CN1934141A - Orthoester-protected polyols for low VOC coatings - Google Patents

Abstract

The invention relates to a coating composition wherein orthoester groups block the hydroxyl groups of the poly(meth)acrylate wherein the orthoester groups can be removed through hydrolysis in order to facilitate cross-linking through reaction with isocyanate compounds. The invention also relates to a process for curing the aforementioned coating composition. The invention also relates to a process for coating substrates wherein a clear coat comprising the aforementioned coating composition is coated over a base coat. The invention also relates to a process for blocking the hydroxyl groups of a poly(meth)acrylate compound through reaction with an orthoester compound.

Description

The orthoester-protected polyvalent alcohol that is used for low VOC coatings

The reference of related application

It is No.60/555 that the application requires application number according to 35U.S.C. § 119, the right of priority of 162 U.S. Provisional Application (applying date is on March 22nd, 2004), and described document is incorporated this paper into, as providing in full, as a reference.

Invention field

The present invention relates to be used for prepare the hydroxyl protection in poly-(methyl) acrylate of the low coating of content of volatile organic compound, described coating adopts multi isocyanate crosslinking.

Background of invention

The key of trimming coating is that the vehicle after can will rebuilding with the outward appearance of optimum extent as quickly as possible consigns to client.Client want to have as quickly as possible outward appearance beautiful, repair good vehicle to reduce the inconvenience that does not have car to greatest extent.The manually total and cost that repair shop wants farthest to optimize his fund input and will keep in repair a car minimizes.Thus, productivity in the whole maintenance process and good surface appearance are very important.

In addition, exploitation low VOC (" VOC "), that is: the pressure extend over the entire globe of eco-friendly coating system.A key that addresses these problems is to reduce or eliminate solvent used in the coating significantly.These are novel, low VOC coatings need satisfy crucial user's quality, comprise productivity, outward appearance and film properties, also must be firm, user-friendly system simultaneously.

Current, automobile trimming market mainly is made up of two-component coating, this two-component coating can be solidified at ambient temperature crosslinked, three-dimension film.These coating mainly are solvent type and adopt hydroxyl/isocyanate to solidify.One of component of this system comprises the hydroxyl functional material; Another component comprises isocyanic ester.Be about to before spraying on the vehicle, to mix these components.These two-component coatings need remain on enough low viscosity still can spray after long-time, after this, after the spraying, requirement fast setting on vehicle is that three-dimensional net structure is so that productivity and physicals the best.

When the damage of reparation such as car body indenture, reach former coating on every side in sand milling or this damage field of milling mechanically usually.Sometimes, divest this former coating with the naked metal under exposing from part car body or whole locomotive body.After repairing this damage, angle healthy from the operator and the discharging nuisance is considered, usually with in atmosphere passes between the portable or fixed low-cost japanning of removing organic solvent from the lacquering of new coating in the mode of safety mutually, preferably adopt the low VOC coatings composition to apply the surface that this is repaired.Usually, the drying of the lacquer of this new coating takes place with being solidificated in these enclosed spaces.And aforesaid drying and curing schedule take place in this enclosed space to prevent that this wet paint is infected with the dirt in air or other pollutent.

Owing to a large amount of spatial areas that occupied as a rule smaller car body japanning service shop between these japannings, so these workshops are preferably dry as quickly as possible and these lacquers of curing.Comparatively Ang Gui enclosed space provides thermal source usually, such as the routine heating fluorescent tube that is positioned at this enclosed space inside, so that the new lacquer that applies solidifies at faster speed.Therefore, in order to provide the better utilization of workshop spatial area cost benefit and will to drop to minimum by the fire that the wet coating of solvent based coating composition is caused, seeking always and can solidify at ambient temperature, the fast-curing paint composition of outstanding performance characteristics, particularly scaling resistance, anti-galled spots, weather resistance and outward appearance still can be provided simultaneously.

An ability that critical aspects is a physical dryness of trimming coating material production rate.Large-duty coating needs to be dried to the degree that can touch very apace, to allow to apply follow-up coating.Be used for repairing the less partial clear lacquer on the damage vehicle (point is repaired the clear lacquer) and require alap overspray, reduce to minimum will protect the required flow quantity in unspoiled japanning zone.In the product of these types, high glass-transition temperature (" Tg "), higher weight-average molecular weight (" M _w") acrylic resin can physical dryness show very goodly because of it.

Therefore, in order to develop the product system of a kind of low VOC, importantly preparation can be used as the high Tg of production system component, higher relatively M _wAcrylic resin, described system is applicable to physical dryness and can be to disadvantageous effect is not arranged working life.

WO02/10298 discloses the sealing polyvalent alcohol with hydrolysable silyl group.JP2001-163922 has described and has made oligopolymer that contains poe (α-or β-ethylene glycol) and ethylenically unsaturated group and the resin reaction with at least two hydroxyls.WO02/057339 discloses by using the spiro orthocarbonate group to protect hydroxyl.The U.S. Pat 6 that people such as Van den Berg proposed October 2 calendar year 2001,297,329 disclose a kind of coating composition, comprise a kind of at least one dicyclo-or first compound of volution-ortho ester group and a kind ofly contain at least two second compounds that hydroxyl had reactive group that contains.The U.S. Pat 6,045,870 that people such as Noura proposed on April 4th, 2000 discloses by silylation protects carboxyl.

Hope improves physical dryness and prolongs working life by the new polymers that use has protected hydroxyl.Coating disclosed herein is stable under anhydrous condition, but after applying, by absorbing atmospheric moisture, discharges original hydroxyl, has activity and become, and perhaps has been disengaged sealing.In case hydroxyl is released, it will with the isocyanate crosslinking rapid reaction generating three-dimensional net structure, and very fast film forming will appear.

The invention summary

The present invention relates to a kind of coating composition, wherein, ortho ester group has sealed the hydroxyl of poly-(methyl) acrylate.This ortho ester group can be removed by hydrolysis, so that by crosslinked with the reaction of polyisocyanate compound.The invention still further relates to a kind of method that is used to solidify aforementioned coating composition.The invention still further relates to a kind of method that is used for coated substrate, wherein, on undercoat, apply the Clear coating that contains aforementioned coating composition.The invention still further relates to a kind of method by sealing the hydroxyl of poly-(methyl) acrylic compound with the reaction of ortho ester compound.

Detailed Description Of The Invention

Especially all the are cited full content of document of applicant is incorporated this paper into.It is that No.____, name are called the reference of applying for of " polyvalent alcohol that is used for the ketal protection of low VOC coatings " that the applicant has also incorporated sequence number total and that propose simultaneously into.

Quote the numerical range part herein, except as otherwise noted, this scope all means all integers and the mark that comprises within its end points and this scope.When limiting a scope, do not wish to limit the scope of the invention to the concrete numerical value that this is quoted.

In this manual, will use some terms.

Term " (methyl) acrylate " expression acrylate and methacrylic ester the two.

" polymolecularity " of term polymer is M _wWith number-average molecular weight (" M _n") ratio.

Term " low VOC coatings composition " means the coating composition that every liter of coating composition comprises 0.1 kilogram (1.0 pounds/gallon)-0.72 kilogram (6.0 pounds/gallon), preferred 0.3 kilogram (2.6 pounds/gallon)-0.6 kilogram (5.0 pounds/gallon), more preferably 0.34 kilogram (2.8 pounds/gallon)-0.53 kilogram of (4.4 pounds/gallon) solvent.All VOC all measure according to the method that provides among the ASTM D3960.

In an embodiment, the present invention relates to a kind of coating composition that contains poly-(methyl) acrylate and at least a polyisocyanate compound, described poly-(methyl) acrylate comprises at least two hydroxyls that sealed by hydrolyzable ortho ester group.

In another embodiment, the present invention relates to a kind of method that is used for the hydroxyl of poly-(methyl) acrylate of sealing, comprise making poly-(methyl) acrylate and at least a ortho ester compound that comprise at least two hydroxyls carry out thermal response.

