated the ratio of absorption of two radio frequencies to identify oil and water deposits. Wheeler (U.S. Pat. No. 2,517,951) employed a wide band antenna, tuned inductively at several points along its length in an effort to transmit more energy into the earth from a radar transmitter. Feder (U.S. Pat. No. 3,351,936) employed two complete radar transmitters and receivers to achieve identification of subsurface reflections. Barret et al. (U.S. Pat. No. 2,901,689) used transmitting and receiving antennas at various angles of incidence and reflection to plot earth cross sections. Chapman (U.S. Pat. No. 4,008,469) employed short pulse, conventional radar equipment along with relatively sophisticated signal processing equipment for subsurface plotting. Fowler et al. (U.S. Pat. No. 4,504,833) uses a synthetic pulse made up of Fourier component frequencies in order to obtain more easily interpreted reflection signals. Thomas (U.S. Pat. No. 5,113,192) employs audio frequency seismic reflection data to help interpret the findings from a ground penetrating radar. Kimura et al. (U.S. Pat. No. 5,130,711) utilizes a polarization-advancing scheme to achieve recognition of signals reflected from underground formations. It is believed that no known systems can achieve penetrations to a depth of a mile, which is frequently required for oil/gas and mineral exploration.
Applicants have recognized that, to obtain electromagnetic wave subsurface maps to depths of one mile or more, the radiated frequency should be about 1-3 Megahertz or less. However, to obtain good resolution, the bandwidth should be as large as possible. To achieve both of the above goals, a large "percentage bandwidth" spectrum must be radiated into the earth. These two conflicting requirements, that of very low operating frequency and a wide percentage bandwidth, represent a challenging design problem for the radar antenna system designer.
As used herein, lower frequency electromagnetic spectrum may be generally divided into bands for the purpose of description, as shown in TABLE 2 (Reference Data For Radio Engineers, Sixth Edition, Howard W. Sams & Co., Inc., page 27-6.):
TABLE 2 ______________________________________ NOMENCLATURE OF ELECTROMAGNETIC FREQUENCY BANDS DESIGNATION FREQUENCY RANGE ______________________________________ ELF--Extremely Low Frequency 3-300 Hz VF--Voice Frequency 300-3,000 Hz VLF--Very Low Radio Frequency 3-30 KHz LF--Low Radio Frequency 30-300 KHz MF--Medium Frequency 300-3,000 KHz ______________________________________
Reception and processing of large-percentage-bandwidth signals using ELF, VF, VLF, LF, and MF electromagnetic waves necessary for earth probing radar systems, require unique instrumentation methods to overcome problems not adequately dealt with by known systems. These problems include proper waveform selection and generation, radiation, reception, and signal processing to detect and enhance subsurface returns. Also, short pulse and linear frequency-modulated pulse compression systems generate spurious signal components due to resonant ringing of the antenna and impedance matching system.
A further design problem has derived from the facts that low frequencies entail long wavelengths, and that antennas which are small compared to the radiated wavelength have very low efficiency and very low gain. Therefore, to use low frequencies would require use of either large antennas or use of high-magnitude currents. Large antennas are impractical, and high-magnitude currents have not been found in systems suitable for high resolution deep-earth probing.
Still another design problem, relating more specifically to signal reception, has derived from the facts that antennas which are small compared to the radiated wavelength have very low efficiency and very low receiving aperture area, and that radar receiving antennas generally display non-uniformity in their frequency response over the large percentage bandwidth required for high resolution earth probing applications. These applications require a high degree of isolation between the transmitting and receiving antennas, to provide adequate sensitivity to the much weaker subsurface return signals. This design problem has not been dealt with adequately in known systems.
Applicants have also recognized that transmission and reception of such signals require unique electrical properties in the antenna system, and special processing techniques for received signals. To achieve sufficient radiated power for ground penetration, a means of maintaining antenna efficiency across the entire operating band must be provided. Reliable detection and location of buried objects by a deep probing radar system further requires precise control and compensation of antenna phase and amplitude response, in order to perform sensitive signal processing operations on the received data.
The present invention embodies unique concepts for solving these and other problems which limit the performance of conventional pulsed radar systems when operating at low frequencies and large percent bandwidths. The novel, heretofore unknown, technology for radar operation in these frequency bands is the subject of the present invention.

