CN100542691C

CN100542691C - In substrate, form the paint line and the method for multi-layer composite coatings

Info

Publication number: CN100542691C
Application number: CNB038039176A
Authority: CN
Inventors: S·珀迪; D·A·辛普森; R·J·福克斯; D·A·艾肯; J·P·罗利
Original assignee: PPG Industries Ohio Inc
Current assignee: PPG Industries Ohio Inc
Priority date: 2002-02-13
Filing date: 2003-02-13
Publication date: 2009-09-23
Anticipated expiration: 2023-02-13
Also published as: CN1735465A; ES2358191T3

Abstract

A kind of method that forms multi-layer composite coatings in substrate is disclosed.Thereby this method comprises by the coating composition electro-deposition with curable electro-deposition form electrodeposited coating in substrate at least a portion substrate.Not necessarily, the substrate that applies is heated to uniform temperature and keeps the sufficiently long time so that electrodeposited coating solidifies.By at least a portion electrodeposited coating, directly depositing the aqueous curable ground coating composition, on electrodeposited coating, form priming coat.Not necessarily, this priming coat is dried.By at least a portion priming coat, directly depositing the curable top coating combination that is substantially devoid of pigment, on priming coat, form top coat.Solidify simultaneously top coat, priming coat and, not necessarily, cured electrodeposition coating simultaneously.

Description

In substrate, form the paint line and the method for multi-layer composite coatings

Technical field

The present invention relates to a kind of method that in substrate, particularly motor vehicle substrate, forms multi-layer composite coatings, and a kind of paint line of this method of application.

Background technology

Multi-layer composite coatings, for example, coloured-clear coat system, be included in the substrate that to apply one deck coloured or contain the priming coat of pigment, on priming coat, apply layer of transparent or varnish coat then, as the basic covering with paint of many consumer goods, comprise, for example, the basic covering with paint of motor vehicle, increased popularity.Coloured-transparent body cording has the outstanding appearance property such as gloss and clear image, and excellent coating system can be provided, the hostile environment condition of for example anticorrosion, anti-scratch rub resistance and tolerance such as acid rain.Coloured-clear coat system so has been widely used in motor vehicle, aircraft substrate, such as the floor coating of ceramic tile and timber floor, packaging material etc.

Traditional painting dressing automobiles method comprises that typically coating successively is generally the electrodepositable coating composition of cationic compositions, primer coating surfacer coating composition on electrodeposited coating, on priming paint surfacer coating, apply hyperchromic and/or synergy ground coating composition, and on priming coat, apply transparent or varnish paint composition.In some cases, electrodeposited coating can be coated on that (mill-applied) that be coated in factory's application on the steel metallic substrates of spiraling can weld, on the heat-curable coating, the described steel metallic substrates of spiraling is used to form car body (or automobile component, as dashboard, door and Peng Gai).

For example, as mentioned above, on most of automobile coating production lines, the at first coated electrodeposited coating that forms by the cationic electrodepositable coatings composition usually on the car body.This electrodeposited coating is typically subsequently by heat cure.This electrodeposited coating must be adhered in the substrate fully and protect the substrate that has applied it not corroded.In the electrocoating paint of routine, excellent adherence and Corrosion Protection can and/or can contain aromatic series crosslinking agent partly from the electrodepositable material in the ion film-forming resin.Though excellent adherence and Corrosion Protection is provided, these resins and/or crosslinking agent can be able to be penetrated the visible light and/or the ultraviolet light of the coating that applies subsequently and be degraded.Such light degradation meeting causes electrodeposited coating leafing from the substrate, causes the catastrophic failure of multi-layer composite coatings system.

Priming paint surfacer coating composition typically is coated on the electrodeposited coating of curing, and this priming paint surfacer coating is by heat cure then.Priming paint surfacer coating composition contains the polymer composition that provides pliable and tough and flexible coating is arranged usually; And typically, for example, add such as filling materials such as talcum and clays, and often contain anti-light degradation pigment by heavy painted, for example, carbon black.The film thickness of the priming paint surfacer coating of solidifying can be up to 100 microns, still usually between 25 to 50 microns.Like this, priming paint surfacer coating can strengthen the flaking resistance of multi-layer composite coatings system, and can cover up any blemish that occurs on the electrodeposited coating, has guaranteed the smooth outward appearance of top coat that applies subsequently thus.In addition, the priming paint surfacer also provides the opacity of visible light and ultraviolet light, to prevent the light degradation of the previous electrodeposited coating that applies.A kind of known priming paint surfacer coating is available from the PPG Industries of Pittsburgh, Pennsylvania, the GPX 45379 of Inc..

Bottom coating composition is generally waterborne compositions, is coated on subsequently on the priming paint surfacer coating of curing.Bottom coating composition contains hyperchromic and/or synergy pigment usually.

Priming coat is typically dodged the sufficiently long time of baking at a certain temperature getting rid of unnecessary solvent, but is not enough to the cured base coating composition.On uncured priming coat, apply transparent or varnish coat then.This is commonly referred to the wet wet application of bumping.Varnish coat can provide excellent gloss and visual clearly, and anti-zoned trace and damage, and anti-harsh environmental conditions.

In known paint line, substrate is carried out electrophoretic painting at the electropaining station, moves into priming paint zone primer coating surfacer then.As mentioned above, the priming paint surfacer typically is thick relatively coating, to cover up suprabasil blemish.The priming paint surfacer coating that applies is cured, and the priming paint surfacer of Gu Huaing can be with sand papering to remove blemish and to serve as that the coating of further coating provides smooth outer surface then.Yet this bruting process can form the granule of grit or dust, and they must be brushed or sticking removing from substrate before applying further coating.After process should stickingly be removed operation, substrate was moved into the primary coat zone, and painted ground coating composition is coated on the part of substrate insertion fully herein.At one or more primary coats station subsequently, same complete painted ground coating composition is coated on the priming paint surfacer of substrate outside.The ground coating composition of Tu Fuing is toasted so that priming coat is predrying then, and on the priming coat of substrate outside the varnish coating composition.Typically, clear coat composition is not coated on some regional priming coat of insertion portion.

In order to save cost, recently in painting dressing automobiles market to reducing the cured film thickness of one or more layers coating in the multi-layer composite coatings, and/or subdue one or more application steps and produced interest.For example, in some multiple coating process, the coating and the curing schedule of priming paint surfacer coating can be cut out.That is, bottom coating composition directly is coated on the electrodeposited coating of curing.In improved like this coating process, require electrodeposited coating and priming coat all will satisfy harsh durability, outward appearance and physical property standard.

Further, as previously mentioned,, can factory's application (mill-applied) one deck on metallic substrates weldingly press down rotten primer coating for some application.Direct coating base coat composition on the weldable primer layer that solidifies does not insert electrodeposited coating and priming paint surfacer coating then.

Equally, automobile component and accessory, for example nonmetal or elastomer automobile component, as bumper and side mo(u)lding, also typically " offed normal " (off site) applies and is transported to automobile assembling factory.Such substrate does not need to require anticorrosive as metallic substrates discussed above.Therefore, ground coating composition can directly be coated on the non-metal base basal surface, perhaps, alternately, directly is coated on the primer coating of the improvement bonding force that previous coating inserts.

U.S. Patent No. 6,221,949 B1 have disclosed a kind of coating composition that is used for the multiple coating coating system, its contain water-dilutable, acid number is that 10-60, number-average molecular weight are 4000 to 25,000 polyurethane resin.This polyurethane by number-average molecular weight be have in mixture, PIC or its mixture, the molecule of the polyester of 400-5000 and/or PPG or these polyester and PPG the mixture of the group of at least one and isocyanate groups reaction and compound that at least one can form anionic group or these compounds and not necessarily molecular weight be 40-400, contain hydroxyl and/or amino organic compound reaction, and the product that obtains to the small part neutralization and being prepared.Composition further contains pigment and/or filler, and wherein the ratio of adhesive and pigment is 0.5:1-1.5:1.In such composition, the amount of talcum in the overall weight of pigment, requires to be 20wt-80wt%.Said composition is used to form in the processing procedure of laminated coating coating system, in this system, use the electrocoating paint coated substrate, the not necessarily predrying or oven dry of described electrocoating paint, on electrodeposited coating, apply the composition of foregoing description and not necessarily carry out predrying and do not dry, on the coating that the composition by foregoing description forms, apply second layer water paint and not necessarily carry out predrying and do not dry, on the coating that forms by second layer waterborne compositions, apply clear coat, and whole coating system is dried.

U.S. Patent No. 5,976,343 have disclosed a kind of substrate that is used at the ground floor electrodeposited coating with oven dry, the surfacer coating that is the 10-30 micron by applying dry thickness, forms by the basic varnish reagent that contains first water-based polyurethane resin, and wetting and bumping wet coating dry thickness is the 3rd coating reagent of 7-15 micron, carries out the method that multilayer varnish applies.The 3rd coating is made up of the second water-based varnish reagent that contains polyurethane resin.Need not to toast the 3rd coating reagent then, apply the clear varnish layer, toast this multi-coating system with mutual curing second, third and layer of varnish.The first basic varnish reagent has than the second basic varnish reagent polyurethane resin of high-load more.Further, this invention has disclosed the first basic varnish reagent by the polyurethane resin and the second basic varnish reagent mix with appropriate amount, is made by the second basic varnish reagent.

U.S. Patent No. 4,820,555 have disclosed a kind of method that forms multi-coating system in substrate, at first apply electrodeposition composition and cured electrodeposition composition in substrate, on electrodeposited coating, apply the seal coat composition, and not necessarily, toast this seal coat, metallizing bottom coating composition on seal coat, perhaps dry, sudden strain of a muscle baking, perhaps solidify this metal bottom coating, varnish coating coating composition on this metal bottom coating, and toast this multi-coating system.The seal coat composition can be wet solvent type or water-based, and metallic pigments orientation, priming coat slickness and the bonding force of improvement are provided.

In order to alleviate some problems relevant with known coating process, developed another paint line, wherein, the coating of priming paint surfacer has been cancelled.But in the method, the structure of paint line and operation must be changed the problem that causes owing to above-mentioned change to adapt to significantly.For example, apply electrodeposited coating in the method after, on outer surfaces of substrates, apply first ground coating composition.This first ground coating composition is a kind of flaking resistance, the painted composition of color pigment, and its color can be approximate with the required final color of coated substrate.This first ground coating composition is heated so that first priming coat is predrying then, and second ground coating composition with required final color is coated on first ground coating composition on the outer surface.Applying between first and second ground coating compositions, the part of insertion is applied by second ground coating composition.Need carry out such change is because if as apply insertion portion earlier in traditional coating process, the color transition zone can be clearly.Yet this change in the application order means that this method is difficult for and the existing paint line compatibility of setting up for first coated substrate insertion portion before applying the outside.Must need extra-pay to set up new paint line to implement this method or to change existing production line the insertion portion application is moved to the end in primary coat zone.

In view of the foregoing, a kind of method that forms the multi-layer composite coatings system is provided expediently, this method has been subdued coating and cured primer surfacer coating, thereby first ground coating composition can directly be coated on the electrodeposited coating, perhaps, replacedly, directly be coated in the substrate that handled or untreated; Then wetly bumping wet second color-or effect-the enhancings priming coat that applies, color-or the composition of effect-enhancings priming coat can be identical or different with first ground coating composition, then wets and bumps the varnish coating coating that wets.Further, such multi-layer composite coatings system preferably is applied to need not on the conventional paint line great change.

Summary of the invention

In a specific embodiment, the present invention relates to a kind of method that in substrate, forms multi-layer composite coatings, this method comprises:

By the coating composition of the curable electro-deposition of electro-deposition at least a portion of substrate, in substrate, form electrodeposited coating;

Not necessarily, solidify this electrodeposited coating;

By at least a portion of electrodeposited coating, directly depositing the aqueous curable ground coating composition, on electrodeposited coating, form priming coat;

Not necessarily, dry this priming coat;

By at least a portion of priming coat, directly depositing the curable top coating combination that is substantially free of pigment, on priming coat, form top coat; And

Solidify this top coat, priming coat simultaneously, and, not necessarily, while cured electrodeposition coating.

In another embodiment, the present invention relates to a kind of method that forms multi-layer composite coatings in substrate, this method comprises:

Not necessarily, solidify this electrodeposited coating;

By at least a portion of electrodeposited coating, directly depositing aqueous curable first ground coating composition, on electrodeposited coating, form first priming coat;

Not necessarily, dry this first priming coat;

By at least a portion of first priming coat, directly depositing and identical or different aqueous curable second ground coating composition of first ground coating composition, on first priming coat, form second priming coat;

Not necessarily, dry this second priming coat;

By at least a portion of second priming coat, directly depositing the curable top coating combination that is substantially free of pigment, on second priming coat, form top coat; And

Solidify this top coat, second priming coat, first priming coat simultaneously, and, not necessarily, while cured electrodeposition coating.

The invention still further relates to a kind of method that forms multi-layer composite coatings in substrate, this method comprises:

Not necessarily, solidify this electrodeposited coating;

This first ground coating composition contains:

(i) first resin binder, and

(ii) be scattered in first color compositions that contains one or more pigment in first resin binder;

Not necessarily, dry this first priming coat;

By at least a portion of first priming coat, directly depositing aqueous curable second ground coating composition, on first priming coat, form second priming coat;

This second ground coating composition contains:

(i) with the second identical or different resin binder of first resin binder, and

The second (ii) different color compositions with first color compositions, it is scattered in second resin binder, contains one or more hyperchromic and/or synergy pigment;

Not necessarily, dry this second priming coat;

Solidify this top coat, second priming coat, first priming coat simultaneously, and, not necessarily, while cured electrodeposition coating,

Wherein first ground coating composition further contains a kind of composition, and said composition contains second color compositions that is scattered in second resin binder, and

Wherein the ratio of the pigment of second coating composition and adhesive is 0.1-4.0:1.

In a further specific embodiment, the invention provides a kind of method that in substrate, forms multi-layer composite coatings, this method comprises:

Not necessarily, solidify this electrodeposited coating;

This first ground coating composition contains:

(i) first resin binder, and

Not necessarily, dry this first priming coat;

This second ground coating composition contains:

Not necessarily, dry this second priming coat;

Solidify this top coat, second priming coat, first priming coat simultaneously, and, not necessarily, while cured primer coating, and

The light transmission that first priming coat after wherein solidifying is 15 microns at film thickness, measure in 400 nanometers is 5% or littler.