" be closed " at least two hydroxyls meaning by poly-(methyl) acrylate and the reaction between at least a ortho ester compound to form hydrolyzable ortho ester group, form a kind of hydrolyzable ester.In an embodiment, approximately the hydroxyl of 30%-100% is sealed by the ortho ester compound.In a preferred embodiment, the ortho ester compound has sealed all hydroxyls on substantially." all basically hydroxyls " mean vinyl ether compound and have sealed at least 70% hydroxyl.

In a preferred embodiment, comprise gathering (methyl) acrylic compound and, allocating coating composition of at least two hydroxyls by protecting these hydroxyls with the acid catalyzed reaction of at least a ortho ester compound by at first getting.This etherification reaction obtains a kind of poly-(methyl) acrylic compound, and wherein, hydroxyl is sealed by ortho ester group.When needs are used for coating composition, before adding polyisocyanate compound or simultaneously, optionally in the presence of acid catalyst,, poly-(methyl) acrylic compound of this sealing are removed sealed by these ortho ester groups of water hydrolysis.The hydroxyl that is disengaged sealing in poly-(methyl) acrylic compound can freely react with the preparation coating composition with polyisocyanate compound by any method known to those skilled in the art.

The non-limitative example that is used for poly-(methyl) acrylate of coating composition is the vinylformic acid of 1-20 carbon atom straight chain or branched monobasic alcohol and the polymerization single polymerization monomer of methacrylic ester.Preferred ester is alkyl acrylate and the alkyl methacrylate that has 1-12 carbon atom in the alkyl, methyl acrylate for example, ethyl propenoate, propyl acrylate, isopropyl acrylate, butyl acrylate, the vinylformic acid pentyl ester, Ethyl acrylate, the 2-ethylhexyl acrylate, vinylformic acid ester in the ninth of the ten Heavenly Stems, the vinylformic acid laurate, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, the methacrylic acid pentyl ester, N-Hexyl methacrylate, 2-ethylhexyl-methacrylic ester, nonyl methacrylate, the methacrylic acid laurate, or the like.Isobornyl methacrylate and isobornyl acrylate monomer also can use.Alicyclic (methyl) acrylate also can use, for example trimethylcyclohexyl acrylate, tert-butylcyclohexyl acrylate, methacrylic acid cyclohexyl ester, isobornyl methacrylate, 2-ethylhexyl-methacrylic ester, or the like.Vinylformic acid aryl ester such as vinylformic acid benzyl ester and methacrylic acid benzyl ester also can use.

Can use the ethylenically unsaturated monomer that contains hydroxy functional group, comprise acrylic acid hydroxy alkyl ester and hydroxyalkyl methacrylate, wherein, alkyl has 1-4 carbon atom.Suitable monomers comprises Hydroxyethyl acrylate, Propylene glycol monoacrylate, vinylformic acid hydroxyl isopropyl esters, 2,3-dihydroxypropyl acrylate, vinylformic acid hydroxy butyl ester, vinylformic acid dihydroxy butyl ester, hydroxyethyl methylacrylate, Rocryl 410, hydroxyethyl methacrylate isopropyl esters, methacrylic acid hydroxy butyl ester, methacrylic acid dihydroxypropyl ester, methacrylic acid dihydroxy butyl ester etc., and composition thereof.Hydroxy functional group can also be obtained by monomer presoma (for example, the unitary epoxy group(ing) of glycidyl methacrylate in the polymkeric substance).Such epoxy group(ing) can be in post-polymerization be converted into hydroxyl with water or small amount of acid reaction.

Operable other suitable olefinic unsaturated comonomer comprises that acrylamide and Methacrylamide reach the derivative such as alkoxyl-methyl (methyl) acrylamide monomer, for example, Methacrylamide, N-isobutyl oxygen methyl-Methacrylamide and N-methylol-Methacrylamide; Maleic anhydride, itaconic anhydride and fumaric acid anhydride and half ester thereof and diester; Vinyl aromatic compounds, for example vinylbenzene, αJia Jibenyixi and Vinyl toluene; And the mono acrylic ester of polyoxyethylene glycol and monomethacrylates.

Other functional monomer; for example the reaction product of itaconic anhydride or maleic anhydride, its half ester, vinyl cyanide, allyl methacrylate(AMA), methacrylic acid acetoxyl acetyl 2-ethoxyethyl acetate, methacryloyl acid amides glycolate methyl ether, methacrylic acid ethylidene-urea ethyl ester, 2-acrylamide-2-methyl propane sulfonic acid, methacrylic acid trialkoxysilyl ethyl ester, monobasic epoxy ester or monobasic ether epoxy and alpha-beta unsaturated acid and the monacid reaction product of (methyl) glycidyl acrylate and maximum 22 carbon atoms also can be used.

Preferably, the M of poly-(methyl) acrylate _nAbout 200 to about 50,000 scope.Comparatively preferably, the M of poly-(methyl) acrylate _nAbout 300 to about 20,000 scope.More preferably, the M of poly-(methyl) acrylate _nAbout 500 to about 6,000 scope.All molecular weight of indication are all measured by the gel permeation chromatography (" GPC ") that adopts polystyrene standards herein.

Poly-(methyl) acrylic compound of the poly-preferred per molecule of (methyl) acrylate comprises 2-200, more preferably 2-50,2-20 hydroxyl most preferably.

In a preferred embodiment, poly-(methyl) acrylate has about 1.5 polymolecularity to about 10.0 scopes.In a comparatively preferred embodiment, poly-(methyl) acrylate has about 1.5 polymolecularity to about 5.0 scopes.In a more preferred embodiment, poly-(methyl) acrylate has about 1.5 polymolecularity to about 3.0 scopes.

The polyisocyanate compound of coating composition comprises that one or more have the linking agent of at least two isocyanate groups.The isocyanic ester of the aromatic series of any routine, aliphatics, alicyclic isocyanic ester, trifunctional and the isocyanate-functional adducts of polyvalent alcohol and vulcabond all can use.Usually the available vulcabond is 1, the 6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4 '-Ya biphenyl diisocyanate, tolylene diisocyanate, the dicyclohexyl vulcabond, the tetramethylene Xylene Diisocyanate, the ethyl ethylidene diisocyanate, 2,3-dimethyl ethylidene diisocyanate, 1-methyl trimethylene vulcabond, 1,3-cyclopentylidene vulcabond, 1,4-cyclohexylidene vulcabond, 1, the 3-phenylene vulcabond, 1, the 5-naphthalene diisocyanate, two-(4-isocyanate group cyclohexyl)-methane, and 4,4 '-diisocyanate based diphenyl ether.

Typical trifunctional isocyanates comprises triphenylmethane triisocyanate, 1,3,5-benzene triisocyanate and 2,4,6-toluene triisocyanate.The tripolymer of vulcabond also can use, the tripolymer of hexamethylene diisocyanate for example, and by Bayer Corp., Pittsburgh, Pa. is with trade name Desmodur ^N 3300A provides.Other suitable polyisocyanates from Bayer Corp. comprises Desmodur ^N 3390A BA/SN and Z 4470BA polyisocyanates.

The relative quantity that is used for the linking agent of coating composition is adjusted to the molar equivalent that makes NCO/ (OH+NH) than about 0.5 to about 5 scope, preferably about 0.7 to about 3 scope, more preferably about 0.85 to about 2 scope.

Coating composition is suitable for use as transparent or coloured composition.This coating composition can be used as single coating, is used as undercoat or is used as priming paint.

Coating composition can comprise other component such as solvent, catalyzer, pigment, filler and conventional additives.

Some suitable solvent comprises aromatic hydrocarbon based, as petroleum naphtha or xylene; The ester class is as butylacetate, tert.-butyl acetate, isobutyl acetate or hexyl acetate; And glycol ether ester, as propylene glycol monomethyl ether.The amount of added organic solvent depends on desirable level of solids of composition and desirable VOC amount.If desired, all can add organic solvent in two of this coating composition kinds of components.