System and method for earth probing with deep subsurface penetration using low frequency electromagnetic signals


The present invention relates to an anti-loose socket and a pull-out locking mechanism thereof, wherein inside the anti-loose socket, there are a pull-out locking mechanism composed of a bevelled sleeve (15) and two cylinders (16) arranged in a symmetrical manner at two sides within the bevelled sleeve; an inside longitudinal section of the bevelled sleeve has a cone angle in an umbrella shape, the middle portion of the bevelled sleeve allows a plug pin (61) to pass through; the cylinder is mounted on a floating block (14) movable up and down, and can move up and down along the inside conical surface of the bevelled sleeve by the floating block. When the plug (6) is pulled out upwards, the cylinder moves upwards, however due to the limiting action of the bevel surface, the cylinders stick to the two bevel surfaces more and more tightly.

Common sockets are various, wherein the connection ways between the plug and the socket are mainly insert in structures. The anti-loose sockets in prior art are as follows:
One. An anti-loose socket in Application 200820192348.5 comprises: a socket (1), a boss (2) is mounted on the bottom of the socket (1), oblique wedged slots (3) are provided at two sides of the boss (2), pulleys on the lower ends of the two fixed arms (4),(5) slide within the wedged slots (3), hook-shaped upper ends of the two fixed arms (4),(5) pass through the holes in the upper lid of the socket (1) and out of the socket (1), a connecting rod (6) is connected to the two fixed arms (4),(5) via rotating shafts (7),(8), respectively, and mounted below the inserting hole composed of elastic metal copper sheet; a supporting rod (9) passes through one end of the connecting rod (6) and is fixed on the boss (2), a spring (10) on the supporting rod (9) is connected to the connecting rod (6) on one end, and is connected to the boss (2) on the other end. Its advantage is: the plug can be inserted in and pulled out easily and securely, the plug does not easily drop off, its use is safe and convenient, ensuring the normal use and power utilization safety of the electrical appliance.
Two. An anti-loose socket which can fix plug wirings in Application 200820165244.5 comprises socket components, an inserting hole is provided in the middle portion of the socket, two supporting rods are provided below the inserting hole, a movable fixture is mounted on the top end of the supporting rod. Its advantages are: it is simple in structure, convenient and safe to use; and it can fix wirings, so as to prevent the plug from being pulled out.
Three. An anti-loose safety socket in Application 200810116688.4 comprises an insulated housing having several inserting holes, an electrode is provided in each inserting hole, wherein: at least one one way interference member is disposed within the insulated housing, which prevents the inserting of the plug from being influenced, however, the pulling out of the plug will be interference. This invention conclusively achieves the invention objective of simple structure and convenient operation.
The three types of anti-loose sockets utilize a torsion fixed structure, a supporting rod-movable fixture fixed structure, and a transversal interference fixed structure; the three fixed structures each has its own character, but is not so convenient during use. The current problem in the art of anti-loose socket is that, the plug after being inserted into the socket can be automatically secured and locked, and will not loose under a general external force, the plug can be pulled out of the socket only after the secured position has been opened by a particular structure.

Anti-loose socket and pull-out locking mechanism thereof


An example damp can include a first post, a first clamping element rotatably oupled to the first post, a second post separate from the first post, a second clamping lement rotatably coupled to the second post, and a biasing device that couples the first lamping element to the second damping element.

Apparatus, such as imaging systems (e.g., copiers, printers, and the like), can have doors, drawers, panels, and the like for accessing the interior of the apparatus, such as for maintenance, repairs, etc. For example, panels and/or doors can provide access to an interior of an imaging system for clearing print media (e.g., paper, plastic, etc.) jams. Some apparatus can include replaceable units, such as field replaceable units (FRUs), that can include a number of components, such as servomechanisms, motors, etc. For example, such a unit can be removed from an apparatus and replaced by another unit.

Clamps having rotatable clamping elements

Hewlett-Packard Development Company, L.P.


A transistor formed on a semiconductor substrate is covered with a first insulating film, and first conductive vias which pierce the first insulating film and which reach the transistor and a second conductive via which pierces the first insulating film and which reaches an inside of the semiconductor substrate are formed. After the formation of the first conductive vias and the second conductive via, a second insulating film is formed over the first insulating film. Conducive portions connected to the first conductive vias leading to the transistor and a conductive portion connected to the second conductive via which reaches the inside of the semiconductor substrate are formed in the second insulating film. By doing so, a multilayer interconnection is formed.