In addition, the invention still further relates to a kind of method that forms multi-layer composite coatings in substrate, this method comprises:

Not necessarily, solidify this electrodeposited coating;

This first ground coating composition contains:

(i) first resin binder, and

Not necessarily, dry this first priming coat;

This second ground coating composition contains:

Not necessarily, dry this second priming coat;

Wherein the ratio of the pigment of second coating composition and adhesive is 0.1-4.0:1

Wherein first resin binder and second resin binder all contain identical or different polyether polyols with reduced unsaturation,

The light transmission that first priming coat after wherein solidifying is 15 microns at film thickness, measure in 400 nanometers is 5% or littler, and

Wherein first ground coating composition further contains a kind of composition, said composition contains second color compositions that is scattered in second resin binder, before first ground coating composition directly was deposited on electrodeposited coating, described composition directly mixed with first ground coating composition.

In a concrete embodiment, the present invention relates to a kind of method that in substrate, forms multi-layer composite coatings, this method comprises:

Not necessarily, solidify this electrodeposited coating;

This first ground coating composition contains:

(i) first resin binder, and

Not necessarily, dry this first priming coat;

This second ground coating composition contains:

Not necessarily, dry this second priming coat;

Wherein, first resin binder and second resin binder all contain identical or different polyether polyols with reduced unsaturation, the content of the described polyurethane that exists in first ground coating composition is equal to or less than the content of the described polyurethane that exists in second ground coating composition, and content wherein is in the amount of total resin solid thing of existing in first and second ground coating compositions.

The invention further relates to a kind of method that forms multi-layer composite coatings in substrate, this method comprises:

Need not to insert priming paint surfacer layer by deposition aqueous curable first ground coating composition at least a portion of substrate, in substrate, form first priming coat;

Not necessarily, dry this first priming coat;

Not necessarily, dry this second priming coat;

Solidify this top coat, second priming coat and first priming coat simultaneously.

In a specific embodiment, the invention provides a kind of method that in the vehicle substrate, applies composite coating, comprise the following steps:

(a) at least a portion of vehicle substrate, apply electrodeposited coating;

(b) provide the first aqueous basecoat composition that contains first resin binder and first color compositions;

(c) provide the second aqueous basecoat composition that contains second resin binder and second color compositions, second color compositions is compared different with first color compositions;

(d) second ground coating composition is coated on the insertion portion of vehicle substrate inside;

(e) first ground coating composition is coated on the electrodeposited coating; And

(f) bumping wet directly be coated on first ground coating composition and drying-free first ground coating composition with second ground coating composition is wet, having the compound priming coat of first priming coat and second priming coat with formation.

The invention further relates to a kind of improved method that in the motor vehicle substrate, forms multi-layer composite coatings, comprise following continuous step:

(1) substrate of conductor motor vehicle is sent to the electro-deposition station that is positioned on the paint line;

(2) electrodeposition coating is carried out in the substrate of serving as charged electrode in circuit, this circuit comprises the counterelectrode of described electrode and oppositely charged, described electrode is dipped in a kind of water-based electrodepositable composition, between described electrode, form by electric current, so that electrodepositable composition is deposited on the continuous basically electrodeposited coating film of formation in the substrate;

(3) substrate with the coating in the step (2) transmits by being positioned at the electrodeposited coating heat cure baking oven on the paint line, with the electrodepositable composition on the cured substrate, forms electrodeposited coating thereon;

(4) substrate with the coating in the step (3) is sent to the priming paint surfacer application station that is positioned on the paint line;

(5) direct primer coating surfacer coating composition at least a portion surface of electrodeposited coating is to form priming paint surfacer coating thereon;

(6) substrate with the coating in the step (5) transmits by being positioned at the priming paint surfacer heat cure baking oven on the paint line, so that priming paint surfacer coating is solidified;

(7) substrate with the coating in the step (6) is sent to the primary coat station that is positioned on the paint line;

(8) at least a portion surface of priming paint surfacer, directly apply the aqueous basecoat composition, to form priming coat thereon;

(9) not necessarily, the substrate that applies in the step (8) is transmitted by being positioned at the sudden strain of a muscle baking oven on the paint line, so that coating is dry but do not solidify this priming coat;

(10) substrate with the coating in step (8) or the nonessential step (9) is sent to the varnish coated station that is positioned on the paint line;

(11) at least a portion of priming coat, directly apply the coating composition that is substantially free of pigment, to form varnish coat thereon; And

(12) substrate that applies in the step (11) is transmitted by being positioned at the top coat curing station on the paint line, to solidify this priming coat and varnish coat simultaneously.Improvement comprises: the substrate of the coating in the step (3) directly is sent to the primary coat station that is positioned on the paint line, on at least a portion of electrodeposited coating directly wet successively bumping wet apply independent, the composite water soluble ground coating composition, not necessarily dry every layer of continuous ground coating composition of while, to form the multilayer priming coat thereon, and need not between electrodeposited coating and priming coat to insert priming paint surfacer coating, the substrate that applies is sent to the varnish coated station that is positioned on the paint line, on at least a portion of multilayer priming coat, directly apply the coating composition that is substantially free of pigment, to form varnish coat thereon, and the substrate transmission that applies is coated with curing station by the top that is positioned on the paint line, so that multilayer priming coat and varnish coat solidify simultaneously.

In addition, the invention still further relates to a kind of paint line, comprising:

The electrodeposition coating zone comprises at least one electrophoresis tank;

The primary coat zone is positioned at the downstream in electrodeposition coating zone and closes on the electrodeposition coating zone, and the primary coat zone comprises inserts station, the first primary coat station and the second primary coat station; And

The top is coated with the zone, is positioned at the downstream in primary coat zone and closes on the primary coat zone.

Not necessarily, the substrate of this coating is heated to uniform temperature and keeps the sufficiently long time, to solidify this electrodeposited coating;

Not necessarily, dry this first priming coat;

By the directly deposition and aqueous curable second ground coating composition of the identical or different composition of first ground coating composition at least a portion of first priming coat, on first priming coat, form second priming coat;

Not necessarily, dry this second priming coat;

Wherein, first ground coating composition contains one or more water-borne dispersions by the polymer particles of monomer mixture preparation, and this monomer mixture contains one or more and has the monomer of the unsaturated point of two or more reactive olefinics and/or the combination with two kinds of different monomers of reacting to each other property group.

Description of drawings

Fig. 1 is the schematic block figure (not in scale) with application system of feature of the present invention; And

Fig. 2 is the primary coat zone schematic block figure (not in scale) of another specific embodiment with application system of feature of the present invention.

The specific embodiment

As used in this article, as " inside ", " outside ", " left side ", " right side ", " on ", the space of D score, " level ", " vertically " etc. or the term of direction, as with related to the present invention shown in the numeral in the accompanying drawing.Yet, be appreciated that the present invention can adopt different alternative orientation, and thus, these terms should not be considered limiting.Same, as used in this article, term " is deposited on ", " being coated on " or " being provided in " means deposition, applies or be provided on the something, but needn't contact on the surface.For example, a kind of material " be deposited on " in the substrate and be not precluded within this material of deposition and substrate between also have other materials of one or more identical or different compositions.In addition, term " upstream " and " downstream " refer to the moving direction of substrate in above-mentioned coating process.

Except in operation embodiment, explanation is perhaps arranged in addition, used all are represented the numerical value of component quantity, reaction condition and so in this specification and claims, should be understood to the numerical value of modifying with term " approximately " in all instances.Thereby unless opposite indication is arranged, the numerical parameter that occurs in specification below and additional claims is similar to, and can depend on that the performance of the expection of attempting reaching by the present invention changes.At least, be not to attempt to limit the scope that doctrine of equivalents is used for claim, each numerical parameter should make an explanation according to described concrete numeral and by using common approximate number skill at least.

Although having set the number range and the parameter of broad range of the present invention is approximation, the numerical value that occurs in specific embodiment is accurate as far as possible.Yet any numerical value contains the error that some must be caused by the standard deviation of finding in its corresponding experimental measurement inherently.

In addition, should be appreciated that any number range of quoting means and comprises that all are included in subrange wherein herein.For example, the scope of " 1-10 " mean comprise all between and comprise all subranges between described minimum of a value 1 and the described maximum 10, that is, have minimum of a value that is equal to or greater than 1 and the maximum that is equal to or less than 10.

In addition, as used in this article, term " polymer " " implication be meant oligomer and homopolymer and EVA.Except as otherwise noted, as used in this specification and claims, molecular weight is the number-average molecular weight of the polymeric material that obtains by gel permeation chromatography with methods known in the art with " Mn " expression and with polystyrene standards.

Before describing the specific embodiment of the present invention in detail, simply introduce earlier exemplary paint line (application system) with feature of the present invention.

Fig. 1 has schematically described the application system 10 with feature of the present invention.This system 10 is suitable for application substrate in partial or continuous process, for example, and metal or polymeric substrates.In process in batches, substrate is fixed motionless in each treatment step, and in continuous process, substrate is moved continuously along paint line.An exemplary process of the present invention will at first be discussed under the situation of application substrate in continuous paint line.

The method according to this invention, the useful substrate that can be coated comprise metallic substrates, such as the polymeric substrates of thermosets and thermoplastic, and their combination.Substrate can be used as the parts of assembly machine motor-car, includes, but are not limited to automobile, truck and tractor.Substrate can have Any shape, but is the form of car body in a specific embodiment, as the decoration of car body (framework), Peng Gai, door, dashboard, bumper and/or automobile.

With reference to Fig. 1, metallic substrates 12 can be cleaned and removes degreasing in predetermined zone 14.Pretreatment coating is as CHEMFOS 700

Trbasic zinc phosphate or BONAZINC

Rich zinc pretreating agent (all can Inc.), can be deposited on the surface of metallic substrates 12 available from the PPG Industries of Pittsburgh, Pennsylvania.

Alternately or additionally, in nonessential electro-deposition zone 16, can one or more nonessential electrodeposition coating compositions of electro-deposition at least a portion of metallic substrates 12.A kind of suitable electrocoating paint is available from the PPG Industries of Pittsburgh, Pennsylvania, the POWER PRIME of Inc.

Coating.Electro-deposition method that is suitable for and electrodeposition coating composition comprise conventional anion or cationic electrodepositable coatings composition, as epoxy or polyurethane-based paints.The electrodepositable coating that is suitable for is in U.S. Patent No. 4,933, discusses to some extent in 056,5,530,043,5,760,107 and 5,820,987, is incorporated herein this paper as a reference.Before carrying out further operation, the electrocoating paint that is suitable for can not necessarily be dried in the drying device such as baking oven 18 grades or solidify.Perhaps, additional coating as described below can be wet and be bumped wet being coated on the electrodeposited coating.

Different with the paint line of routine, paint line of the present invention does not comprise and is used to apply, solidify and/or the priming paint surfacer zone of the priming paint surfacer of polishing.By having cut down the needs of priming paint surfacer, the priming paint surfacer applies the coating equipment that needs, and for example, paint spray booth, sprayer, drying oven, grinding apparatus and binding appts also can be cut down.In addition, the reduction of priming paint surfacer can also be quickened whole coating process and dwindle the required bottoming space of application substrate 12.

In the primary coat zone 20 that comprises one or more applications station, the multilayer priming coat can be coated in the substrate 12 by multistep processes.Primary coat zone 20 can be positioned at the downstream in electro-deposition zone 16 and/or be close in electro-deposition zone 16.As used in this article, term " is close in " to mean in adjacent locations does not have other application station or main treating stations at interval.In the specific embodiment shown in Figure 1, substrate 12 is conveyed into has one or more insertion stations 22 of revolving the conventional paint spraying device 24 of cup or spray gun such as routine.As known to the those of skill in the art in painting dressing automobiles field, revolve the cone that glass coater typically comprises a main part or has rotating cup.Revolve cup link to each other with high voltage source with revolve glass and substrate between form electrostatic field.Electrostatic field makes, and coating material charged, atomizing forms conical pattern from revolving the cup emission, and its shape can change by the shaping air of being penetrated by the shaping air ring spray of revolving on the cup.The non-limitative example that the routine that is suitable for is revolved glass coater comprises available from the Eco-Bell of Michigan Auburn Hills Behr Systems Inc. or Eco-MBell coater, available from the Meta-Bell coater of Tokyo ABB/Ransburg Japan Limited, available from the G-1 Bell coater of Michigan Auburn Hills ABB Flexible Automation; Perhaps available from the Sames PPH 605 of Michigan Livonia Sames or 607 coaters etc.

Coater 24 is connected with ground coating composition source 26 and flow communication.In a specific embodiment, the ground coating composition in the source 26 is " second ground coating composition " that describes in detail below.In another embodiment, source 26 comprises the mixture of " first and second ground coating compositions " that the following describes.In inserting station 22, ground coating composition is coated on the insertion portion of substrate 12 from source 26.As known to the those of skill in the art in painting dressing automobiles field, those are not exposed to zone in the corrosive atmosphere environment usually term " insertion portion " basidigitale.The example of insertion portion comprises inner Men Sai, the inboard of skirt-type plug etc.Non-essential drying device, baking oven 28 or dodge to do the chamber for example, can be positioned at the downstream of inserting station 22 and/or be close in insert that the station is done to carry out nonessential sudden strain of a muscle before applying further coating, dry or cured coated is in the coating of insertion portion.

After inserting station 22, substrate 12 can be delivered into the first primary coat station of adjoining 30, and it has one or more conventional coaters 32, as revolves cup or spray gun, with the first primary coat material or source 34 link to each other or flow communication described in detail as follows.At the first primary coat station 30 by one or more coaters 32 in one or multi-channel spraying, first ground coating composition can be coated on, as is sprayed at, in the substrate 12, to form first priming coat in substrate 12.Will describe in detail as following, first ground coating composition comprises a kind of first resin binder and first color compositions, and described color compositions contains one or more and is scattered in pigment in first resin binder.

Nonessential drying device, baking oven 36 or dodge to do the chamber for example, do to carry out nonessential sudden strain of a muscle before applying further coating in the downstream that can be positioned at the first primary coat station 30, the dry or coating (and not necessarily dry coating of being coated on insertion portion) of cured coated on the first primary coat station 30.Can control the temperature and humidity in the drying device, first priming coat that has enough humidity or " moistening " with the evaporation of controlling first ground coating composition that deposits with formation, can obtain substantially uniform smooth, the smooth basically film of thickness thus, and can sagging.In a specific embodiment, before second ground coating composition that coating the following describes, first ground coating composition of moist coating.

The second primary coat station 40 can be positioned at the downstream at the first primary coat station 30 and/or be adjacent to the first primary coat station 30, and can have one or more conventional coaters 42, as revolve cup or spray gun, link to each other with the following second ground coating composition source 46 described in detail and flow communication.By one or more coaters 42, in one or multi-channel spraying, second ground coating composition can be coated on, as is sprayed at the second primary coat station 40, on first ground coating composition, to form second priming coat on first priming coat.In a specific embodiment, second ground coating composition " wetting, it is wet to bump " is coated on first ground coating composition, that is, before applying second ground coating composition, moist coated first ground coating composition.Like this, by on one or more layers first priming coat, applying one or more layers second priming coat, can form the MULTILAYER COMPOSITE priming coat.As used in this article, term " layer " or " multilayer " refer to can be by one or multi-channel spraying coated general coating area or scope, but and not necessarily mean adjoin two-layer between have clear and definite or discontinuous interface, that is, there is some migration in component between first and second priming coats.Described in detail as follows, second ground coating composition comprise can be identical or different with first resin binder second resin binder.Second ground coating composition also comprise can be identical or different with first color compositions second color compositions.