Coating composition preferably includes the catalyzer of catalytic amount to promote solidification process.Usually, use about 0.001% to about 5% scope, preferably approximately 0.002% to about 3% scope, more preferably about 0.005% catalyzer to about 1.5% the scope, all with the weight percent meter of crosslinkable component and linking agent component total weight of solids.Various catalyzer be can use,, dibutyl tin dilaurate and oxalic acid two fourth tin comprised as tin compound; And tertiary amine, as triethylenediamine.These catalyzer can be separately or are used jointly with carboxylic acid such as acetate.Specially suitable is a kind of with trade name Fastcat ^4202 dibutyl tin dilaurates (Elf-Atochem North America, Inc., Philadelphia, Pa.) commercial catalyst of Chu Shouing.

Make the hydrolysis of protectiveness group can recover to have to can be used for initial poly-(methyl) acrylate of crosslinked hydroxyl.Hydrolysis can, optionally in the presence of a kind of acid catalyst, in water, take place.Suitable acid for example, comprises acetate etc., phosphorus and phosphoric acid and ester, hydrochloric acid, perchloric acid, Hydrogen bromide, sulfuric acid and half ester thereof, as the sulfonic acid of Witco 1298 Soft Acid and by the acidic compound of hydrolysis, as POCl ₃, SOCl ₂, and PCl ₅

Hydrolysis reaction can or carry out before adding linking agent simultaneously.Preferably, poly-(methyl) acrylate of sealing is disengaged sealing, regains hydroxyl thus, adds linking agent simultaneously.Should be appreciated that because the ortho ester group that exists in water and the composition contacts, so these ortho ester groups will begin hydrolysis, and finally make composition be crosslinked.Can introduce water in every way.For example, particularly in the situation of coating, can be by introducing water uncrosslinked by the mode that absorbs moisture in the air or just in crosslinked (taking place crosslinked in) coating.For preparation very stable always uncrosslinked coating composition before being exposed to (wetting) air, the mode that absorbs moisture is very convenient.Perhaps, can be about to take place water to be sneaked into (being used for applying) mixing head or spraying mixing head before crosslinked.

Coating composition can comprise one or more tinting materials or produce the pigment of special effects.Example inorganic or organic coloring pigment comprises titanium dioxide, micronized titanium dioxide, iron oxide pigments, carbon black, azo pigment, phthalocyanine pigment, quinoline a word used for translation ketone pigment and pyrrolopyrrole pigment.The example that produces the pigment of special effects comprises aluminum slice, copper (bronze) thin slice and other sheet metal; Coated interference pigment, as the metallic pigment of metal oxide-coated, for example, aluminium titanium dioxide-coated or mixed oxide coated; The mica that applies, for example, the mica of titanium dioxide-coated and graphite special effects pigment.

The example of filler comprises silicon-dioxide, pure aluminium silicate, barium sulfate and talcum.

Coating composition can also comprise conventional additives, as, wetting agent; Levelling and flow control agent, for example BYK ^320 and 325 (high molecular weight polypropylene acid esters; BYK-Chemie USAInc., Wallingford, Conn.), BYK ^347 (siloxanes of polyethers-modification) and BYK ^306 (dimethyl polysiloxanes of polyethers-modification); Rheological control agent such as aerosil; Defoamer; Tensio-active agent; And emulsifying agent, to help stablizing said composition.Can also add other additive that is used to improve resistance to marring, for example silicon sesquialter alkane and other particulate based on silicate.Certainly, this class additive will depend on the desired use of coating composition.When said composition is used as Clear paint, will not comprise that any meeting is to solidifying the additive that back coating transparency has disadvantageous effect.According to the desired use of coating composition, above-mentioned additive can add in one of any in two kinds of components or its two in.

In order to improve the weathering resistance of coating, can add about 0.1 weight % to about 5 weight %, preferably approximately 0.5 weight % to about 2.5 weight %, more preferably about 1 weight % is to ultraviolet light stabilized screener, quencher and the antioxidant of about 2 weight % in composition, this per-cent is based on binding agent and linking agent component total weight of solids meter.Typical ultravioletlight screening agent and stablizer comprise following:

Benzophenones, for example, hydroxyl dodecyloxy (dodecycloxy) benzophenone, 2,4 dihydroxy benzophenone and the hydroxy benzophenone that contains sulfonic acid group.

Benzoates, for example, the p t butylbenzoic acid ester of the dibenzoate of dihydroxyphenyl propane and dihydroxyphenyl propane.

Triazines, for example, 3 of triazine, 5-dialkyl group-4-hydroxyphenyl derivant and the sulphur that comprises the derivative of dialkyl group-4-hydroxyphenyltriazinuv and hydroxy phenyl-1,3,5-triazines.

Triazole species, for example, 2-phenyl-4-(2,2 '-dihydroxy-benzene formyl radical)-triazole and such as the benzotriazole of the replacement of hydroxyl-Phenyltriazole.

The steric hindrance amine, for example, two (1,2,2,6, methyl (entamethyl) in the 6--4-piperidyl-) sebate) and two [4 (2,2,6, the 6-tetramethyl-piperidyl)] sebate; And any mixture of above-mentioned any material.

Preferably, hydrolyzable ortho ester group is the ortho-formiate group.More preferably, hydrolyzable ortho ester group has the following chemical structure:

Wherein, R ₁And R ₂Be the alkyl substituent of 1-6 carbon atom or the cyclic substituents of 5-7 carbon atom independently; R ₃Be the alkyl substituent or the aromatic substituents of H, a 1-6 carbon atom.

In another embodiment, the present invention relates to a kind of method that is used for cure coating compositions, comprise and make poly-(methyl) acrylate and at least a ortho ester compound generation thermal response that comprises at least two hydroxyls, the product of this thermal response step of hydrolysis is so that this poly-(methyl) acrylate that comprises at least two hydroxyls is removed sealing, and this poly-(methyl) acrylate that comprises at least two hydroxyls that is disengaged sealing is reacted with at least a polyisocyanate compound.

Preferably, the ortho ester compound has the following chemical structure:

Wherein, R ₁And R ₂Be the alkyl substituent of 1-6 carbon atom or the cyclic substituents of 5-7 carbon atom independently; R ₃Be the alkyl substituent or the aromatic substituents of H, a 1-6 carbon atom, R ₄It is the alkyl substituent of 1-6 carbon atom.Preferred ortho ester compound comprises triethyl orthoformate, trimethyl orthoformate, former propionic acid three propyl ester, former propionic acid trimethyl and 2-oxyethyl group-1,3-dioxolane (dixalane).In a preferred embodiment, the ortho ester compound is a triethyl orthoformate.

Capping is a thermal initiation, this means by heating to be undertaken, and need not catalyzer.Yet, if desired, also can use catalyzer.The hydroxyl of poly-in order to seal (methyl) acrylic compound will gather (methyl) acrylate and excessive ortho ester compound heating.This thermal response preferably about 70 ℃ to about 200 ℃, more preferably about 110 ℃ carry out to about 150 ℃ temperature range.Hydroxyl passes through, and for example, following reaction is sealed:

Wherein, R ₁And R ₂Be the alkyl substituent of 1-6 carbon atom or the cyclic substituents of 5-7 carbon atom independently; R ₃Be the alkyl substituent or the aromatic substituents of H, a 1-6 carbon atom, R ₄It is the alkyl substituent of 1-6 carbon atom.Poly-(methyl) acrylate backbone of " polyvalent alcohol " expression.

The hydroxyl of poly-(methyl) acrylic compound of sealing can reduce the viscosity of coating composition, can prepare the coating composition of higher solids content, low VOC thus.If desired, can use, for example, ethyl acetate, the viscosity of regulating poly-(methyl) acrylate of sealing.