A technique for forming a conductive via in a semiconductor substrate used in a semiconductor device and electrically connecting the upper and under sides of the semiconductor device by the use of the conductive via is known. For example, such a semiconductor device is used in plurality for fabricating an apparatus having a stacked structure in which they are stacked and in which they are electrically connected to one another. For example, the following method is known as a method for forming a conductive via in a semiconductor substrate. A wiring layer is formed on an upper side of a semiconductor substrate. After that, a via hole is made in the semiconductor substrate and the via hole is filled in with a conductive material.
Japanese Laid-open Patent Publication No. 2009-016773
Japanese Laid-open Patent Publication No. 2009-064820
When a semiconductor device in which conductive vias are formed in a semiconductor substrate is fabricated, the conductive vias are formed in the semiconductor substrate in addition to elements, such as transistors. As a result, a fabrication process may become complex. Furthermore, if the conductive vias are formed in the semiconductor substrate, for example, after the formation of a wiring layer, then it may be impossible from the viewpoint of a fabrication process to form the conductive vias with accuracy. Alternatively, there may be need for determining the arrangement of wirings and the like in the wiring layer with the arrangement of the conductive vias taken into consideration.


A method and a system for controlling quality of service of a storage system, and a storage system. The method includes: collecting information about processing capabilities of the hard disks in the storage system and obtaining processing capabilities of the hard disks according to the information about processing capabilities; dividing a cache into multiple cache tiers according to the processing capabilities of the hard disks; and writing, for a cache tier in which dirty data reaches a preset threshold, data in the cache tier into at least one hard disk corresponding to the cache tier. The method avoids a phenomenon of preempting page resources in the cache.

A cache is a component introduced to improve performance of a storage system and is mainly configured to improve input/output (I/O) performance of the entire system. Some temporary data is stored in this cache, thereby accelerating an I/O response of a host. For a read operation of the host, the system temporarily stores read data in the cache and the cache can be hit directly during the read operation of the host, thereby omitting the operation of accessing at least one hard disk. For a write operation of the host, the system directly caches write data of the host into the cache, thereby omitting the operation of writing data into at least one hard disk. In order to perform the read or write operation smoothly, the data can be prefetched from at least one hard disk into the cache according to a certain policy, where the data is likely to be read by the host next time. This operation can raise a cache hit ratio. In addition, the data written into the cache can be combined based on a certain combination policy before writing the data into the hard disk, thereby reducing the time of implementing the write operation. As can be seen from the above, for read operation, the cache hit ratio can be raised by optimizing a prefetch algorithm or increasing the size of the cache, thereby improving the read performance of the entire storage system. However, when the cache is enlarged to a certain extent, a performance improvement of the read operation and an increase in the size of the cache are disproportionate. Quality of service (QoS) is a quality convention on information transmission and sharing between a network and a user and between users that communicate with each other on the network. The quality of service may include a transmission bandwidth, a transmission delay, a packet loss rate of data, and the like. On the network, the quality of service can be improved by taking measures such as ensuring the transmission bandwidth and reducing the transmission delay, the packet loss rate, and delay variation.
A current storage system supports mixed insertion of various types of hard disks. However, rotational speeds and throughput of different types of disks are different. This always leads to a processing performance difference during writing data into different hard disks. In addition, even for disks of a same type, a processing capability difference may also be caused due to manufacturers or an aging problem. In this scenario, data written into a cache cannot be released in time because of a processing capability difference of back-end disks. As a result, a slow-processing disk occupies more and more page resources, and a processing speed of a fast-processing disk is affected because no cache page is allocated to the fast-processing disk. In addition, even the processing performance of the entire system levels off to that of the slowest disk on the system, that is, the cask effect occurs.
In the prior art, the preceding problem is solved by using a cache partition technology. FIG. 1 is a schematic diagram of an application scenario of a cache partition technology in the prior art. In the prior art, the cache partition technology is used to divide cache resources into multiple cache partitions according to services on a host, each cache partition corresponds to one or more hosts, and the cache partitions are independent of each other and do not affect each other. However, in the prior art, a page resource preemption phenomenon still occurs in each cache partition. As a result, the performance (such as a transmission delay and a packet loss rate) of a service corresponding to a cache partition is affected by the slowest back-end disk, and the quality of service of the storage system is reduced.

Quality of service control method for storage system