Conventional drying device as baking oven 50, can be positioned at the downstream at the second application station 40 and/or be adjacent to the second application station 40,, is inserting station 22 herein, and/or the first primary coat station 30, and/or the coating that the second primary coat station 40 applies can be dried or solidify.For aqueous primer, the implication of " drying " is that the water in the composition that applies does not almost completely exist.As described below, drying bottom coating makes can apply follow-up protective top layer or layer of varnish, and like this, the character of layer of varnish can not be subjected to the adverse effect of the further drying of priming coat.If the water in the priming coat is too many, the layer of varnish of subsequent coated can be owing to attempt to ftracture, occur bubble or " blast hole " by layer of varnish from the water of priming coat evaporation in the process of layer of varnish drying.Baking oven 50 can be conventional drying oven or drying device, as the infra-red radiation baking oven available from Minnesota BGK-ITW Automotive Group of Minneapolis.

Ground coating composition in the substrate 12 is by not necessarily dry back is (if desired in baking oven 50, can solidify and/or cool off), can on priming coat, apply one or more layers conventional layer of varnish or top coat in the varnish coated district 52 that includes one or more varnish coated stations 54.Each varnish coated station comprises one or more conventional coaters 56 (for example, revolving a glass coater), links to each other and flow communication with varnish paint substance source 58.

In the specific embodiment as shown in Figure 1, dry station 60 is positioned at the downstream at varnish coated station 54 and/or is adjacent to varnish coated station 54, with dry and/or solidify coated varnish coat material and/or not necessarily dry and/or solidify one or more previous coated ground coating compositions.

As used in this article, " curing " means described in detail as follows, and crosslinkable component all in the coating all have been crosslinked basically.This curing schedule can adopt any conventional drying technology to carry out, as the hot-air convection drying of using convection oven is (as automobile radiant wall/convection oven, available from Durr.Haden or Thermal Engineering Corporation), perhaps, if desired, use infrared heating, all crosslinkable component in the liquid varnish coating material are linked to a certain degree like this, so that it is accepted by auto industry as the coating process that does not enough destroy varnish coat fully to carry the car body that applies.Usually, the liquid varnish coating material is heated to 120 ℃-150 ℃ temperature and keeps time of 20-40 minute to solidify this liquid varnish coating.

Perhaps, if before applying liquid varnish paint material, one or more layers ground coating composition does not also solidify, by using conventional equipment to carry out hot-air convection and/or infrared heating to solidify all ground coating compositions and this liquid varnish coating material, all ground coating compositions and this liquid varnish coating material can be solidified together.

Fig. 2 has enumerated a kind of primary coat zone 20a that selects to use, and it can be used to implement the present invention.Shown in dotted line, in this specific embodiment, insert station 22 not necessarily between the first and second primary coat stations 30,40 (that is the downstream at the first primary coat station 30).Perhaps, insert the downstream that station 22 can be positioned at the second primary coat station 40.If desired, nonessential drying device (not shown) also can not necessarily be positioned at one or more first primary coat stations 30, insert the downstream at the 22 and/or second primary coat station 40, station.

Describe the exemplary application system of the present invention, will describe exemplary coating process of the present invention now.

As mentioned above, in a specific embodiment, the present invention relates to a kind of method that in substrate, forms multi-layer composite coatings.This method comprises: by the coating composition of the curable electro-deposition of electro-deposition at least a portion of substrate, form electrodeposited coating in substrate; Not necessarily, the substrate with this coating is heated to uniform temperature and keeps time enough to solidify this electrodeposited coating; By at least a portion of electrodeposited coating, directly depositing the aqueous curable ground coating composition, on electrodeposited coating, form priming coat; Not necessarily, dry this priming coat; By at least a portion of priming coat, directly depositing the curable top layer coating composition that is substantially free of pigment, on priming coat, form top coat; And, solidify this top coat, priming coat simultaneously, and, not necessarily, while cured electrodeposition coating.

Electrodeposition coating composition can be coated on exposed metallic substrates or the pretreated metallic substrates of process, " exposed metal " means untreated metallic substrates, and it is not used such as pretreatment compositions such as conventional phosphate solution, heavy metal purificants and handled.In addition, in order to realize purpose of the present invention, " exposed metal " substrate can comprise the cut edge of substrate, the non-edge surface of described substrate or processed and/or coated mistake.

Before handling or apply with any coating composition, substrate not necessarily can be made into target product.The combination of more than one metallic substrates can be assembled together and form such target product.

" substrate " that has deposited electrodeposition coating composition on it can comprise any conductive substrates that has applied one or more preliminary treatment and/or primer base on it in advance, and described conductive substrates comprises those that describe in detail below.For example, " substrate " can comprise the substrate of metal and the weldable primer coating at least a portion substrate surface.Above-mentioned then electrodepositable coating composition is by electro-deposition and be solidificated on its at least a portion.One or more layers topcoat compositions of describing in detail below is coated on the electrodeposited coating that at least a portion solidified successively.

For example, substrate can comprise any aforesaid conductive substrates and be coated on the suprabasil pretreatment compositions of at least a portion, this pretreatment compositions comprises a kind of one or more solution that contains IIIB or IVB group element compound or its mixtures that contain, described compound is dissolved or dispersed in the mounting medium, typically is aqueous medium.IIIB or IVB family element usefulness, for example, at the CAS period of element table definition shown in chemistry and the physics handbook (the 60th edition, 1980).Transistion metal compound and rare earth compound typically are compound of zirconium, titanium, hafnium, yttrium and cerium and composition thereof.Typical zirconium compounds can be selected from hexafluoro zirconate, its alkali metal and ammonium salt, zirconium carbonate ammonium, and zirconyl nitrate, carboxylic acid zirconium and hydroxycarboxylic acid zirconium such as fluorine zirconic acid, the acetic acid zirconium, the oxalic acid zirconium, Glycolic acid zirconium ammonium, the zirconium lactate ammonium, citric acid zirconium ammonium, and composition thereof.

The pretreatment compositions carrier also can contain film-forming resin, for example, one or more alkanolamines and contain the product of the epoxy functionalized material of at least two epoxide groups, as at US5, those disclosed in 653,823.Other resin that is suitable for comprises as at US3, the water-soluble and water dispersible polyacrylic acid of those disclosed in 912,548 and US5,328,525; As at US5, disclosed phenolic resins in 662,746 is incorporated this paper into as a reference at this; As those disclosed water soluble polyamides in WO95/33869; As Canadian patent application 2,087, the maleic acid of describing in 352 or the copolymer of acrylic acid and allyl ether; And as US5, the water-soluble and dispersion resin of discussing in 449,415 comprises epoxy resin, aminoplast, phenolic resins, tannin, and polyvinylphenol.

Further, non-iron or ferrous metal substrate can be used such as US5, and organic phosphate or the organic phosphonate non-insulated layer described in 294,265 and 5,306,526 are carried out preliminary treatment.This organic phosphate or organic phosphonate pretreating agent can be available from PPG Industries, Inc., and commodity are called NUPAL

Behind the non-conductive coating layer that applies in the substrate such as NUPAL, before the coating film coalescence, typically then use the step of rinsed with deionized water substrate.This can guarantee that non-conductive coating layer is enough thin to guarantee being nonisulated, and is promptly enough thin so that non-conductive coating layer can not influence the electric conductivity of substrate, allows the electrodepositable coating composition of follow-up electro-deposition.The pretreatment coating composition can further contain surfactant, and it improves the wetability of substrate as auxiliary agent.Usually, the amount of surfactant materials in the pretreatment coating composition total weight less than about 2wt%.The nonessential material of in the mounting medium other comprises defoamer and substrate wetting agent.

Consider factor of environmental, can not contain the chromium material in the pretreatment coating composition, promptly said composition contains and is less than about 2wt% and contains the chromium material (with CrO ₃Expression), typically contain and be less than about 0.05wt% and contain the chromium material.

In preprocessing process, before pretreatment compositions is deposited on the surface of metallic substrates, usually by thoroughly to the surface clean, oil removing, and remove foreign matter from the metal surface.Metal substrate surface can be by the method cleaning of physics or chemistry, as by the mechanical polishing surface or with commercially available alkalescence well known by persons skilled in the art or acidic cleaner such as sodium metasilicate and NaOH cleaning/oil removing.The non-limitative example of the cleaning agent that is suitable for is CHEMKLEEN

163, a kind of available from PPG Pretreatment and Specialty Products of Troy, the alkaline cleaner of Michigan.Also can use acidic cleaning.Behind the cleaning, usually with the water rinse metallic substrates to remove any residue.This metallic substrates can be carried out the air drying with air knife, by substrate being exposed to simply high temperature or compression roller being passed through in substrate, moisture content is dodged baking fall.The pretreatment coating composition can be deposited at least a portion outer surface of metallic substrates.Preferably, handle the whole outer surface of metallic substrates with pretreatment compositions.The thickness of preliminary treatment film can change to some extent, but usually less than about 1 micron, preferably in the scope of about 1-500 nanometer, more preferably in the scope of 10-300 nanometer.

By the paint-on technique of routine, as batch or continuously spraying, dipping or roller coat, the pretreatment coating composition is coated on substrate surface.The temperature of pretreatment coating composition is generally about 10 ℃-85 ℃ during coating, is preferably about 15 ℃-60 ℃.The pH value of pretreatment coating composition in the scope of 2.0-5.5, typically is 3.5-5.5 usually during coating.The pH value of medium can be regulated with following material: inorganic acid such as hydrofluoric acid, fluorine bromic acid, phosphoric acid etc. comprise its mixture; Organic acid such as lactic acid, acetic acid, citric acid, sulfamic acid, or its mixture; And water-soluble or water dispersible alkali such as NaOH, ammonium hydroxide, ammoniacal liquor, perhaps amine such as triethylamine, Methylethyl amine or its mixture.

Continued operation is generally used for coil painting industry, also is used for factory's application (millapplication).The pretreatment coating composition can apply with any of these conventional methods.For example, in coiled material industry, substrate is cleaned and rinsing usually, contacts with the pretreatment coating composition by roller coat with chemical coating machine then.Then, the band of handling is dried by heating, the coated and baking by conventional coil painting method.

Factory's application pretreatment compositions can be coated on coating on the new metal tape of handling by dip-coating, spraying or roller coat and carry out.Unnecessary pretreatment compositions is removed by dehydration roll usually.After pretreatment compositions is coated on the metal surface, can use the rinsed with deionized water metal, and dry to remove redundant moisture from the substrate surface of handling and to solidify any curable coating component under the temperature of room temperature or rising to form pretreatment coating.Perhaps, the substrate of handling can be heated to and keep 2-30 second to form the substrate of the coating that has the residue after the pretreatment coating composition dries thereon under the uniform temperature in 65 ℃ of-125 ℃ of scopes.If substrate by being heated in the hot melt production process, then need not the substrate of handling is being carried out the back heating so that dry.The temperature and time of dry coating will depend on the percentage composition of solids in the coating, the component of coating composition and the type of substrate.

The film coverage rate of pretreatment compositions residue is usually at every square metre of 1-10,000 milligram of (mg/m ²) scope in, and be generally 10-400mg/m ²

No matter whether this substrate passes through preliminary treatment, can also apply the weldable primer layer in substrate.The non-limitative example of the weldable primer that is suitable for is included in US5, those that describe in 580,371,5,652,024,5,584,946 and 3,792,850.Weldable primer can contain the film forming polymer of reactive functional groups, for example polyepoxide polymer or have the acrylate copolymer of epoxy-functional; And be suitable for crosslinking agent with the functional group reactions of film forming polymer.The weldable primer composition further contains one or more conducting pigments such as carbon black etc., and its amount is enough to make the priming paint of curing to weld.Typical weldable primer is BONAZINC

, it is the organic film-forming composition of rich zinc of a kind of factory application, available from the PPG Industries of Pittsburgh, Pennsylvania, Inc..The thickness of the BONAZINC that applies can be at least 1 micron, is generally the 3-4 micron.Other weldable primer as rich iron phosphide priming paint, can commercially availablely obtain.

Nonessential electrodeposition step in any method of the present invention can comprise conductive substrates is immersed in the electrophoresis tank of water-based electrodepositable composition that in the circuit that comprises negative electrode and anode, negative electrode is served as in substrate.Between electrode, apply enough big electric current, with the electrodepositable coating composition film continuous basically, adhesion of deposition one deck at least a portion surface on conductive substrates surface.In addition, be to be understood that, as used in this article, at least a portion surface of " substrate " " on " electrodepositable composition or the coating that form refer to the composition that directly forms at least a portion substrate surface, and in any composition or coating that forms on coating on substrate at least a portion or the pre-treatment substance that be coated in advance.Electro-deposition is carried out under the burning voltage in 1 volt to thousands of volts scope usually, is generally between the 50-500 volt.Current density is between every square feet of 1.0-15 ampere (every square metre of 10.8-161.5 ampere) usually, and reduces rapidly in electrodeposition process, shows the film that has formed continuously, insulated certainly.

In case electrodepositable coating composition (describing in detail below) is coated as mentioned above, in substrate, form one deck electrodeposited coating thus, this electrodeposited coating not necessarily, is heated to uniform temperature and keeps the sufficiently long time with the cured electrodeposition coating.The substrate that applies can be heated to 250 ° of uniform temperatures to 450 ℉ (121.1 ° to 232.2 ℃), is generally 250 ° to 400 ℉ (121.1 ° to 204.4 ℃), typically is 300 ° to 360 ℉ (148.9 ° to 180 ℃).Can depend on solidification temperature and other variable hardening time, for example, the film thickness of electrodeposited coating, the amount of the catalyst in the composition and kind etc.In order to realize purpose of the present invention, the necessary coating that is necessary long enough of time with effective cured electrodeposition in substrate.For example, can in 10 minutes to 60 minutes scope, typically be 10 to 30 minutes hardening time.The thickness of the electrodeposited coating of resultant curing is usually in 15 to 50 microns scope.

As used in this article, the term of relevant use " curing " with composition, for example " cured compositions " means crosslinkable component all in the composition by partial cross-linked at least.In some specific embodiment of the present invention, the crosslink density of crosslinkable component, that is, crosslinked degree is in 5% to 100% complete crosslinked scope.In other the specific embodiment, crosslink density is in 35% to 85% complete crosslinked scope.In the other specific embodiment, crosslink density is in 50% to 85% complete crosslinked scope.Those skilled in the art are appreciated that crosslinked existence and degree thereof, that is, crosslink density can be determined by a lot of methods, as use the dynamic mechanics heat analysis (DMTA) of the TA device DMA 2980 DMTA analyzers of operating under nitrogen.This method is measured the glass transition temperature and the crosslink density of coating or polymer free film.These physical properties of curing material are relevant with the structure of cross-linked network.