In an alternative embodiment, coating of the present invention can comprise at least a spiro orthocarbonate compound and a kind of acid amides acetal compound.The spiro orthocarbonate compound is at unsettled, all application No.60/261 jointly jointly, describes to some extent in 450, and the acid amides acetal compound is at unsettled, all application No.60/509 jointly jointly, describes to some extent in 885.

Preferably, the spiro orthocarbonate compound has the following chemical structure:

Wherein, R ₅And R ₆Be to have the alkylene of at least two bridge carbon atoms or replace the alkylene bridge bond group independently.2 or 3 atoms preferably have an independent existence in the bridged bond of each between Sauerstoffatom.Alkylene is represented only to contain and is had two free valence bond and this two free valence bonds that are bonded to carbon atom and not all be bonded to the carbon of same carbon atom and the group of hydrogen.The alkylene that replaces represents that one or more hydrogen atoms are replaced by functional group, and described functional group can not influence the allied compound desired response or not influence the formation of allied compound.Suitable functional group comprises halogen, comprises alkoxyl group, the ether of hydroxyl etc.

R ₅And R ₆Preferred group has structural formula-CR independently of one another ₇R ₈-CR ₉R ₁₀-(CR ₁₁R ₁₂) _n-, wherein n is 0 or 1, R ₇-R ₁₂Be the alkyl of hydrogen, alkyl or replacement independently of one another, as long as R ₇-R ₁₂In any two groups located adjacent one another or paired combine and can form a ring and get final product.In a preferred form, R ₅With R ₆Identical.R ₇-R ₁₂Preferred independently group is a hydrogen; Alkyl particularly contains the alkyl of 1-10 carbon atom, is more preferably methyl or ethyl; And hydroxyalkyl, particularly methylol.The substitute mode of particularly preferred compound provides in table 1.

Table 1

Compound	R 3							R 6
																R 7	R 8	R 9	R 10	R 11	R 12	n	R 7	R 8	R 9	R 10	R 11	R 12	n
															A	CH 3	H	H	H	H	H	1	CH 3	H	H	H	H	H	1
B	H	H	CH 2OH	C 2H 5	H	H	1	H	H	CH 2OH	C 2H 5	H	H	1
															C	H	H	H	H	-	-	0	H	H	CH 2OH	C 2H 5	H	H	1
D	H	H	H	H	H	H	1	H	H	CH 2OH	C 2H 5	H	H	1
															E	H	H	H	H	H	H	1	H	H	H	H	H	H	1
F	CH 3	H	H	H	-	-	0	CH 3	H	H	H	-	-	0
															G	H	H	H	H	-	-	0	H	H	H	H	-	-	0
H	H	H	n-C 4H 9	C 2H 5	H	H	0	H	H	n-C 4H 9	C 2H 6	H	H	0
															I	H	H	n-C 8H 17	H	-	-	0	H	H	n-C 8H 17	H	-	-	0

Preferably, the acid amides acetal compound has the following chemical structure:

Wherein, R ₁₃-R ₂₁Be hydrogen, C independently ₁-C ₂₂Alkyl, C ₁-C ₂₀Alkenyl, C ₁-C ₂₀Alkynyl, C ₁-C ₂₀Aryl, C ₁-C ₂₀Alkyl ester or C ₁-C ₂₀Aralkyl; Described alkyl, alkenyl, alkynyl, aryl or aralkyl optionally have at least one substituting group that is selected from halogen, alkoxyl group, nitro, amino, alkylamino, dialkyl amido, cyano group, organoalkoxysilane and acid amides acetal (two is functional) and formamyl separately.

In a further alternative embodiment, coating of the present invention can comprise at least a in conventional acrylate copolymer, polyester, reactive oligomers, dispersive acrylate copolymer, aldimine or ketoimine and the polyaspartate.

Be applicable to conventional acrylate copolymer among the present invention can have surpass 5,000, preferably 5,000-20, in 000 scope, more preferably 6,000-20, in 000 scope, most preferably 8,000-12, the GPC M in 000 scope _wThe Tg of acrylate copolymer is in 0 ℃ of-100 ℃ of scope, preferably change in 30 ℃ of-80 ℃ of scopes.

Be applicable to that the acrylate copolymer among the present invention usually can be by conventional monomer, for example, has (methyl) alkyl acrylate of 1-18, preferred 1-12 alkyl carbon atoms and vinylbenzene and such as the functional monomer of Hydroxyethyl acrylate and hydroxyethyl methylacrylate, polymerization obtains.

Be applicable to polyester among the present invention can have surpass 1,500, preferably 1,500-100, in 000 scope, more preferably 2,000-50, in 000 scope, more preferably 2,000-8, in 000 scope, most preferably 2,000-5, the GPC M in 000 scope _wThe Tg of polyester is in-50 ℃ of-100 ℃ of scopes, preferably change in-20 ℃ of-50 ℃ of scopes.

Suitable polyester can be obtained by suitable polyprotonic acid (comprising alicyclic polycarboxylic acid) and suitable polyol (comprising polyvalent alcohol) polymerization usually.The example of suitable alicyclic polycarboxylic acid is tetrahydrophthalic acid, hexahydro-phthalic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 4-methylhexahydrophthalic acid, interior methylene radical tetrahydrophthalic acid, tristane dicarboxylic acid, interior ethylidene hexahydro-phthalic acid, dextrocamphoric acid, hexanaphthene tetracarboxylic acid and tetramethylene tetracarboxylic acid.The cyclic aliphatic polycarboxylic acid not only can use also and can use with its trans forms with its cis form, and can use with the mixture of two kinds of forms.The example of suitable polycarboxylic acid is aromatic series and aliphatics polycarboxylic acid, for example, phthalic acid, m-phthalic acid, terephthalic acid, halogeno-benzene dioctyl phthalate, as tetrachloro-or tetrabromo-benzene dioctyl phthalate, hexanodioic acid, pentanedioic acid, nonane diacid, sebacic acid, fumaric acid, toxilic acid, trimellitic acid and pyromellitic acid, if desired, can use with alicyclic polycarboxylic acid.

Suitable polyvalent alcohol comprises ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, neopentyl glycol, glycol ether, cyclohexanediol, cyclohexanedimethanol, neopentyl glycol, ethyl butyl propanediol, ditrimethylolpropane, trimethylolethane, TriMethylolPropane(TMP), glycerol, tetramethylolmethane, Dipentaerythritol, three (hydroxyethyl) isocyanic ester, polyoxyethylene glycol and polypropylene glycol.If desired,, can also comprise monohydroxy-alcohol, as the phenol of butanols, octanol, lauryl alcohol, ethoxyquin or third oxidation with polyvalent alcohol.U.S. Pat 5,326 further provides the details that is applicable to the polyester among the present invention in 820.Particularly preferred a kind of commercially available polyester is SCD ^-1040 polyester, by Etna Products Inc., Chagrin Falls, Ohio provides.

Useful reactive oligomers is in U.S. Pat 6,221, has in 494 disclosed.If desired, non-acrylic acid or the like (linear or aromatic series) oligopolymer also can use.The non-acrylic acid or the like oligopolymer of this class can make by using non-acrylic acid or the like acid anhydrides, for example, and succinyl oxide or phthalate anhydride or its mixture.U.S. Pat 5,286, the caprolactone oligopolymer of describing in 782 also can use.

Typical case's available dispersive acrylate copolymer prepares by at least a vinyl monomer of dispersion polymerization in the presence of polymeric dispersion stabilizer and organic solvent.Polymeric dispersion stabilizer can be any known stabilizers commonly used in the dispersive acrylate copolymer field.These dispersive acrylate copolymer are in U.S. Pat 5,763, have in 528 disclosed.