Used electrodepositable coating composition can be any anion known in the art or cationic electrodepositable coatings composition in the method for the present invention.As previously mentioned, the electrodepositable cationic compositions is generally used for the electrodeposition coating of metal motor vehicle or automobile substrate.

Electrodepositable coating composition contains a kind of resin phase that is scattered in the aqueous medium usually, and this resin contains (a) ion exchange resin non-gel, that contain active hydrogen group mutually and (b) has a curing agent with the functional group of (a) active hydrogen group reaction.This electrodepositable coating composition is generally the form of electrodeposition bath.

It is crosslinked basically and have in being dissolved in appropriate solvent the time as for example according to inherent viscosity that ASTM-D1795 or ASTM-D4243 measured that " non-gel " means resin.The inherent viscosity of product is the indication of its molecular weight.On the other hand, because molecular weight infinite height in essence, the inherent viscosity of the product of gel can be too high and can't measure.As used in this article, " not crosslinked basically " product means weight average molecular weight (Mw) by gel permeation chromatography less than 1,000,000 product.

Term " active hydrogen " mean those can with the group of isocyanate reaction, as JOURNAL OFTHE AMERICAN CHEMICAL SOCIETY, Zerewitnoff measuring of describing among the Vol.49 the 3181st page (1927).For example, active hydrogen can derive from oh group, primary amine groups and/or secondary amine.

The example that is applicable to the film-forming resin in the anionic electrodeposition deposition bath composition is the alkali solubilising, contains the polymer of carboxylic acid, as the product or the additive compound of drying oil or semi-drying fatty acid ester and dicarboxylic acids or acid anhydrides; And fatty acid ester, unsaturated acids or acid anhydrides and any interpolation can be further and the product of the unsaturated modified material of polyol reaction.The copolymer that also has unsaturated carboxylic acid hydroxy alkyl ester, unsaturated carboxylic acid and at least a other ethylenically unsaturated monomer that is suitable for to the small part neutralization.The electrodepositable resin of Shi Yonging comprises alcohol acid amido plastics excipient in addition,, contains the excipient of alkyd resins and amine aldehyde resin that is.Other anion electrodepositable resin composition contains the mixed ester of resinae polyalcohol.These compositions are at US3, and 749,657 the 9th hurdle 1-75 are capable and the 10th hurdle 1-13 is capable describes to some extent, and all these are incorporated herein this paper as a reference.Other sour functionality polymer also can use, as those skilled in the art known phosphatization polyepoxide or phosphatization acrylate copolymer.

Be applicable to that the cationic polymer in the electrodepositable coating composition can comprise any cationic polymer in many cationic polymers as known in the art, as long as this polymer is " water is dispersible ", that is, be easy to dissolved, disperse or be emulsifiable in the water.This base polymer contains Cationic functional groups to give its electropositive.

The example of the cation film-forming resin that is suitable for comprises the resin that contains amine salt group, as polyepoxide with such as at US3, those uncles that describe in 663,389,3,984,299,3,947,338 and 3,947,339 or the sour solubilising product of secondary amine.Usually, these resins that contain amine salt group are used in combination with the isocyanate curing agent of end-blocking.Isocyanates can be as above-mentioned US3, described in 984,299 by complete closed, perhaps this isocyanates also can be as US3, partly closed described in 947,338 also reacts with resin backbone.In addition, as US4,134,866 and DE-OSNo.2, described in 707,405, the one-component composition also can be used as film-forming resin.Except the epoxy-amine product, film-forming resin can also be selected from acrylic cationic resin, as at US3, and 455,806 and 3,928, those described in 157.

Except the resin that contains amine salt group, the resin that contains quaternary ammonium salt group also can be used.The example of these resins is those resins that formed by organic polyepoxide and tertiary ammonium salt reaction.These resins are at US3, describe to some extent in 962,165,3,975,346 and 4,001,101.The example of other resin cation is to contain the resin of trivalent sulfonium group and contain the resin of Si Jia phosphonium salt group, as at US3, and institute's those of description respectively in 793,278 and 3,984,922.In addition, the film-forming resin that solidifies by the ester exchange reaction of describing among the european patent application No.12463 also can use.Further, as US4, the cationic compositions of describing in 134,932 by the Mannich base preparation also can use.

Usually, resin (a) is the resin that contains uncle and/or secondary amine group, positively charged.These resins are at US3, describe to some extent in 663,389,3,947,339 and 4,116,900.At US3, in 947,339, the ketimide derivative of polyamines as diethylenetriamines or trien, reacts with polyepoxide.When with sour neutralization reaction product and when being scattered in the water, can produce free primary amine groups.Equally, when polyepoxide and unnecessary polyamines reaction such as diethylenetriamines and trien, form the equivalent product, unnecessary polyamines is come out by vacuum desorption in the product.These products are at US3, describe to some extent in 663,389 and 4,116,900.

Foregoing description contain content in the used in the methods of the invention electrodeposition bath of active hydrogen, ion electrodepositable resin, in the gross weight of electrodeposition bath, can in the scope of 1-60wt%, be generally 5-25wt%.

The resin that is applicable to the electrodeposition bath in the inventive method further contains the curing agent (b) that is easy to the active hydrogen group reaction of the ion electrodeposition resin (a) of above-mentioned firm description mutually.The organic PIC and the aminoplast curing agent of sealing all are applicable among the present invention, although the isocyanates of sealing is generally used for cathode electrodeposition.

Amino resin as the curing agent of anionic electrodeposition deposition, is the condensation product of amine or acid amides and aldehyde usually.The amine that is suitable for or the example of acid amides are melamine, benzoguanamine, urea and similar compounds.Usually, used aldehyde is formaldehyde, although also can as acetaldehyde and furfural, obtain product by other aldehyde.Condensation product contains methylol groups or similar hydroxyalkyl group, depends on used concrete aldehyde.Preferably, these methylol groups are by reacting by etherificate with alcohol.Used various alcohol comprise the monohydric alcohol that contains 1-4 carbon atom, as methyl alcohol, ethanol, isopropyl alcohol, and n-butanol, particular methanol.Amino resin can obtain by Solutia is commercially available by Cytec with by trade mark RESIMENE with trade mark CYMEL.

The aminoplast curing agent is generally used for and the anion electrodepositable resin crosslinks that contains active hydrogen, and in the gross weight of resin solid thing in the electrodeposition bath, consumption is extremely about 60wt% of about 5wt%, is preferably 20wt% to about 40wt%.

Typically, the curing agent that is used for cathode electrodeposition comprises the organic isocyanate of sealing.PIC can be as US3,984,299 the 1st hurdle 1-68 are capable, the 2nd hurdle and the 3rd hurdle 1-15 are capable described by complete closed, perhaps as US3,947,338 the 2nd hurdle 65-68 are capable, the 3rd hurdle and the 4th hurdle 1-30 capable described partly closed and with the main polymer chain reaction, incorporate this paper into as a reference at this." sealing " means isocyanate groups and reacted with compound, so that the blocked isocyanate group of gained is at room temperature stable for active hydrogen, but at elevated temperatures, be generally between 90 ℃-200 ℃, have reactivity with active hydrogen in the film forming polymer.

The PIC that is suitable for comprises aromatic series and aliphatic polymeric isocyanate, comprise cycloaliphatic polyisocyanates, representative example comprises diphenyl-methane-4,4 '-vulcabond (MDI), 2,4-or 2,6-toluene di-isocyanate(TDI) (TDI), comprise its mixture, right-phenylene diisocyanate, tetramethylene diisocyanate and two isocyanic acids, six methylene esters, two cyclohexyl methanes-4,4 ' vulcabond, IPDI, phenylmethane-4, the mixture of 4 '-vulcabond and polymethylene polyphenyl isocyanate.Higher polyisocyanates as triisocyanate, also can use, for example, and triphenylmenthane-4,4 ', 4 ' '-triisocyanate.With polyalcohol such as neopentyl glycol and trimethylolpropane, and with the isocyanate pre-polymer of polymer polyatomic alcohol such as pcl-diol acid lactone and the crosslinked preparation of triol (the NCO/OH equivalent proportion is greater than 1), also can use.

Polyisocyanate curing agent is generally used for the electrodepositable resin cation that contains active hydrogen crosslinked, and in the gross weight of resin solid thing in the electrodeposition bath, consumption is extremely about 60wt% of about 5wt%, typically is 20wt% to about 50wt%.

The water-based electrodepositable coating composition is the form of aqueous liquid dispersion.Term " dispersion " is thought transparent, the translucent or opaque resin system of two-phase, wherein resin in decentralized photo and water in continuous phase.The average particle size particle size of resin phase is usually less than 1.0 and usually less than 0.5 micron, preferably less than 0.15 micron.

The percentage by weight of resin phase in the aqueous medium is in the gross weight of water-borne dispersions, for 1wt% at least and usually be 2wt%-60wt%.When composition of the present invention was the form of resin concentrate, they had the resin solid content in aqueous liquid dispersion weight 20wt%-60wt% usually.

In a specific embodiment of the present invention, electrodepositable coating composition is the composition that contains the fast light degraded of resin phase, resin comprises mutually: resin one or more the non-gels of (1) electrodepositable on negative electrode, that contain active hydrogen, cation amine salt group and (2) one or more partially enclosed at least aliphatic polymeric isocyanate curing agent.The amine salt group of resin cation (1) derives from has following array structure (I) or amino of side (II) and/or end amino:

(I) —NHR

Or

Wherein R represents H or C ₁To C ₁₈Alkyl; R ¹, R ², R ³And R ⁴Identical or different, represent H or C respectively independently ₁To C ₄Alkyl; X and Y can be identical or different, represent hydroxyl or amino respectively independently.

" end group and/or side group " means uncle and/or secondary amino group as overhanging main polymer chain or being positioned at the substituting group of its terminal location, perhaps, alternately, is the end group substituting group that overhangs main polymer chain and/or be positioned at the group of its terminal location.In other words, the cation amine salt group amino of being originated is not on main polymer chain.

" alkyl " means alkyl and aralkyl, the univalence hydrocarbyl of ring or acyclic, straight or branched.Alkyl can be not replace or replace with one or more hetero atoms, and for example, non-carbon, non-hydrogen atom are as one or more oxygen, nitrogen or sulphur atom.

With above-mentioned structural formula (I) and (II) expression side and/or end is amino can derive from the compound that is selected from following material: ammonia, methylamine, diethanol amine, diisopropanolamine (DIPA), N-hydroxyethyl-ethylenediamine, diethylenetriamines, and composition thereof.The compound that one or more are such and one or more above-mentioned polymer react, for example, react with polyepoxide polymer, wherein epoxide group is open loop by reacting with polyamines, therefore end amino and secondary hydroxyl are provided, perhaps with the acrylate copolymer reaction with epoxy-functional, described epoxy-functional derives from epoxy functional, ethylenically unsaturated monomer, as GMA.

In a specific embodiment of the present invention, the polymer that contains cationic salt groups contains and derives from have said structure one or more sides and/or the amino amine salt group of end of (II), therefore when electrodepositable coating composition by electro-deposition with when solidifying, have at least two electron-withdrawing groups (following detailed description) to be bonded on the β position of all nitrogen-atoms basically that exist in the electrodeposited coating with respect to curing.In the further specific embodiment of the present invention, when electrodepositable coating composition by electro-deposition with when solidifying, three electron-withdrawing groups are bonded on the β position with respect to all nitrogen-atoms basically that exist in the electrodeposited coating that solidifies." basically all " nitrogen-atoms that exists in the electrodeposited coating that solidifies means at least 65% of all nitrogen-atoms of existing in the electrodeposited coating of curing, typically is 90%, and it derives from the amine that is used to form the cation amine salt group.

As discussed below, draw in this article for the electron withdraw group of reference is formed by polyisocyanate curing agent and the side of representing with X and Y in structural formula (II) and/or terminal hydroxy group and/or amino reaction, it is bonded in this structure on the β position with respect to nitrogen-atoms.Electrodepositable composition solidifies exist in the free film free or the amount of bonding amine nitrogen can be by following mensuration.The free coated film of solidifying can be pulverized by low temperature and be used acetate dissolution, uses total alkali content in the perchloric acid constant-current titration working sample of acetate then.Primary amine content in the sample can be reacted the reaction that forms not titratable azomethine by primary amine and salicylide and be determined.Any then unreacted second month in a season or tertiary amine can be measured by constant-current titration with perchloric acid.Difference between total alkalinity and this titration is represented primary amine.Tertiary amine content in the sample can be measured with the perchloric acid constant-current titration after primary amine and secondary amine and acetic anhydride reaction formation corresponding amide.

In a specific embodiment of the present invention, end amino has structural formula (II), and wherein X and Y contain primary amine group, for example, derive from the amino of diethylenetriamines.Should be appreciated that, in this case, with polymer reaction before, primary amine group can be closed, for example, by with reactive ketone such as MEK etc., form two ketimides.This two ketimide is at US4, and 104,147 the 6th hurdles the 23rd walk to those that describe in the 7th hurdle the 23rd row.Amine-epoxy reaction product is scattered in the water back diketone imido grpup and can decomposes, thereby provides free primary amine group as the curing reaction position.

On a small quantity (for example, be less than or equal to 5% with total amine azotometer in the composition) amine, as hydroxyl not single, two and aryl-the alkylamine of trialkylamine and mixing, perhaps the amine that replaces with the group beyond the hydroxyl provides the material that contains these amine can adverse effect not arranged to the light degradation resistance of the electrodeposited coating that solidifies.Concrete example comprises MEA, N-methylethanolamine, ethamine, methyl ethylamine, triethylamine, N-benzyl dimethylamine, two cocoa amines and N, N-dimethyl cyclohexyl amine.

Being reflected at when mixing this amine and polymer of epoxide group taken place on above-mentioned amine and the polymer.Amine be introduced in the polymer, and vice versa.This reaction can self be carried out or carry out in the presence of appropriate solvent such as methylisobutylketone, dimethylbenzene or 1-methoxyl group-2-propyl alcohol.This reacts normally heat release, may need cooling.Yet, can be heated to about 50 ℃ to 150 ℃ neutral temperature to quicken this reaction.

The polymer that contains active hydrogen, cation alkali that is used for electrodeposition composition is prepared so that the light degradation resistance maximum of polymer and resulting cured electrodeposition composition by the component of selecting.Be not bound by any theory although do not want, it is relevant with the position and the characteristic of the cationic nitrogenous group that is used to contain active hydrogen, cation amine salt base resin dispersion that but the light degradation resistance (that is, anti-visible light and ultraviolet degradation) of the electrodeposited coating that solidifies is considered to.

In order to realize purpose of the present invention, the amino amine of being originated of side and/or end contains uncle and/or secondary amine, and therefore the active hydrogen of described amine will be by forming urea groups or crosslinked consumption with partially enclosed at least aliphatic polymeric isocyanate curing agent reaction in the process of solidifying.As if the urea groups that forms in solidify reaction process do not have severe bad influence to the light degradation resistance of the electrodeposited coating that solidifies.

In a specific embodiment of the present invention, polyepoxide polymer can " be gone functionalized " with excess of ammonia, obtains containing the polymer of one or more following construction units (III).By being mixed with the dispersion of promotion in water, this polymer and suitable solubilization acid can form cationic salt groups subsequently.

In a selectable specific embodiment of the present invention, cationic polymer (1) can contain the polyepoxide polymer with side and/or end amino group, and described amino contains the primary amine group that can form the cation amine salt.This polymer can pass through, and for example, diethylenetriamines diketone amine and the polymer reaction that contains epoxide group then are hydrolyzed to decompose this ketimide, are prepared.This polymer can contain one or more following construction units (IV):

Be surprisingly found out that although there is uncle's nitrogen in this construction unit, the electrodeposition composition that contains this polymer shows the light degradation resistance of improvement.Do not want to be bound by any theory, this be considered to since with the solidify reaction process of polyisocyanate curing agent in formed two and be bonded to respect to the strong electron-withdrawing group group on the tertiary N atom β position (in this case, being urea groups).

Similarly, find to contain the polymer that has other construction unit of isocyanate-reactive group on respect to tertiary N atom β position and also can show similar light degradation resistance.This polymer can contain, for example, and following construction unit (V) and (VI):

Or

The polymer by having one or more construction units (VI) and the reaction of polyisocyanate curing agent form the electrophilic carbamate groups on respect to tertiary N atom β position, described tertiary N atom derives from side and/or end is amino.Similarly, the polymer by having one or more construction units (V) and the reaction of polyisocyanate curing agent form electrophilic carbamate and urea groups on respect to tertiary N atom β position, and described tertiary N atom derives from side and/or end is amino.

As used in this article, " electron withdraw group " means the group (for example, carbamate or urea groups) that is easy to from the amino nitrogen atom electrophilic or negative electrical charge, thereby gives amine nitrogen less alkalescence.This electron withdraw group can derive from polyisocyanate curing agent and hydroxyl of representing with X and Y and/or amino reaction in said structure formula (II), be the side and/or the end group of resin.In addition, should be appreciated that in order to realize purpose of the present invention, carbamate groups is not in the scope of term " electron withdraw group ", described carbamate groups derives from hydroxyl on polyisocyanate curing agent and the main polymer chain, and/or the reaction of the secondary hydroxyl that forms by epoxy ring-opening.

Have been found that the polymer that contains such as following construction unit (VII) and/or basic structural unit (VIII), wherein R represents the unsubstituted alkyl group, with top those polymer phases of just having described than the light degradation resistance that shows non-constant.Do not want to be bound by any theory, contain basic structural unit (VII) and/or the relatively poor light degradation resistance of polymer (VIII) like this and be considered to owing to basic nitrogen (not being polymer side and/or end group) being arranged on the main polymer chain and/or not being reflected at two electron withdraw groups of generation on the alkaline amido β position with polyisocyanate curing agent.

And/or

Those skilled in the art are by containing a lot of construction units (VII) and cation epoxides (VIII) relatively poor solidification effect usually, can infer on (VII) main chain and can not participate in effectively solidifying on the phenoxy group β position and near the terminal oh group of construction unit (VIII), that is, they can not fully be converted into the electrophilic carbamate groups in curing schedule.Similarly, should be noted that with the consumption degree of polyisocyanate curing agent reaction basic nitrogen and can measure by the electrodepositable composition of cryogenic grinding behind titration such as the above-mentioned curing schedule.

If desired, can contain a spot of have construction unit (VII) and/or polymer (VIII) in the electrodepositable coating composition of the present invention, as long as the amount of these polymer is not enough to the light degradation resistance of the electrodeposited coating that solidifies is had a negative impact.

Contain active hydrogen, contain the amino polymer of end by being endowed electropositive and water-dispersible with acid to small part neutralization.The acid that is suitable for comprises organic and inorganic acid such as formic acid, acetate, lactic acid, phosphoric acid, dihydromethyl propionic acid and sulfamic acid.Acid blend also can use.The degree of neutralization changes to some extent according to contained concrete product.Yet, should use enough acid so that electrodepositable composition is scattered in the water.Typically, the amount of used acid provide in the theory and total amount at least 30%.Also can use and surpass in 100% theory and the excessive acid of total amount aequum.

The degree that cationic salt groups forms should be when polymer mixes with aqueous medium and other composition, can form the stable dispersion of electrodepositable composition." stable dispersion " if mean some sedimentation take place, and it can sedimentation or is easy to disperse again.And dispersion equally has enough cationic characteristics, so that when applying voltage between anode in immersing water-borne dispersions and the negative electrode, dispersed particles can be to cathodic migration and electro-deposition thereon.

Usually, cationic polymer be non-gel and contain the about 0.1-3.0 of every gram polymer solids, the millinormal cationic salt groups of preferably about 0.1-0.7.

The active hydrogen relevant with cationic polymer comprise any in about 93 ℃ of-204 ℃ of scopes with the active hydrogen of isocyanate reaction, temperature is preferably about 121 ℃-177 ℃.Usually, active hydrogen is selected from the group of hydroxyl and primary and secondary amino, comprises the mixed group such as hydroxyl and primary amino radical.Preferably, polymer has the about 1.7-10 milliequivalent of every gram polymer solids, is preferably the active hydrogen content of about 2.0-5 milliequivalent active hydrogen.

The amount of polymer in the used fast light degraded electrodepositable composition of the inventive method that contains cationic salt groups, resin solid gross weight in cation salt based polyalcohol and curing agent, at 20wt-80wt%, be generally in the scope of 30wt-75wt%.

As mentioned above, the resin of fast light degraded electrodepositable coating composition further contains the curing agent (2) that is easy to the reaction of the active hydrogen group of the top cationic electrodepositable resin of just having described mutually.In a specific embodiment of the present invention, curing agent contains one or more partially enclosed at least aliphatic polymeric isocyanates.In this specific embodiment, can comprise on a small quantity (promptly, the 10wt% that is less than curing agent resin solids gross weight in the composition, preferably be less than 5wt%) aromatic poly-isocyanate, as long as this aromatic poly-isocyanate does not exist with the amount of the light degradation resistance of the electrodeposition composition that is enough to have a strong impact on curing.

Aliphatic polymeric isocyanate can be as US3, and 984,299 the 1st hurdle 1-68 are capable, the 2nd hurdle and the 3rd hurdle 1-15 are capable described, by complete closed; Perhaps as US3,947,338 the 2nd hurdle 65-68 are capable, the 3rd hurdle and the 4th hurdle 1-30 are capable described, and part is closed and reacts with main polymer chain.In a specific embodiment of the present invention, polyisocyanate curing agent be substantially free of isocyanate groups by the PIC of complete closed.

Higher PIC typically uses vulcabond, although also can be used to substitute or be used in combination with vulcabond.The example that is suitable for the aliphatic polymeric isocyanate of making curing agent comprises cyclic aliphatic and araliphatic PIC, as 1, hexamethylene-diisocyanate, IPDI, two-(isocyanato-cyclohexyl) methane, poly-1, hexamethylene-diisocyanate, trimerization IPDI, norbornane group diisocyanate and composition thereof.In a specific embodiment of the present invention, curing agent contain be selected from poly-1, the PIC of hexamethylene-diisocyanate, IPDI and composition thereof, complete closed.Polyisocyanate curing agent contains the Desmodur N3300 from Bayer Corporation in another specific embodiment of the present invention

, complete closed 1, the hexamethylene-diisocyanate tripolymer.

In a specific embodiment of the present invention, the aliphatic polymeric isocyanate curing agent is partially enclosed at least by at least a sealer, sealer is selected from 1, the 2-alkane diol is as 1,2-propane diols, 1, the 3-alkane diol is as 1,3-butanediol, benzene metynodiol such as benzylalcohol, allyl alcohol such as allyl alcohol, caprolactam, dialkylamine such as dibutylamine, and composition thereof.In the further specific embodiment of the present invention, the aliphatic polymeric isocyanate curing agent is had 1 of three or more carbon atoms by at least a, the 2-alkane diol, and as 1, the 2-butanediol, partially enclosed at least.

If desired, sealer can further contain a small amount of other known sealer such as aliphatic, cyclic aliphatic or aromatic series alkyl monocarbon alcohol or phenolic compounds, comprise, for example, low carbon fat alcohol such as methyl alcohol, ethanol and n-butanol; Cycloaliphatic alcohol such as cyclohexanol; Aromatic series-alkylol such as phenyl methanol and methyl phenyl carbinol; And the phenol of phenolic compound such as phenol self and replacement, wherein replacing part does not influence the application operation, as cresols and nitrophenol.Glycol ethers and glycol amine also can be used as sealer.The glycol ethers that is suitable for comprises butyl glycol ether, butyl carbitol, Ethylene Glycol Methyl ether and methyl proxitol.Other sealer that is suitable for comprises oxime such as methyl ethyl ketone oxime, acetoxime and cyclohexanone oxime.As mentioned above, these conventional sealers can be with a small amount of use, as long as their quantity not sufficient is with the light degradation resistance of the electrodeposited coating that has a strong impact on curing.

In used in the methods of the invention fast light degraded, the electrodepositable composition, the amount of partially enclosed at least polyisocyanate curing agent (2), resin solid gross weight in cation salt based polyalcohol and curing agent, can be in the scope of 80-20wt%, be generally 75-30wt%, typically be 70-50wt%.

The fast light degraded, the electrodepositable coating composition that are suitable for are No.10/005 at sequence number, describe to some extent in 830 the U.S. Patent application, incorporate this paper herein into as a reference.

Be applicable to any electrodepositable coating composition of the inventive method, typically can further contain other nonessential component.For example, resin binder is scattered in the aqueous medium that contains connate water.Except water, aqueous medium can also contain agglomerated solvent, for example, hydrocarbon, alcohol, ester, ether and ketone are as single ethylether, single-butyl ether and single hexyl ether of isopropyl alcohol, butanols, 2-Ethylhexyl Alcohol, isophorone, 2-methoxyl group pentanone, ethylene glycol and propane diols and ethylene glycol.Can also contain color compositions in the dispersion liquid, for example, below with reference to ground coating composition described those, and, if desired, also contain various additives such as surfactant, wetting agent or catalyst.Other component can comprise anticorrosive, for example, rare earth compound, as solvable, insoluble, the organic and inorganic salts of rare earth metal, described rare earth metal such as yttrium, bismuth, zirconium and tungsten and other.Equally, also can contain resistance amine light stabilizer and/or UV absorbers in the electrodeposition coating composition.

In the method for the invention, any curable electrodeposition coating composition of foregoing description can be at least a portion of various conductive substrates electrophoretic deposition, described conductive substrates comprises various metallic substrates.The metallic substrates that is suitable for can comprise ferrous metal or non-ferrous metal.The ferrous metal that is suitable for comprises iron, steel and alloy thereof.The non-limitative example of available steel class material comprises cold-rolled steel, zinc-plated (that is: zinc coating) steel, electrolytic zinc-coated steel sheet, stainless steel, pickling steel, GALVANNEAL

, GALVALUME

, and GALVAN

Steel and combination thereof that Zn-Al alloy applies.Available non-ferrous metal comprises material, aluminium, copper, zinc, magnesium and the alloy thereof that conductive carbon applies.When use such as the phosphate metal salting liquid of discussing below, the aqueous solution that contains at least a IIIB family or IVB family metal, organic phosphoric acid salting liquid, organic phospho acid salting liquid and in conjunction with etc. the solution preliminary treatment time, cold-rolled steel also can be suitable for.The composition of iron class and non-ferrous metal or compound also can use.

In a specific embodiment, method of the present invention further comprises by directly deposit the aqueous curable ground coating composition at least a portion of electrodeposited coating, form the step of priming coat on electrodeposited coating.Ground coating composition typically contains a kind of aqueous basecoat composition, as known in the art any in the aqueous basecoat composition.

As used in this article, composition is applied " in " or " directly " coatings " in " substrate or before at least a portion of the coating of formation " on ", mean said composition and be coated on substrate or the coating, and contact, do not have intervention coating therebetween with substrate or coating surface.

The aqueous basecoat composition that is used for method of the present invention typically contains (i) resin binder, contains a kind of polymer, and it typically contains active function groups; And (ii) color compositions, contain one or more and be scattered in pigment in the resin binder (i).Polymer can serve as the main film forming polymer of ground coating composition, and it can be used as color sizing vector, and perhaps the two all can.

The polymer (i) that contains first resin binder (or second resin binder as described below) can be selected from any in the various polymer as known in the art, for example be selected from acrylate copolymer, polyester polymers, polyether polyols with reduced unsaturation, polyether polymer, polyepoxide polymer, silicon-containing polymer, its mixture, with and those polymer of copolymer, described copolymer is " hydridization " resin binder for example, as the polymer by one or more ethylenically unsaturated monomers (as described below is any) copolymerization in the presence of polyester polymers (hereinafter having a detailed description).As used in this article, " silicon-containing polymer " means the polymer that contains one or more-SiO-unit on the main chain.Such silicon-based polymer can comprise hybridized polymer, as containing the polymer of organic polymer block and one or more-SiO-unit on those main chains.Resin binder (i) also contains curing agent usually, described curing agent have can with the functional group of the functional group reactions of film forming polymer.

Polymer can contain at least a active functional group group, and active functional group group is selected from the mixture of NCO, primary amine groups, secondary amine, amide groups, carbamate groups, urea groups, amido formate base, vinyl, unsaturated ester group, dimaleoyl imino, fumaric acid radical, anhydride group, hydroxyalkylamides group, epoxy radicals and these groups of hydroxyl, carboxyl, NCO, sealing.For example, the hydroxyl polymer-containing of Shi Yonging can comprise acrylic polyol, PEPA, polyurethane polyol, PPG, and composition thereof.

The hydroxyl that is suitable for and/or the acrylate copolymer of carboxyl can be prepared by polymerizable ethylenically unsaturated monomer, and normally (methyl) acrylic acid and or the copolymer of (methyl) acrylic acid hydroxy alkyl ester and one or more other polymerizable ethylenically unsaturated monomers, and vinyl aromatic compounds such as styrene, AMS and vinyltoluene, described ethylenically unsaturated monomer is as (methyl) acrylic acid Arrcostab of comprising (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate and hexyl acrylic acid 2-ethyl ester etc.As used in this article, terms such as " (methyl) acrylate " mean acrylate and methacrylate the two.