Suitable aldimine can be by the aldehyde such as acetaldehyde, formaldehyde, propionic aldehyde, isobutyric aldehyde, butyraldehyde-n, enanthaldehyde and hexamethylene aldehyde, by preparing with the amine reaction.The representational amine that can be used for forming aldimine comprises quadrol, ethylidene triamine, propylene diamine, tetramethylene-diamine, 1,6-hexamethylene-diamine, two (the amino hexyl of 6-) ether, tristane diamines, N, N '-dimethyl diethyl triamine, cyclohexyl-1,2,4-triamine, cyclohexyl-1,2,4,5-tetramine, 3,4,5-triamino pyrans, 3,4-diamino furans and alicyclic diamine.

Suitable polyaspartate is usually by such as two amines of isophorone diamine and prepared in reaction such as the dialkyl maleate class of ethyl maleate.

Above-mentioned polyaspartate and selected aldimine by Bayer Corp. with trade name Desmophen ^The amine coreagent is commercially available to be provided.

Suitable ketoimine is the prepared in reaction by ketone and amine usually.The representational ketone that can be used for forming ketoimine comprises acetone, methylethylketone, methyl isopropyl Ketone, methyl iso-butyl ketone (MIBK), diethyl ketone, benzyl methyl ketone, diisopropyl ketone, cyclopentanone and pimelinketone.The representational amine that can be used for forming ketoimine comprises quadrol, ethylidene triamine, propylene diamine, tetramethylene-diamine, 1,6-hexamethylene-diamine, two (the amino hexyl of 6-) ether, tristane diamines, N, N '-dimethyl diethyl triamine, cyclohexyl-1,2,4-triamine, cyclohexyl-1,2,4,5-tetramine, 3,4,5-triamino pyrans, 3,4-diamino furans and alicyclic diamine.Preparation method and other suitable imines are in U.S. Pat 6,297, shown in 320.

In another embodiment, the present invention relates to a kind of method that is used for coated substrate, be included in and apply one deck undercoat on the base material, on this undercoat, apply the layer of transparent coating, wherein, this Clear coating contains a kind of poly-(methyl) acrylate and at least a polyisocyanate compound, and described poly-(methyl) acrylate comprises at least two hydroxyls that sealed by hydrolyzable ortho ester group; This comprises the ortho ester group of poly-(methyl) acrylate of at least two hydroxyls hydrolysis; And make from poly-(methyl) that be disengaged sealing of hydrolysing step acrylate cross linked by reaction with at least a polyisocyanate compound.

This coating composition can provide with the form of two-pack coating composition.Usually, before being about to use, crosslinkable component and linked are mixed, to form canned mixture (potmix).This mixing can be undertaken or carry out in container individually by conventional mixing nozzle.On base material, for example, apply this canned mixture coating that a layer thickness is generally 15 μ m-200 μ m on the car body or scribbled on the car body of precoated layer (for example electrodeposited primer).Above-mentioned application step can or be brushed this canned mixture and finish usually by spraying on base material, electrostatic spraying, roller coat, dip-coating.Coating after applying is dried usually to reduce the solvent in the coating, solidifies to about 204 ℃ temperature range in room temperature then.In the application of the typical original-pack factory of automobile (" OEM "), the dry coating of said composition can solidify to the temperature of about 160 ℃ lifting, in about 10 to 60 minutes at about 60 ℃ usually.Preferably, for the application of automobile refinisher, curing can be carried out under to about 60 ℃ in about room temperature, and for the heavy truck car coating, curing can be carried out under about 60 ℃ to about 80 ℃.Being solidificated in about 30 minutes to 24 hours under the room temperature condition takes place, and takes place in about 30 minutes to 4 hours usually, has the coating of desirable coating performance to form one deck on base material.Can further understand, can depend on thickness, solidification value, humidity and any extra mechanical assistance means of coated coating actual set time, fan for example, it helps the air continuous flow of substrate to be coated top to accelerate curing speed.Should be appreciated that actual solidification value will change according to the thickness of catalyzer and consumption thereof, the coating that is cured and the amount of used linked.

The suitable substrate that applies this coating composition comprises car body; Any and all parts of automobile supplier production and application; The framework fence; Commercially available truck and truck car body, include, but are not limited to beverage item, common user item, now mixed concrete delivery truck body, rubbish haul car body and fire alarm and emergent car body, and any possible additional unit of this class truck car body or assembly, motorbus, agricultural vehicle and preparation of construction; The truck cover cap; Commercial trailer; The life trailer; Recreation vehicle includes, but are not limited to caravan, camper, conversion covered truck, covered truck class, tourist coach, the manual snowmobile of visit, all terrain vehicles, private ship, motorcycle, ship and aircraft.Base material further comprises industry and commercial new building and maintenance thereof; Cement and wood floors; The wall of commercialization and resident's buildings, for example wall of office building and residential building; The amusement park facility; Concrete surface, for example parking lot and traffic route; Pitch and concrete road surface; Wood surface; The boats and ships surface; Outdoor structure, for example bridge; Tower; The coil coating; Tramway; The circuit card of printing; Machinery; The OEM instrument; Signalling set; Glass fibre structure; Tool movement; And athletic equipment.

Embodiment

In the following example the present invention has been done further qualification.Indicated preferred implementation of the present invention although it should be understood that these embodiment, as just illustrating.By above-mentioned discussion and these embodiment, those skilled in the art can determine preferred feature of the present invention, and under the situation that does not depart from its purport and scope, can make various adjustment and improvement to the present invention, so that it adapts to various purposes and condition.

The connotation of shortenings is as follows: " hr. " expression hour, " min. " expression minute, " sec. " represent the second, " d. " represents the sky, " ml " represents milliliter, " cm " expression centimetre, and " mm " represent millimeter, " g " represents gram, " N " represents newton, " HEMA " expression 2-hydroxyethyl-methacrylic ester, and " IBOA " represents isobornyl acrylate, " MMA " represents methyl methacrylate, " M _n" the expression number-average molecular weight, " M _w" the expression weight-average molecular weight, " cps " represents centipoise.

Embodiment 1

Ortho ester composition A

With 200ml HEMA/IBOA multipolymer (HEMA/IBOA=37/63; M _n=1,700; M _w=2,450) 55% aromatic hydrocarbon solution joins in the 0.5L flask that magnetic stirring apparatus, thermopair and downward condenser are housed.Use the nitrogen purging flask, and add the 2-oxyethyl group-1 of 100ml, 3-dioxolane (dioxalane).Flask inserted in 150 ℃ the oil bath 1.5 hours.The vacuum tightness that applies 15 holders then under 140 ℃ in oil bath is to remove all volatile components.After 1 hour, be full of flask, and add the dried N-BUTYL ACETATE of 30ml to regulate viscosity with nitrogen.With the polymers soln cool to room temperature and be poured in the sealed vessel.The IR spectrum of mixture shows, at 3,100～3 of hydroxyl, 300cm ^-1Significantly do not absorb in the zone.

Embodiment 2

Ortho ester composition B

With 1700ml HEMA/MMA/IBOA multipolymer (HEMA/MMA/IBOA=22/15/63; M _n=1,490; M _w=2,330) 55% aromatic hydrocarbon solution joins in the 2L flask that mechanical stirrer, thermopair and downward condenser are housed.Use the nitrogen purging flask, and add the 2-oxyethyl group-1 of 350ml, 3-dioxolane (dioxalane).Flask inserted in 150 ℃ the oil bath 1 hour.The vacuum tightness that applies 15 holders then under 140 ℃ in oil bath is to remove all volatile components.After 1 hour, be full of flask, and add the dried vinyl acetic monomer of 100ml to regulate viscosity with nitrogen.With the polymers soln cool to room temperature and be poured in the sealed vessel.The IR spectrum of mixture shows, at 3,100～3 of hydroxyl, 300cm ^-1Significantly do not absorb in the zone.