In a specific embodiment of the present invention, the polymerizable acrylic monomer thing can be by ethylenically unsaturated monomer, β hydroxy ester functional monomer preparation.These monomers can derive from the ethylenic unsaturated acid functional monomer, and as monocarboxylic acid, acrylic acid and do not participate in the epoxide of the polymerisation that free radical causes for example is with the reaction of unsaturated acid monomer.The example of this epoxide comprises glycidol ether and ester.The glycidol ether that is suitable for comprises the glycidol ether of pure and mild phenol, as butyl glycidyl ether, octyl glycidyl ether, phenyl glycidyl ether etc.The ethylene oxidic ester that is suitable for comprises to be buied by Shell Chemical Company with trade mark CARDURA E; And buy by Exxon Chemical Company with trade mark GLYDEXX-10 those.Perhaps, β hydroxy ester functional monomer can, epoxide-functional monomer unsaturated by olefinic, for example (methyl) glycidyl acrylate and allyl glycidyl ether, and saturated carboxylic acid, and as the saturated mono carboxylic acid, for example isostearic acid preparation.

Epoxy functionalized group can be by containing the monomer of ethylene oxide group, for example (methyl) glycidyl acrylate and allyl glycidyl ether, with other polymerizable ethylenically unsaturated monomer, as discussed above those, carry out copolymerization and be incorporated in the polymer by polymerizable ethylenically unsaturated monomer preparation.The preparation of this epoxy functional acrylic polymer is at US4, and there is detailed description on 001,156 3-6 hurdle, incorporates this paper into as a reference at this.

Carbamate-functional group can pass through, for example, the ethylenically unsaturated monomer of foregoing description with the carbamate-functional Arrcostab of carbamate-functional vinyl monomer such as methacrylic acid, carries out copolymerization and is incorporated in the polymer that is prepared by polymerizable ethylenically unsaturated monomer.The carbamate-functional Arrcostab that is suitable for can pass through, and for example, hydroxyalkyl carbamate as the product of ammonia and ethylene carbonate or propylene carbonate, with methacrylic anhydride, reacts and prepares.Other carbamate-functional vinyl monomer that is suitable for comprises, for example, and the product of hydroxyethyl meth acrylate, IPDI and hydroxypropyl carbamate; The perhaps product of hydroxypropyl methyl acrylate, IPDI and methyl alcohol.Other carbamate-functional vinyl monomer also can use, as the product of isocyanic acid (HNCO) and hydroxy-functional acrylic or methacrylic acid monomer such as hydroxy ethyl methacrylate, these are at US3, and 479, describe to some extent in 328, incorporate this paper into as a reference at this.Carbamate-functional group also can pass through, and hydroxy-functional acrylic polymer and low molecular weight amino alkyl formate such as methyl carbamate react and be incorporated in the acrylate copolymer.The carbamate groups of side chain also can be introduced in the acrylate copolymer by " carbamyl group-transfer " reaction; in " carbamyl group-transfer " reaction, the hydroxy-functional acrylic polymer reacts with the low molecular weight carbamate that derives from alcohol or glycol ethers.Carbamate groups and the oh group that produces the carbamate-functional acrylate copolymer and original alcohol or glycol ethers exchange.In addition, the hydroxy-functional acrylic polymer can with isocyanate reaction so that the carbamate groups of side chain to be provided.Similarly, the hydroxy-functional acrylic polymer can react so that the carbamate groups of side chain to be provided with urea.

Polymer by the polymerizable ethylenically unsaturated monomer preparation can be by solution polymerization technique as known in the art; at suitable catalyst such as organic peroxide or azo-compound, for example, benzoyl peroxide or N; N-azo two (isobutyronitrile) exists down, is prepared.Polymerisation can be carried out in the soluble organic solution of monomer by this area routine techniques.Perhaps, these polymer also can be by water-based emulsion as known in the art or the preparation of dispersion liquid polymerization technique.Ratio and reaction condition to reaction reagent are selected to obtain having the acrylate copolymer of required side chain functionalities.

Polyester polymers also can be used in the coating composition of the present invention as film forming polymer.The polyester polymers that is suitable for typically comprises the condensation product of polyhydroxy-alcohol and polybasic carboxylic acid.The polyhydroxy-alcohol that is suitable for can comprise ethylene glycol, neopentyl glycol, trimethylolpropane and pentaerythrite.The polybasic carboxylic acid that is suitable for can comprise adipic acid, 1,4-cyclohexyl dicarboxylic acid ester, and hexahydro-phthalic acid.Except the above-mentioned polybasic carboxylic acid of mentioning, the functional equivalents of acid such as they are present in acid anhydrides wherein, and perhaps Suan low-carbon alkyl such as methyl ester also can be used.In addition, a spot of monocarboxylic acid such as stearic acid also can use.Ratio and reaction condition to reaction reagent are selected to obtain having required side chain functionalities, that is, and and the polyester polymers of carboxyl or hydroxy functional group.

For example, acid anhydrides such as hexahydro phthalic anhydride that the polyester of hydroxyl group can be by dicarboxylic acids are with the molar ratio reaction preparation with 1:2 of glycol such as neopentyl glycol.Need to strengthen air from the dryness part, can use suitable drying oil fatty acid, comprise the oil that those are obtained by linseed oil, soya-bean oil, tall oil, dehydrated castor oil or tung oil.

The carbamate-functional polyester can be by at first forming and can preparing with the hydroxyalkyl carbamate of polyacid that is used to form polyester and polyol reaction.Perhaps, Mo Duan carbamate-functional also can be introduced in the polyester by isocyanic acid and hydroxyl-functional pet reaction.In addition, carbamate functional can also be introduced in the polyester by hydroxyl polyester and urea reaction.In addition, carbamate groups can be introduced in the polyester by the carbamoyl transfer reaction.The preparation of the polyester that contains amino-carbon acid esters functional group that is suitable for is at US5, and 593,733 the 2nd hurdles the 40th walk in the 4th hurdle the 9th row and describe to some extent, incorporate this paper into as a reference at this.

In a specific embodiment of the present invention, first ground coating composition can contain the hybrid resin that is less than 50wt%, is less than 40wt% and is less than 30wt%, described hybrid resin by as any above with those one or more polymerizable ethylenically unsaturated monomers of acrylate copolymer relevant discussion, as any above those one or more polyester polymers of just having described in the presence of copolymerization.

The polyether polyols with reduced unsaturation that contains terminal isocyanate group or oh group also can be used as polymer in coating composition of the present invention.The polyurethane of operable polyurethane polyol or NCO-end-blocking is those the polyalcohols by comprising polymer polyatomic alcohol and the polyurethane of PIC prepared in reaction.Also operable, contain terminal isocyanate or uncle and/or the polyureas of secondary amine group and be those the polyamines by comprising the polymer polyamines and the polyureas of PIC prepared in reaction.Adjust the equivalent proportion of hydroxyl/isocyanate or amine/isocyanates, and reaction condition is selected to obtain required end group.The example of the PIC that is suitable for is included in US4, and 046,729 the 5th hurdle the 26th walks to those of the 6th hurdle the 28th line description, incorporates this paper into as a reference at this.The example of the polyalcohol that is suitable for is included in US4, and 046,729 the 7th hurdle the 52nd walks to those of the 10th hurdle the 35th line description, incorporates this paper into as a reference at this.The example of the polyamines that is suitable for is included in US4, and 046,729 the 6th hurdle the 61st walks to the 7th hurdle the 32nd row and at US3,799,854 the 3rd hurdles the 13rd walk to those of the 50th line description, and the two all incorporates this paper into as a reference at this.

Carbamate-functional group can introduce in the polyether polyols with reduced unsaturation by PIC and the pet reaction that has hydroxyl functional and contain the side chain carbamate groups.Perhaps, polyurethane can be prepared as reaction reagent reaction independently by PIC and the pure and mild hydroxyalkyl carbamate of polyester polyols or isocyanic acid.The example of the PIC that is suitable for is an aromatic isocyanate, as 4, and 4 '-methyl diphenylene diisocyanate, 1,3-phenylene vulcabond and toluene di-isocyanate(TDI); And aliphatic polymeric isocyanate, as 1,4-tetramethylene and 1,6-hexamethylene diisocyanate.Cycloaliphatic diisocyanates, as 1,4-cyclohexyl diisocyanate and IPDI also can use.

The example of the PEPA that is suitable for comprises the polyalkylene ethoxylated polyhydric alcohol, as has following structural (IX) or (X) those:

Or

Wherein substituent R is hydrogen or the low-carbon alkyl that contains 1 to 5 carbon atom, comprises the mixing substituting group, and the value of n is typically in 2 to 6 scope, and the value of m is in 8 to 100 scope or higher.Exemplary polyalkylene ethoxylated polyhydric alcohol comprises poly-(oxygen tetramethylene) glycol, poly-(oxygen four ethylidene) glycol, poly-(oxygen-1,2-propylidene) glycol and poly-(oxygen-1,2-butylidene) glycol.

That can also use has, and by the PPG that the alkoxylation of various polyalcohols forms, described polyalcohol is, for example, glycol such as ethylene glycol, 1,6-hexylene glycol, bisphenol-A etc., or other more senior polyalcohol are as trimethylolpropane and pentaerythrite etc.The polyalcohol of operable higher functionality can pass through as indicated, for example, and such as the alkoxylation preparation of the compound of sucrose and sorbierite etc.A kind of alkoxylating method commonly used is polyalcohol and alkylene oxide, as expoxy propane or oxirane, reacts in the presence of acidic catalyst or base catalyst.The object lesson of polyethers comprise with trade name TERATHANE and TERACOL sell, by E.I.DU Pontde Nemours and Company, those that Inc. obtains.

Polyepoxide as following and curing agent associated description those, also can use.

In a specific embodiment of the present invention, resin binder (i) contains and has number-average molecular weight (Mn) is at least 2000 polyether polyols with reduced unsaturation.The number-average molecular weight of polyether polyols with reduced unsaturation can be in 2000 to 500,000 scope, typically in 3000 to 200,000 scope.

Film forming polymer is in the weight of total resin solid thing in the ground coating composition in the ground coating composition, exists with the amount of 2wt% at least, is at least 5wt% usually, typically is at least 10wt%.In addition, the polymer that has active function groups in the ground coating composition of the present invention can exist with the amount that is less than 80wt% in the weight of total resin solid thing in the coating composition, is generally to be less than 60wt%, typically is to be less than 50wt%.The amount of film forming polymer can be in the scope that these numerical value that comprise above-mentioned numerical value make up arbitrarily in the ground coating composition of the present invention.

As previously mentioned, except the polymer that contains functional group, the ground coating composition that is used for the inventive method can further contain at least a curing agent with the functional group of reacting with polymers functionality.

The active function groups that depends on film forming polymer, this curing agent can be selected from the mixture of isocyanates, polyepoxide, polyacid, acid anhydrides, amine, polyalcohol and above-mentioned any material of amino resin, PIC, sealing.In a specific embodiment, this at least a curing agent is selected from amino resin and PIC.

The amino resin that can contain phenoplasts as the curing agent of the material of hydroxyl, carboxylic acid and amido-containing acid ester functional group, is known in the art.The amino resin that is suitable for, as, example as discussed above those, be that those skilled in the art are known.Aminoplast can be obtained by the condensation reaction of formaldehyde and amine or acid amides.The non-limitative example of amine or acid amides comprises melamine, urea or benzoguanamine.Also can use with the condensation product of other amine or acid amides; For example, the aldehyde condensate of glycoluril, it provides a kind of high fusion-crystallization product that can be used in the powdery paints.Though used aldehyde is generally formaldehyde, other aldehyde such as acetaldehyde, crotonaldehyde and benzaldehyde also can use.

Amino resin contains imino group and methylol, and to a certain extent, to the small part methylol by pure etherificate to change cure response (cure response).Any single hydroxyl alcohol may be used to this purpose, comprises methyl alcohol, ethanol, n-butanol, isobutanol and hexanol.

The non-limitative example of aminoplast comprise melamine-, urea-or benzoguanamine-formaldehyde condensation products, to a certain extent for monomer and with one or more alcohol that contain from 1 to 4 carbon atom to the small part etherificate.The non-limitative example of the amino resin that is suitable for can commercially availablely obtain, for example, from Cytec Industries, Inc., trade mark is

And from Solutia, Inc., trade mark is

In another specific embodiment of the present invention, curing agent contains polyisocyanate curing agent.As used in this article, term " PIC " means (or end-blocking) isocyanates and untight (gathering) isocyanates that comprises sealing.PIC can be aliphatic or aromatic poly-isocyanate, or the mixture of said two devices.Vulcabond also can use, although the PICs such as isocyanuric acid ester of higher PIC such as vulcabond also often use.Higher PIC also can be used in combination with vulcabond.Isocyanate prepolymer, for example, the product of PIC and polyalcohol also can be used.The mixture of polyisocyanate curing agent also can use.

If PIC is closed or end-blocking, any suitable aliphatic, cyclic aliphatic or aromatic series alkyl monocarbon alcohol known in the art can be as the end-capping reagents of PIC.Other end-capping reagent that is fit to comprises oxime and lactams.During use, in the time of in adding other component that forms coating composition, polyisocyanate curing agent is in the gross weight of the resin solid thing that exists in the composition, usually exist with the amount in the 0.5wt-65wt% scope, can exist with the amount in the 10wt-45wt% scope, and exist with the amount in the 15wt-40wt% scope usually.

Other curing agent that is suitable for comprises the isocyanate compound of sealing, as, for example, US5, the triamido formoxyl triaizine compounds of describing in 084,541 is incorporated this paper into as a reference at this.During use, in the time of in adding other component that forms coating composition, the polyisocyanate curing agent of sealing can exist with the amount in the 1wt-20wt% scope to exist up to the amount in the 20wt% scope in the gross weight of the resin solid thing that exists in the composition.

Acid anhydrides is as known in the art as the curing agent of hydroxy functional groups material, and can be used for ground coating composition of the present invention.The non-limitative example that is suitable for use as the acid anhydrides of the curing agent in the present composition comprises that per molecule has those of at least two carboxylic acid anhydride groups, derive from the monomer mixture that contains ethylenically unsaturated carboxylic acids acid anhydride and at least a vinyl comonomer, described vinyl comonomer such as styrene, AMS, vinyltoluene etc.The non-limitative example of suitable ethylenically unsaturated carboxylic acids acid anhydride comprises maleic anhydride, citraconic anhydride and itaconic anhydride.Perhaps, acid anhydrides can be the anhydride adduct of diene polymer such as the butadiene copolymer of maleinization polybutadiene or maleinization, for example, and butadiene/styrene copolymers.These and other suitable anhydride curing agent is at US4, and 798,746 the capable and US4 of the 10th hurdle 16-50 describes during 732,790 the 3rd hurdle 41-57 is capable to some extent, and the two all incorporates this paper into as a reference at this.

Polyepoxide is as known in the art as the curing agent that contains the carboxylic acid functional material.The non-limitative example that is applicable to the polyepoxide in the present composition comprises the polyglycidyl ether of poly glycidyl ester (as the acrylic resin from GMA), polyhydric phenols and aliphatic alcohol, it can pass through polyhydric phenols, or aliphatic alcohol and prepare such as the etherification reaction of epihalohydrin in the presence of alkali of table chlorhydrin etc.These and other suitable polyepoxide is described during 681,811 the 5th hurdle 33-58 is capable to some extent at US4, incorporates this paper into as a reference at this.

The curing agent that is fit to that contains the epoxy-functional material contains the polyacid curing agent, as the acrylate copolymer that contains acid groups by the ethylenically unsaturated monomer that contains at least one carboxyl and not carboxylic at least one ethylenically unsaturated monomer preparation.This acid functionalized propylene acid polymer can have the acid number in the 30-150 scope.The polyester that contains acid functional group also can use.Above-mentioned polyacid curing agent is at US4, and 681,811 the 6th hurdle the 45th walks in the 9th hurdle the 54th row and further describes, and incorporates this paper into as a reference at this.

The curing agent as containing isocyanate functional group's material that also is known in the art is a polyalcohol, that is, per molecule has the material of two or more oh groups, and when component (b) was polyalcohol, (b) was different with component.The non-limitative example that is applicable to this class material in the present composition comprises the polyalkylene ethoxylated polyhydric alcohol, comprises thioether; PEPA comprises the polyhydroxy polycarboxylic esteramides; And hydroxyl polycaprolactone and hydroxy acryl acid copolymer.Can also with the PPG that is formed by various polyalcohol alkoxide arranged, used polyalcohol is for for example, glycol such as ethylene glycol, 1,6-hexylene glycol, bisphenol-A etc., perhaps higher polyol such as trimethylolpropane, pentaerythrite etc.PEPA also can use.These and other suitable polyalcohol curing agent is at US4, and 046,729 the 7th hurdle the 52nd walks to the 8th hurdle the 9th row, the 8th hurdle the 29th walks to the 9th hurdle the 66th row; And US3,919,315 the 2nd hurdle the 64th walks in the 3rd hurdle the 33rd row and describes to some extent, and the two all incorporates this paper into as a reference at this.

Polyamines also can be used as the curing agent that contains isocyanate functional group's material.The non-limitative example of the polyamine curing agent that is fit to comprises uncle or secondary diamine or polyamines, wherein is connected in group on the nitrogen-atoms and can is the aliphatic that saturated or undersaturated, aliphatic, alicyclic, aromatic series, aromatic series replaces, aromatic series and the heterocycle that aliphatic replaces.The suitable aliphatic and the limiting examples of alicyclic diamine comprise 1,2-ethylenediamine, 1,2-propane diamine, 1,8-octane diamines, IPD, propane-2,2-cyclo-hexylamine etc.The non-limitative example of suitable aromatic diamine comprises phenylenediamine and toluenediamine, for example, and ortho-phenylene diamine and right-toluenediamine.These and other suitable polyamines is at US4, and 046,729 the 6th hurdle the 61st walks in the 7th hurdle the 26th row and describes to some extent, incorporates this paper into as a reference at this.

If desired, can use suitable curing agent mixture.What should be mentioned in that is that ground coating composition can be made into the one-component composition, and wherein, those curing agent as described above such as the isocyanate compound of amino resin and/or sealing mix with the component of other composition.One-component composition as prescription can be stored stable.Perhaps, composition can be made into two component compositions, and for example, wherein, aforesaid polyisocyanate curing agent can be added in the mixture of preformed other composition component before applying.Preformed mixture can contain curing agent, the amino resin for example as described above and/or the isocyanate compound of sealing.

As mentioned above, used ground coating composition further contains (ii) color compositions in the inventive method.Color compositions (ii) can comprise filling material, and for example, talcum and calcium carbonate, color strengthen pigment, for example, and inorganic pigment such as titanium dioxide, red or black iron oxide, chromium oxide, plumbous chromate and carbon black, and/or organic pigment such as phthalocyanine blue and phthalocyanine green; And effect enhancing pigment, for example, metallic pigments such as flake aluminum, sheet of copper or bronze, and the pigments, mica of metal oxide-coated.Used ground coating composition can contain one or more filling materials in any the inventive method, color strengthens pigment and/or effect strengthens pigment and combination thereof.

In another specific embodiment of the present invention, used ground coating composition further contains the aqueous dispersion of polymer particles in the inventive method, typically contains crosslinked polymer particles.This crosslinked particulate can pass through, for example, the preparation of non-aqueous dispersions method, it is the polymerization olefinic unsaturated comonomer mixture of cross-linking comonomer that this method is included at least a in the organic liquid, in organic liquid, but mixture is that the soluble polymer that obtains is insoluble.Usually, the polymer particles in the used ground coating composition of the inventive method can comprise that the olefinic unsaturated comonomer mixture of crosslinkable monomers is prepared by method as known in the art emulsion polymerisation in aqueous medium.The olefinic unsaturated comonomer can be in polymerization in the presence of the polymer, and described polymer typically is hydrophobic polymer, for example hydrophobic acrylic, polyester and/or polyether polyols with reduced unsaturation." crosslinkable monomers " means the polymerizable olefinic monomer that has at least two polymerizable olefinic unsaturated bonds in the molecule, perhaps, alternately, refers to have the combination of two kinds of different monomers of reacting to each other property group.The object lesson of crosslinkable monomers comprise two (methyl) acrylic acid glycol ester, two (methyl) acrylic acid hexylene glycol ester, three (methyl) acrylic acid trihydroxymethylpropanyl ester, divinylbenzene and epoxide-functional monomer as (methyl) glycidyl acrylate and carboxylic acid functional monomers as (methyl) acrylic acid combination.Polymer particles is suitable for but nonrestrictive example is at US5, those that describe in 071,904,4,728,545,4,539,363 and 4,403,003.

First and/or second ground coating composition that is suitable in the inventive method can contain the water-borne dispersions of one or more polymer particles, normally crosslinked polymer particles, consumption mostly is 75wt% most, mostly is 70wt% sometimes most, sometimes mostly be most 60wt%, mostly be 55wt% sometimes most.Ground coating composition can also contain the water-borne dispersions of one or more polymer particles, is generally crosslinked polymer particles consumption and is equal to or greater than 20wt%, is equal to or greater than 25wt% sometimes, is equal to or greater than 30wt% sometimes, is equal to or greater than 35wt% sometimes.The amount of the water-borne dispersions of the polymer particles that exists in the ground coating composition that the inventive method is suitable for can be between any degree of the above-mentioned explanation that comprises above-mentioned numerical value.

Except the component of above-mentioned explanation, used ground coating composition can contain various other nonessential components in any the inventive method.If desired, other resin material also can be included within aforementioned polymer, curing agent and the waterborne polymeric particulate and use together, as long as make the multi-layer composite coatings not influence of suffering damage property aspect physical property and appearance property that obtains.Similarly, ground coating composition can comprise the interpolation material, as, rheology control agent, hindered amine as light stabilizer and/or UV absorbers, catalyst, filler, surfactant and analog.

In case ground coating composition directly is coated at least a portion electrodeposited coating when forming priming coat thereon, priming coat not necessarily dewaters, typically by being heated uniform temperature and keeping one sufficiently long period to remove unnecessary solvent, for example, water, but be not sufficient to make priming coat to solidify.The dehydration of priming coat also can keep one section time enough that solvent is evaporated away from coating under environmental condition by the substrate with primary coat.Suitable dehydration conditions will depend on that concrete primary coat and top are coated with employed composition, and depend on ambient humidity, but generally speaking, just enough at 80 ℉ to following 1 to 5 minute dewatering time of 250 ℉ (20 ℃ to 121 ℃).If this section dewatering time is to combine in the place of hot dehydration conditions or with hot dehydration conditions to carry out, priming coat can expose one section 1 to 20 minutes time under environmental condition.

This method further contains passes through curable top coating combination formation top coat of deposition on priming coat, said composition is substantially free of pigment paste, directly is coated on the uncured priming coat of at least a portion (bumping in the wet coating wet).The top coating combination that is substantially free of pigment that is used for the arbitrary method of the present invention can comprise the composition of water-based paint compositions, solvent-based compositions and solid particulate form, i.e. powder coated coating composition.Arbitrary transparent or varnish paint composition well known in the art all is suitable for this purpose.The nonrestrictive example that is fit to is included in United States Patent(USP) Nos. 4,650,718,5,814,410,5,891,981 and WO98/14379 in the clear coat composition described.The concrete example that is not limited to this comprises TKU-1050AR, and ODCT8000 and those are with DIAMOND With

The composition that trade mark is bought, all come from PPGIndustries, Inc..

The coating composition meaning for " being substantially free of pigment " of here using is meant the coating composition that forms clear coat, as varnish.These compositions do not contain pigment or particle fully so that the optical property of the coating that obtains is not subjected to serious tying down.For the meaning of " transparent " that here use is that the BYK Haze index of solidified coating when the usefulness BYK/Haze Gloss instrument detecting is less than 50.

In case when at least a portion priming coat, forming top coat (being layer of varnish), the substrate of coating be placed in be enough to make top coat, priming coat and, not necessarily, under the condition that deposition layer solidifies simultaneously.In curing operation, solvent is removed away, and the filmogen of different coating takes place crosslinked separately.Can finish the curing of coating with any known curing, comprise the combination of heat energy method, infrared method, Ionized or actinic radiation or its any method.Generally, curing operation can carry out under the temperature of 475 ℉ (10 ℃ to 246 ℃) scope at 50 ℉, yet, can use lower or higher temperature to cause crosslinked mechanism if needed.Solidify as defined above.

In another embodiment, the present invention relates to a kind of method that is used in substrate, forming multi-layer composite coatings, this method comprises: be deposited on by first ground coating composition with aqueous curable and form first priming coat at least a portion substrate in substrate, not necessarily with the first priming coat drying, directly be deposited at least a portion first priming coat and on first priming coat, form second priming coat by second ground coating composition aqueous curable, second ground coating composition can be identical or different with first ground coating composition, not necessarily with the second priming coat drying, by on second priming coat that the curable top coating combination that is substantially free of pigment directly is deposited at least a portion and on second priming coat, form top coat; Top coat, second priming coat and first priming coat are solidified simultaneously.

In this specific embodiment, first ground coating composition can directly be coated to non metallic substrate or not get involved on the substrate surface of metallic substrates of electrodeposited coating.That is, first ground coating composition can directly be coated to metallic substrates (as mentioned above) " untreated metal " surface or be coated to through preliminary treatment or applied in advance on the metallic substrates of the welding primer coating composition application of electrodepositable coating composition (as previously mentioned with reference to).Also be interpreted as realizing this specific embodiment, first ground coating composition is applied " to the substrate of at least a portion ", and be not precluded within and apply before first ground coating composition, apply in advance and not necessarily solidify the suprabasil electrodepositable coating composition of at least a portion.

As previously mentioned, substrate also can comprise non metallic substrate, as, " elastomer " substrate.Suitable elastomeric substrate can comprise any thermoplasticity well known in the art or thermosetting synthetic material.The non-limitative example of suitable flexible elastomer base material comprises polyethylene, polypropylene, TPO (" TPO "), reaction injection molded polyurethane (" RIM ") and thermoplastic polyurethane (" TPU ").

The non-limitative example of thermosets as substrate related to the present invention comprises polyester, epoxides, phenolic aldehyde, as the polyurethane of " RIM " thermosets, and any above-mentioned mixture.The non-limitative example of the thermoplastic that is fit to comprises as polyethylene, polyacrylic TPO, polyamide, thermoplastic polyurethane, thermoplastic polyester, acrylate copolymer, polyvinyl, Merlon, acrylonitrile-butadiene-styrene (ABS) (" ABS ") copolymer, ethylene propylene diene terpolymers (" EPDM ") rubber, copolymer as nylon, and any above-mentioned mixture.

If needed, above mentioned elastomeric substrate can have adhesion promotor on substrate surface, can apply any various coating composition (comprising following described coating composition of the present invention) thereon.In order to promote the bonding of organic coating and these polymeric substrates, substrate can as the thick thin layer of 0.25mils (6.35 microns), or be passed through flame or corona pre-treatment with adhesion promoter layer or binder course preliminary treatment.

The suitable adhesion promotor that uses on polymeric substrates comprises as at United States Patent(USP) Nos. 4,997, and the chloridized polyolefin adhesion promotor of describing in 882,5,319,032 and 5,397,602 is incorporated herein by reference at this.Other available adhesion promotor is at United States Patent(USP) Nos. 6; 001; 469 (coating compositions that contain saturated polyhydroxylated polydiene polymers) with terminal hydroxy groups; 5; 863; 646 (coating compositions) and 5 with blend of saturated polyhydroxylated polydiene polymers and chloridized polyolefin; 135; 984 (coating compositions with adhesion promotion material; this material is by with chloridized polyolefin; maleic anhydride; the per unit molecule of acryloyl group or methacryl modification contains the hydroxylated polybutadiene of at least one acryloyl group or methacryloyl group; obtain with organic peroxide reaction) in have disclosedly, be incorporated herein by reference at this.

When substrate was used as the parts of maker motor-car (including, but are not limited to this, automobile, truck and tractor), they can make Any shape, and can be selected from above-mentioned metal of mentioning and/or non metallic substrate.The type species of car body assembly can comprise side mechanograph, dashboard, bumper, hood and be used for the decoration of automobile.

In arbitrary method of the present invention, second ground coating composition can be identical or different with first ground coating composition.Second ground coating composition comprises (i) second resinous binder compositions and (ii) is scattered in second color compositions of second resin binder.Second resinous binder compositions can be identical or different with first resinous binder compositions; Similarly, second color compositions can be identical or different with first color compositions.

Second resinous binder compositions can comprise and is selected from acrylate copolymer, polyester polymers, polyether polyols with reduced unsaturation, polyether polymer, polyepoxide polymer, silicon-containing polymer, its mixture and its copolymer, as those materials relevant of describing in detail previously with first resinous binder compositions, film forming polymer.In a specific embodiment of the present invention, first resinous binder compositions contains same or different polyether polyols with reduced unsaturation (any as described previously polyether polyols with reduced unsaturation) with second resinous binder compositions.In an alternative specific embodiment, first resinous binder compositions contains same or different polyether polyols with reduced unsaturation with second resinous binder compositions, wherein the degree of the polyether polyols with reduced unsaturation in first ground coating composition is less than or equal to the degree of the polyether polyols with reduced unsaturation that exists in second ground coating composition, and described degree is based on the total resin solid thing meter that exists in the ground coating composition.