Embodiment 3

Ortho ester composition C

With 400ml HEMA/IBOA multipolymer (HEMA/IBOA=37/63; M _n=1,700; M _w=2,450) 55% aromatic hydrocarbon solution joins in the 1L flask that magnetic stirring apparatus, thermopair and downward condenser are housed.Use the nitrogen purging flask, and add the triethyl orthoformate of 400ml.Flask inserted in 150-170 ℃ the oil bath 1.5 hours.The vacuum tightness that applies 15 holders then under 70 ℃ in oil bath is to remove all volatile components.After 1 hour, be full of flask, and add the dried vinyl acetic monomer of 30ml to regulate viscosity with nitrogen.With the polymers soln cool to room temperature and be poured in the sealed vessel.The IR spectrum of mixture shows, at 3,100～3 of hydroxyl, 300cm ^-1Significantly do not absorb in the zone.

Embodiment 4

Prepare three kinds of coating compositions.The first, coating A neither contains not protected HEMA/MMA/IBOA and does not also contain by orthoester-protected HEMA/MMA/IBOA.The second, coating B contains protected HEMA/MMA/IBOA (with the form of ortho ester composition B).The 3rd, coating C contains not protected HEMA/MMA/IBOA.Each component in the table 2 is mixed with the preparation coating composition.All three kinds of coating all contain, and unsettled jointly, total sequence number is No.60/261, spiro orthocarbonate component (3 described in the experiment 2 of 450 application, 9-dibutyl-3,9-diethyl-1,5,7,11-four oxa-volution [5,5] undecanes), wherein use 2-ethyl-1, the 3-hexylene glycol replaces 2-butyl-2-ethyl-1, ammediol.

Table 2

Explanation	Coating A	Coating B	Coating C
				HEMA/MMA/IBOA (22/15/63)	0	0	21.7
Spiro orthocarbonate (from sequence number is No.60/261,450 experiment 2)	16.1	12.1	11.9
				Ortho ester composition B (from embodiment 2)	0	17.6	0
Propylene glycol monomethyl ether acetate	1.63	2.19	0
				The vinyl acetic monomer solution of 2% dibutyltin dilaurate	5.69	5.69	5.45
10％BYK 306 1Xylene solution	1.16	1.16	1.11
				Add up to	24.6	38.8	40.3

¹The polyether-modified dimethyl polysiloxane that Byk-Chemie provides

Each component in the table 3 is mixed.

Table 3

Explanation	Coating A	Coating B	Coating C
				Desmodur Z 4470 BA 1	4.21	0	0
Desmodur N 3300A 2	26.4	21.1	19.7
				Propylene glycol monomethyl ether acetate	4.74	0	0
Add up to	35.4	21.1	19.7

¹The isocyanate trimerization body of the isophorone diisocyanate that Bayer Corp. provides

²The isocyanate trimerization body of the hexamethylene diisocyanate that Bayer Corp. provides

The mixture of each coating of table 3 is joined in the mixture of each coating of table 2 and stir.With Nacure ^XP-221 joins in these mixtures.The final volume of three kinds of coating compositions is listed in the table 4.

Table 4

Part	Coating A	Coating B	Coating C
				Table 1 mixture	24.6	38.8	40.3
Table 2 mixture	35.4	21.1	19.7
				Nacure XP-221 1	0.65	0.65	0.62
Add up to	60.7	60.6	60.6

¹The aqueous isopropanol of 70% Witco 1298 Soft Acid; King Industries, Norwalk, Conn.

Measure the Gardner-Holt viscosity of these three kinds of coating compositions, cotton bonding time of releasing, BK3 time and water stain rank.

Measure Gardner-Holt viscosity according to ASTM test D 1545.

In order to measure cotton bonding time of releasing, the time (for example, 30 minutes) of the dry one section setting of the panel that will be coated with.A cotton balls is dropped to the surface of panel from the height of 2.5cm, and cotton balls is stopped on the surface timed interval (for example, 30 minutes interval) of one section setting.Then with faceplate inverted.Repeating these steps drops (that is cotton bonding time of releasing) from panel in inversion up to cotton balls.

Measure the time of drying of composition coat as the BK3 surface drying time according to ASTM test D 5895.

Water stain rank is the crosslinked quality of fixedly morning of interim coating composition that is determined at coating composition.Water stain destruction on the coating composition shows not exclusively fixing, and before coating composition can or be removed from spray booth by damp sand mill, flour milling, coating composition needed further fixing.Carry out water stain other mensuration of level according to the methods below.To be placed on the smooth surface with the panel that the test coating composition applies, and drip deionized water with pipette with 1 hour interval.The water droplet that diameter is about 1.25cm places on the panel and makes its evaporation.On the inspection panel water stain with determine whether the distortion and variable color.With the wetting cheese cloth of deionized water wiping panel gently, then dry panel gently with cloth.Estimate panel according to 1～10 grade then.10 grades be best-do not have tangible spot or variable color or a distortion; 9 grades-almost check less than; 8 grades-slight annular; 7 grades-very slight variable color or slight deformation; 6 grades-slightly tarnish or light discolouration; 5 grades-lose certain gloss or variable color; 4 grades-slightly corrode or certain deformation; 3 grades-slight protuberance, the serious erosion, or variable color; 2 grades-certain protuberance; The dissolving of 1 grade-coating composition.

Table 5 shows, finds among the coating B to solidify to improve to some extent, and added ortho ester group (ortho ester composition B) because compare with coating A, to essentially no infringement working life.The contrast of coating C and coating B is the contrast of not protected material (C) and protected material (B).Coating B has working life preferably under higher solids content (75% pair 72%), curing performance is similar.

Table 5

Test	Coating A	Coating B	Coating C
				Solid content, %	75	75	72
The WT solid	45	45	43.2
				NCO/OH	1.40	1.03	1.03
Gardner-Holt 0 hour	A	A	A
				Gardner-Holt 1 hour	C	H	H
Gardner-Holt 2 hours	D	I	M
				Cotton bonding time of releasing (in hour)	＞8	5	4
BK3 (in minute)	621	170	156
				Water stain rank after 4 hours	7	10	9

Embodiment 5

For each coating composition D-H, with part 1,2 and 3 formation admixed together coating composition as shown in table 6.That coating G and H contain is unsettled jointly, total sequence number is No.60/509, the acid amides acetal compound described in the embodiment 4 of 885 application.With scraper every kind of coating composition is coated on the independent phosphated cold-pressed steel plate, this steel plate is coated with the PPG that one deck dry coating thickness is 50 μ m, the PowerCron that Pittsburgh, Pa. provide in advance ^Primer priming paint.Coating composition D-F is air-dry at ambient temperature, and second group of plate toasted 20 minutes down at 60 ℃.Coating composition G and H toasted 20 minutes down at 60 ℃.

Table 6

Explanation	Coating D	Coating E	Coating F	Coating G	Coating H
						Part 1
The protected hydroxyl of IBOA/HEMA vinylformic acid-not	30	0	0	0	0
						Ortho ester composition C (from embodiment 3)	0	26.36	39.51	4.0	4.0
Acid amides acetal compound (from sequence number No.60/509, the embodiment 4 in 885)	0	0	0	15.0	15.0
						N-BUTYL ACETATE	11.94	11.11	14.72	0	0
Diisobutyl ketone	0	0	0	2.41	1.42
						Flow agent 1	0.3	0.35	0.47	0.42	0.42
Catalyst solution 2，3	1.5	5.32	7.18	1.51	1.51
						Part 2
Tolonate HDT 4	10.74	10.74	10.74	0	0
						Desmodur Z 4470BA 5	0	0	0	10.39	10.39
Desmodu XP 2410 6	0	0	0	16.96	16.96
						Diisobutyl ketone	0	0	0	2.05	2.05
Part 3
						25% sulfonic acid 7Aqueous isopropanol	0	0.77	1.04	0	1.44
Acetate	0	0	0	0.14	0

¹The propylene glycol monomethyl ether acetate solution of 20% BYK  301 flow agents that BYK-Chemie provides

²The vinyl acetic monomer solution of 1% the dibutyltin dilaurate that coating composition D-F:Elf-Atochem North America provides

³The vinyl acetic monomer solution of 10% the dibutyltin dilaurate that coating composition G-H:Elf-Atochem North America provides

⁴Rhodia, Inc. (Cranbury, the isocyanate trimerization body of the hexamethylene diisocyanate that N.J.) provides

⁵The isocyanate trimerization body of the isophorone diisocyanate that Bayer Corp. provides

⁶The isocyanate trimerization body of the hexamethylene diisocyanate that Bayer Corp. provides

⁷Aromatic sulphonic acid: the aqueous isopropanol of the Nacure  XP-221 that King Industries provides

Measure BK3 time, BK4 time, cotton bonding time of releasing, water stain rank, rate of expansion, Persoz hardness, Fischer hardness, the solvent nature of anti-MEK, gel section, viscosity, gelationization time and the solid content of coating composition.

Carry out cotton bonding time of releasing, BK3 time and other test of water stain level as described in example 5 above.

D5895 measures the time of drying of composition coating as the BK4 surface drying time according to the ASTM test.

By being expanded, film measures the rate of expansion of free film (taking off) from TPO-thermoplastic olefin sheet in methylene dichloride.Should place between the two-layer aluminium foil by free film, and use the LADD press bed to go out diameter to be about the disk of 3.5mm and aluminium foil is removed from film from film.The measurement microscope that use has 10 times of magnifications and band filament lens is the diameter (" D of expanded film not _o").4 methylene dichloride are added drop-wise to film surface and allow film expand several seconds, be put into sheet glass on the film then and measure expansible film diameter (" D _s").Then according to following calculating formula: rate of expansion=(D _s) ²/ (D _o) ²Calculate rate of expansion.

By using Byk-Mallinckrodt, the model that Wallingford, Conn. provide is that the Persoz sclerometer of No.5854 (ASTM D4366) is measured coated membrane hardness (Persoz hardness) over time.The data (being called the Persoz data) that record changes.

Use Fischerscope ^Sclerometer is measured Fischer hardness and (is measured with N/mm ²Metering).

Carry out the mensuration of the solvent nature of anti-MEK by using rubbing machine, use the cloth that has soaked MEK (methylethylketone) on the quilt plate that is coated with, to rub (100 times), and unnecessary MEK is wiped.Then plate is divided into the 1-10 level.10 grades of expression coatings are not significantly destroyed, 9 grades of expressions have 1 to 3 tangible scratch, 8 grades of expressions have 4 to 6 tangible scratches, 7 grades of expressions have 7 to 10 tangible scratches, 6 grades of expressions have 10 to 15 tangible scratches and slight pitting are arranged or slight fading, 5 grades of expressions have 15 to 20 tangible scratches and have slight to medium pitting or medium fading, 4 grades of expression scratches begin intermingling, 3 grades are illustrated in and have only a small amount of unbroken zone between the blended scratch, 2 expressions do not have obvious unspoilt sign, 1 expression completely destroy promptly, shows exposed spot.Multiply by progression by the number that will rub and obtain final evaluation.

According to U.S. Patent No. 6,221, the method that 494 the 8th hurdle, the 56th row provide in going to the 9th hurdle, the 2nd is measured gel section, and this method is incorporated herein by reference at this.

Use ICI Yuan Zhui ﹠amp; Coil viscometer 10,000sec ^-1Be unit with the centipoise under the velocity of shear, and/or use Zahn#2 cup viscometer being second that unit measures viscosity.

The gelationization time is meant that liquid coating becomes the required time of gel.

Use preweighted aluminium dish to measure solid content.

1) (Houston, aromatic series 100 solvents Tex.) add in the aluminium dish from ExxonMobile Chemical Company with 2-4ml;

2) the 0.2-0.4g test materials is weighed in the dish that contains solvent;

3) this polycomponent Clear paint was at room temperature placed 60 minutes;

4) then sample is placed the baking oven 60 minutes of 110+/-5 ℃.

5) sample is taken out from baking oven, make its cool to room temperature, and weigh;

6) be calculated as follows solid content:

Test result is as shown in table 7:

Table 7

Test	Coating D	Coating E	Coating F	Coating G	Coating H
						Solid content (theory)	55	---	---	---	---
Solid content (actual measurement)	---	53.6	55.4	83	85
						ICI viscosity (cps)	30	35	40	---	---
The gelationization time	157min.	＞5.5hr.	＞6hr.	＞24hr.	＞24hr.
						The BK3 time (min.)	203	66.1	87.3	---	---
The BK4 time (min.)	484	212	441	---	---
						Cotton bonding time of releasing (min.)	235	180	225	---	---
APP-is wet	Good	Good	Good	Good	Good
						APP/ is transparent-does	Good	Good	Good	Good	Good
Water stain rank after 4 hours	7	8	8	---	---
						Water stain rank after 1 day	7	8	8	---	---
The water stain rank of curing under 60 ℃-initial	8	8	8	10	10
						60 ℃ are cured+water stain rank after 1 day under the room temperature	8	8.5	8	10	10
Room temperature is the MEK friction after following 4 hours	700	800	750	---	---
						Room temperature is the MEK friction after following 1 day	800	800	800	---	---
The MEK friction of curing under 60 ℃-initial	750	800	800	650	700
						60 ℃ are cured+MEK after 1 day under room temperature friction	800	800	800	800	750
The MEK friction of room temperature after following 30 days	700	800	700	---	---
						60 ℃ are cured+MEK friction under the room temperature after 30 days	700	800	700	800	750
Room temperature swollen after following 1 day	1.86	1.75	1.88	---	---

The rate of expanding
						The rate of expansion of room temperature after following 7 days	1.61	1.66	1.84	---	---
The rate of expansion of room temperature after following 30 days	1.63	1.67	1.82	---	---
						60 ℃ of rate of expansion of curing-initial	2.06	1.88	2.04	1.85	2.31
60 ℃ are cured+rate of expansion after 1 day under the room temperature	1.75	1.74	1.86	1.81	2.18
						60 ℃ are cured+rate of expansion after 7 days under the room temperature	1.68	1.67	1.82	2.1	2.15
60 ℃ are cured+rate of expansion after 30 days under the room temperature	1.63	1.67	1.82	2.1	2.16
						The gelationization part of room temperature after following 30 days	92.49	93.29	91.09	---	---
60 ℃ are cured+gel fraction after 30 days under the room temperature	94.29	93.8	92.27	92.37	91.79
						The Persoz hardness of room temperature after following 4 hours	23	55	61	---	---
The Persoz hardness of room temperature after following 1 day	128	163	159	---	---
						60 ℃ of Persoz hardness of curing-initial	135	166	159	79	145
60 ℃ are cured+Persoz hardness under the room temperature after 1 day	216	206	180	86	130
						The Fischer hardness of room temperature after following 1 day	33.6	62	57.5	---	---
The Fischer hardness of room temperature after following 7 days	106	79	89	---	---
						The Fischer hardness of room temperature after following 30 days	118	122	114	---	---

60 ℃ of Fischer hardness of curing-initial	54.4	54	51	23	43.1
						60 ℃ are cured+Fischer hardness under the room temperature after 1 day	99	83	68	27	31.3
60 ℃ are cured+Fischer hardness under the room temperature after 7 days	162	145	81.6	49	59
						60 ℃ are cured+Fischer hardness under the room temperature after 30 days	154	126	111	73	81
Zahn #2 (being meter second) is initial	---	---	---	21.06	20.19
						Zahn #2-1 hour	---	---	---	27.61	45.56
Zahn #2-2 hour	---	---	---	33.15	64.06
						Zahn #2-3 hour	---	---	---	36.88	71.75
Zahn #2-4 hour	---	---	---	38.54	75.59
						Zahn #2-5 hour	---	---	---	41.03	79.31
Zahn #2-6 hour	---	---	---	42.23	85.68

Coating E compares with coating D with F and shows, uses the polymkeric substance that has protected hydroxyl obviously to be better than using the conventional vinylformic acid that have hydroxyl in the coating more.Coating E and F have gelationization time and the premature curing that obviously is better than coating D, and this can find out the room temperature hardness from the BK3 time and higher 4 hours and 1 day of having improved.

Coating G and H show; the coating that use has the polymkeric substance of protected hydroxyl can prepare under high solids content (83-85%) and the low VOC (＜2.1 pounds/gallon) very much; keep simultaneously well curing and working life (＞24 hours gelationization time, and maximum 6 hours viscosity doubles).

Claims (33)

1, a kind of coating composition, contain:

(a) a kind of poly-(methyl) acrylate comprises at least two hydroxyls that sealed by hydrolyzable ortho ester group; With

(b) at least a polyisocyanate compound.

2, the coating composition of claim 1, wherein, hydrolyzable ortho ester group is the ortho-formiate group.

3, the coating composition of claim 2, wherein, hydrolyzable ortho ester group is

Wherein, R ₁And R ₂Be the alkyl substituent of 1-6 carbon atom or the cyclic substituents of 5-7 carbon atom independently; And

R ₃Be the alkyl substituent or the aromatic substituents of H, a 1-6 carbon atom.

4, the coating composition of claim 1, wherein, the hydroxyl of the poly-about 30%-100% of (methyl) acrylate is sealed by hydrolyzable ortho ester group.

5, the coating composition of claim 1, wherein, the number-average molecular weight of poly-(methyl) acrylate is about 200 to about 50,000.

6, the coating composition of claim 1, wherein, this at least a polyisocyanate compound with poly-(methyl) acrylate be that about 0.5 to about 5 molar equivalent is than existing.

7, the coating composition of claim 1 further contains at least a in pigment, filler, solvent, catalyzer and the conventional additives.

8, the coating composition of claim 1 further contains at least a in spiro orthocarbonate compound and the acid amides acetal compound.

9, the coating composition of claim 8, wherein, the spiro orthocarbonate compound is

Wherein, R ₅And R ₆Be to have the alkylene of at least two bridge carbon atoms or replace the alkylene bridge bond group independently.

10, the coating composition of claim 9, wherein, R ₅And R ₆Be independently-CR ₇R ₈-CR ₉R ₁₀-(CR ₁₁R ₁₂) _n-,

Wherein n is 0 or 1; And

R ₇-R ₁₂Be the alkyl of hydrogen, alkyl or replacement independently, as long as R ₇-R ₁₂In any two groups located adjacent one another or paired combine and can form a ring and get final product.

11, the coating composition of claim 8, wherein, the acid amides acetal compound is

Wherein, R ₁₃-R ₂₁Be hydrogen, C independently ₁-C ₂₂Alkyl, C ₁-C ₂₀Alkenyl, C ₁-C ₂₀Alkynyl, C ₁-C ₂₀Aryl, C ₁-C ₂₀Alkyl ester or C ₁-C ₂₀Aralkyl; Described alkyl, alkenyl, alkynyl, aryl or aralkyl optionally have at least one substituting group that is selected from halogen, alkoxyl group, nitro, amino, alkylamino, dialkyl amido, cyano group, organoalkoxysilane and acid amides acetal (two is functional) and formamyl separately.

12, the coating composition of claim 1 further contains at least a in acrylate copolymer, polyester, reactive oligomers, non-acrylic acid oligomer, dispersive acrylate copolymer, aldimine, ketoimine and the polyaspartate.

13, the coating composition of claim 1, wherein, coating composition is clear coating composition, coloured composition, bottom coating composition, single coating composition or priming paint.

14, a kind of method that is used for cure coating compositions comprises:

(a) make poly-(methyl) acrylate and at least a ortho ester compound generation thermal response that contains at least two hydroxyls;

(b) product of hydrolysing step (a) makes this poly-(methyl) acrylate that contains at least two hydroxyls remove sealing; And

(c) make this poly-(methyl) acrylate that contains at least two hydroxyls that is disengaged sealing and reaction of at least a polyisocyanate compound.

15, the method for claim 14, wherein at least a ortho ester compound is the ortho-formiate compound.

16, the method for claim 15, wherein, at least a ortho ester compound is

Wherein, R ₁And R ₂Be the alkyl substituent of 1-6 carbon atom or the cyclic substituents of 5-7 carbon atom independently;

R ₃Be the alkyl substituent or the aromatic substituents of H, a 1-6 carbon atom; And

R ₄It is the alkyl substituent of 1-6 carbon atom.

17, the method for claim 16, wherein, at least a ortho ester compound is a triethyl orthoformate.

18, the method for claim 14, wherein, the hydroxyl of the poly-about 30%-100% of (methyl) acrylate is sealed by hydrolyzable ortho ester group.

19, the method for claim 14, wherein, the number-average molecular weight of poly-(methyl) acrylate is about 200 to about 50,000.

20, a kind of method that is used for coated substrate comprises:

(a) on base material, apply one deck undercoat;

(b) apply the layer of transparent coating on this undercoat, wherein, this Clear coating contains

(i) a kind of poly-(methyl) acrylate that comprises at least two hydroxyls that sealed by the hydrolyzable ortho ester group and,

(ii) at least a polyisocyanate compound;

(c) hydrolysis this comprise the ortho ester group of poly-(methyl) acrylate of at least two hydroxyls; And

(d) by with the reaction of at least a polyisocyanate compound, make poly-(methyl) that be disengaged sealing of step (c) acrylate cross linked.

21, the method for claim 20, wherein, hydrolyzable ortho ester group is the ortho-formiate group.

22, the method for claim 21, wherein, hydrolyzable ortho ester group is

Wherein, R ₁And R ₂Be the alkyl substituent of 1-6 carbon atom or the cyclic substituents of 5-7 carbon atom independently; And

R ₃Be the alkyl substituent or the aromatic substituents of H, a 1-6 carbon atom.

23, the method for claim 20, wherein, the hydroxyl of the poly-about 30%-100% of (methyl) acrylate is sealed by hydrolyzable ortho ester group.

24, the method for claim 20, wherein, the number-average molecular weight of poly-(methyl) acrylate is about 200 to about 50,000.

25, the method for claim 20, wherein, at least a polyisocyanate compound with poly-(methyl) acrylate be that about 0.5 to about 5 molar equivalent is than existing.

26, the method for claim 20, wherein, base material is motor vehicle or its parts.

27, a kind of method that is used for the hydroxyl of poly-(methyl) acrylate of sealing comprises making poly-(methyl) acrylate and at least a ortho ester compound generation thermal response that comprises at least two hydroxyls.

28, the method for claim 27, wherein, at least a ortho ester compound is the ortho-formiate compound.

29, the method for claim 28, wherein, at least a ortho ester compound is

Wherein, R ₁And R ₂Be the alkyl substituent of 1-6 carbon atom or the cyclic substituents of 5-7 carbon atom independently;

R ₃Be the alkyl substituent or the aromatic substituents of H, a 1-6 carbon atom; And

R ₄It is the alkyl substituent of 1-6 carbon atom.

30, the method for claim 29, wherein, at least a ortho ester compound is a triethyl orthoformate.

31, the method for claim 27, wherein, the number-average molecular weight of poly-(methyl) acrylate is about 200 to about 50,000.

32, a kind of composition that contains poly-(methyl) acrylate, described at least two hydroxyls that sealed by hydrolyzable ortho ester group that comprise that gather (methyl) acrylate, described ortho ester group comprises structural formula

Wherein, R ₁And R ₂Be the alkyl substituent of 1-6 carbon atom or the cyclic substituents of 5-7 carbon atom independently; And

R ₃Be the alkyl substituent or the aromatic substituents of H, a 1-6 carbon atom.

33, use the base material of the coating composition coating of claim 1.