As previously mentioned, in arbitrary method of using first and second ground coating compositions simultaneously of the present invention, second color compositions can be identical or different with first color compositions.Second color compositions can contain any filler pigments, hyperchromic pigment and/or the synergy pigment of describing in detail previously relevant with first color compositions.In a specific embodiment, second ground coating composition contains hyperchromic and/or synergy pigment.

In further embodiment, the present invention relates to a kind of method that is used on any metallic substrates described above, forming multi-layer composite coatings, this method comprises: by the curable electrodeposition coating composition of electro-deposition at least a portion substrate, for example above-described any electrodepositable coating composition forms electrodeposited coating in substrate; Not necessarily, the substrate that applies is heated to enough temperature and sufficiently long time of maintenance so that electrodeposited coating solidifies; Directly deposit to by first ground coating composition (any as described above ground coating composition) on the electrodeposited coating of at least a portion and on electrodeposited coating, form first priming coat aqueous curable, not necessarily, with the first priming coat drying; By direct second ground coating composition (any as described above ground coating composition) of deposition and the identical or different aqueous curable of first ground coating composition on first priming coat of at least a portion, on first priming coat, form second priming coat, not necessarily, with the second priming coat drying; By on second priming coat of at least a portion, directly depositing the curable top coating combination that is substantially free of pigment (any as described above varnish paint composition), on second priming coat, form top coat; Solidify top coat, second priming coat, first priming coat, not necessarily, while cured electrodeposition coating.

First and second bottom coating compositions, or for example only be used on the metallic substrates or directly on electrodeposited coating, form one deck priming coat part at ground coating composition, the pigment of composition and the ratio of adhesive, in solid content, in 0.1 to 4.0:1 scope, generally from 0.1 to 3.0:1, the typical case is to 2.0:1 from 0.1.Should be appreciated that the pigment of bottom coating composition and the ratio of adhesive can change according to different, the pigment type and/or the required color of composition in a big way.

Equally, the film thickness scope of first and second priming coats of curing (perhaps, alternatively, the special-purpose priming coat that is suitable for) is from 1 to 50 micron, and generally from 5 to 30 microns often is from 10 to 25 microns.Similarly, should be appreciated that the film thickness of cured base coating is according to difference and the primary coat color or painted can the variation of ground coating composition in a big way.

In the of the present invention arbitrary method that applies first and second ground coating compositions, first and second priming coats can be solid colours.Promptly, although in resin binder and/or color compositions, form different (forming difference) if exist, first and second priming coats are enough similar on color when solidifying, and the film thickness of second priming coat that can make curing under the appearance property that does not have a strong impact on multi-layer composite coatings is significantly less than first primer thickness of solidifying.

In another specific embodiment of the present invention, first priming coat of curing (perhaps, alternatively, the special-purpose priming coat that is suitable for) is that 15 microns, wavelength are to measure light under 400 nanometers to be transmitted as 5% or lower at thickness.In order to realize purpose of the present invention, the light percent transmission is to have FR Perkin-Elmer Lambda 9 scanning spectrophotometers of 150mm Lap Sphere by use to detect the film thickness scope of freely solidifying be that the light transmission of 14 to 16 microns bottom coating is measured.Use and ASTM E 903, be used to use the standard detecting method of day light absorption, reflection and the transmission of gamut material, the Perkin-Elmer UV WinLab software that is consistent carries out the collection of data.

In containing of the present invention arbitrary method of following consecutive steps, first ground coating composition can further contain a kind of composition that is scattered in second color compositions in second resin binder that contains, this consecutive steps is: any aforesaid first ground coating composition is coated in the substrate or, alternatively, directly be coated at least a portion electrodeposited coating, to form first priming coat thereon; Not necessarily, with the first priming coat drying; With any aforesaid second ground coating composition different, directly be coated on first priming coat to form second priming coat thereon with first ground coating composition.Containing the composition that is scattered in second color compositions in second resin binder can be before first ground coating composition be deposited in the substrate, perhaps, alternatively, directly be coated on the electrodeposited coating before, mix with first ground coating composition immediately.In this specific embodiment, should be appreciated that " containing the composition that is scattered in second color compositions in second resin binder " can comprise any second ground coating composition of forming fully that has, perhaps, alternatively, contain the pigment paste composition that is scattered in second color compositions in second resin binder, second resin binder contains the polymer just like the excipient that grinds.Should be appreciated that also that in this specific embodiment first priming coat can be formed by higher a kind of first ground coating composition of the ratio that contains first ground coating composition, said composition is sneaked into second ground coating composition of low ratio, and vice versa.

In addition, first and/or second ground coating composition can obtaining by the ground coating composition that will select strong mixing of component in a specific embodiment of the present invention.Further, being coated on the ground coating composition of insertion portion can be by obtaining strong mixing of first and second ground coating compositions.Suitable strong mixing apparatus and method be at United States Patent(USP) Nos. 6,291, is described in 018 and 6,296,706, at this it is incorporated herein by reference fully.

In another specific embodiment of the present invention, any aforesaid ground coating composition can be coated at least a portion substrate, perhaps, directly be coated on the electrodeposited coating that at least a portion forms previously (as previously mentioned), to form single priming coat thereon; Not necessarily, priming coat is dried but does not solidify; The top coating combination (any varnish paint composition of using as the front) that is substantially free of pigment directly is coated at least a portion priming coat to form transparent top coat thereon; With the substrate that applies insert be enough to make top coat, priming coat and, not necessarily, in the condition that deposition layer solidifies.In this specific embodiment, the top coating combination directly is coated on the priming coat in wet-bumping-wetting and applying.

Method of the present invention provides to be had excellent appearance and physical property, be particularly suitable for the multi-layer composite coatings that uses in the motor vehicle coating of for example automobile and truck.In a concrete embodiment, the flaking resistance of the multi-layer composite coatings that any method of here describing by the present invention forms is when detecting according to ASTM D 3170-01, and its scope is 4 to 10, is typically 6 to 10.

The invention still further relates to a kind of improved method that is used for forming multi-layer composite coatings in the motor vehicle substrate, this method comprises following consecutive steps:

(1) the motor vehicle conductive substrates is sent to the electro-deposition station that is positioned on the paint line;

(2) electrodeposition coating is carried out in the substrate of serving as charged electrode in circuit, this circuit comprises the counterelectrode of described electrode and oppositely charged, described electrode is dipped in a kind of water-based electrodepositable composition (as described above in the electrodepositable coating composition any), between described electrode, form by electric current, so that electrodepositable composition is deposited on the continuous basically electrodeposited coating film of formation in the substrate;

(3) substrate with the coating in the step (2) transmits by being positioned at the electrodeposited coating curing station on the paint line, with the electrodepositable composition on the cured substrate, forms electrodeposited coating thereon;

(5) direct primer coating surfacer coating composition at least a portion of electrodeposited coating is to form priming paint surfacer coating thereon;

(6) substrate with the coating in the step (5) transmits by being positioned at the priming paint surfacer curing station on the paint line, so that priming paint surfacer coating is solidified;

(8) at least a portion of priming paint surfacer coating, directly apply the aqueous basecoat composition, to form priming coat thereon;

(10) substrate with the coating in step (8) or the non-essential step (9) is sent to the varnish coated station that is positioned on the paint line;

(11) at least a portion of priming coat, directly apply the coating composition that is substantially free of pigment (transparent as described above or varnish paint composition in any), to form layer of varnish thereon; And

(12) substrate that applies in the step (11) is transmitted by being positioned at the top coat curing station on the paint line, to solidify this priming coat and layer of varnish simultaneously.Improvement comprises: the substrate of the coating in the step (3) directly is sent to the primary coat station that is positioned on the paint line, on at least a portion of electrodeposited coating directly wet successively bumping wet apply independent, composite water soluble ground coating composition (as described above in the ground coating composition any), optionally dry every layer of continuous ground coating composition of while, to form the multilayer priming coat thereon, and need not between electrodeposited coating and multilayer priming coat to insert priming paint surfacer coating, the substrate that applies is sent to the varnish coated station that is positioned on the paint line, on at least a portion of multilayer priming coat, directly apply the coating composition that is substantially free of pigment (in for example aforementioned varnish paint composition any), to form layer of varnish thereon, and the top that the substrate that applies is transmitted by being positioned on the curing production line is coated with curing station, so that multilayer priming coat and layer of varnish solidify simultaneously.

The invention still further relates to the paint line that contains the electrodeposition coating zone, described electrodeposition coating zone comprises at least one electrophoresis tank.Primary coat is the zone that is positioned at electrodeposition coating downstream, zone and is adjacent to the electrodeposition coating zone, and insertion station, the first primary coat station and the second primary coat station are contained in the primary coat zone.The top is coated with the zone and is positioned at the downstream in primary coat zone and is adjacent to the primary coat zone.

The following examples are to illustrate of the present invention, and still, they can not be considered to the restriction to details of the present invention.Except as otherwise noted, all umbers below in embodiment and the whole specification and percentage are all by weight.

Embodiment

Following embodiment for example understands method of the present invention.Embodiment A has been described the preparation of first ground coating composition of medium grey.Control methods embodiment 1 has described the traditional silver metal ground coating composition of (with two-layer) coating on the priming paint that the electro-deposition of solidifying applies, and applies transparent coating composition subsequently.Method embodiment 2 has described method of the present invention, and wherein first ground coating composition of embodiment A is coated on the priming paint that the electro-deposition of curing applies, and applies traditional silver metal priming coat subsequently and then applies transparent coating composition.Embodiment B has been described the preparation of the ground coating composition similar to the preparation of embodiment A to embodiment E, but the amount difference of waterborne polyurethane resin.

Embodiment A

This embodiment has described and has been suitable as the preparation of first ground coating composition with the medium grey ground coating composition that forms first priming coat in the method for the invention.First ground coating composition is prepared by following component is mixed under gentle agitation.

Component:	Gross weight (gram)
Component:	Gross weight (gram)	N-butoxy propyl alcohol	15.00
The 1-octanol	5.00	N-butoxy propyl alcohol	15.00
The 1-octanol	5.00	CYMEL 327 ¹	22.22
Phosphorylation epoxy resin ²	1.63	CYMEL 327 ¹	22.22
Phosphorylation epoxy resin ²	1.63	TINUVIN 1130 ³	3.00
Deionized water	10.00	TINUVIN 1130 ³	3.00
Deionized water	10.00	Scentless petroleum solvent ⁴	8.00
Acrylic acid-polyester latex ⁵	41.07	Scentless petroleum solvent ⁴	8.00
Acrylic acid-polyester latex ⁵	41.07	Waterborne polyurethane resin ⁶	39.23
Titania slurry ⁷	148.76	Waterborne polyurethane resin ⁶	39.23
Titania slurry ⁷	148.76	The carbon black slurry ⁸	25.60
SETALUX 6802 AQ-24 ⁹	118.75	The carbon black slurry ⁸	25.60
SETALUX 6802 AQ-24 ⁹	118.75	Dimethylethanolamine ¹⁰	2.86
Deionized water	37.56	Dimethylethanolamine ¹⁰	2.86

¹From CYTEC Industries, the melamine-formaldehyde resin of the methoxy imino group official of Inc. energy.

²By with EPON 880 (from the polyglycidyl ether of the bisphenol-A of Shell Chemicals) and the phosphorylation epoxy resin of phosphoric acid with the ratio prepared in reaction of 83:17.

³From Ciba Specialty Chemicals, the ultraviolet light stabilizing agent of Inc..

⁴From Shell Oil and Chemical Co.

⁵Polyester-acrylic resin by 70.6% (52.8% 1,6-hexylene glycol, 27.2% isophthalic acid, 10% adipic acid, 10% be dissolved in maleic anhydride in 66.7% butyl acrylate and 33.3% hydroxypropyl methacrylate), the latex for preparing of 2.4% GDMA, 20% styrene, 4.7% hydroxypropyl methacrylate, 2.3% acrylic acid, solid content is 45% by weight.

⁶POLYMEG 2000 (coming from BASF) by 53.8%, 23.9% IPDI, 6.4% dihydromethyl propionic acid, 3.2% adipic dihydrazide, 12.7% polyester (54.2% EMPOL 1008 (coming from COGNIS-EMERY Group)), 29.8% 1,6-hexylene glycol, 16.1% isophthalic acid, solid content is 39% by weight.

⁷Be scattered in by 37.0% water-borne acrylic resin (8.5% hydroxyethyl acrylate, 18.0% butyl methacrylate, 30.0% styrene, 35.0% butyl acrylate, 8.5% acrylic acid, prepared solid content is 27.0%), 38.4% acrylic acid-polyester-urethane latex [3.0% GDMA, 11.0% methyl methacrylate, 24% butyl acrylate, 2% acrylic acid, with polyester-acrylic acid-carbamate (dimethyltrimethylene glycol of 60%, adipic acid, hydroxyethyl acrylate-butyl acrylate, 1, the 6-hexamethylene diisocyanate), prepared solid content is 43.5%], rutile titanium dioxide (coming from E.I.Dupont de Nemours and Company such as R900-39) in the resin compound of forming with 24.6% polypropylene glycol 425.The solid content of dispersion liquid is 69.5% by weight, and the ratio of pigment and adhesive is 6.71.

⁸Be scattered in MONARCH 1300 carbon black pigments (available from Cabot) in 100% water-borne acrylic resin.The solid content of dispersion liquid is 24.1% by weight, and the ratio of pigment and adhesive is 0.35.

⁹The water soluble acrylic acid rheology control agent that comes from Akzo Nobel.This material provides for 24% form with resin solid content.

¹⁰Be dissolved in the dimethylethanolamine of 50% in the deionized water.

First ground coating composition of embodiment A be prepared to provide with above method have that the weight solid content is 40.9%, the ratio of pigment and adhesive is 0.91, pH is 8.68, the viscosity of #4DIN cup is 35.6 seconds composition under the room temperature.

Control methods 1

The silver metal aqueous basecoat (coming from PPG such as NHWB-300146) of routine is sprayed to for twice on the steel base (with the cold-rolled steel B952P60DI of the PPG ED 5000 electro-deposition coating that comes from ACT) of coating.The priming coat thickness that obtains is 0.59mils (15 microns).After the coating, silver-colored priming coat was descended dry 10 minutes at 176 ℉ (80 ℃).On the silver-colored priming coat of drying, spray transparent coating composition (coming from PPG Industries, Inc. such as TKU-1050AR) then.The clear coat thickness that obtains is 2.06mils (52 microns).After applying transparent coating composition, the substrate of coating at room temperature stops 10 minutes blink, heats 30 minutes under the temperature of 285 ℉ (140 ℃) then.

Method 2

For method of the present invention is described, the steel base (with the cold-rolled steel B952 P60 DI of the PPG ED 5000 electro-deposition coating that comes from ACT) that the medium grey ground coating composition of embodiment A is once sprayed to coating goes up so that 0.61mils to be provided the thickness of (15 microns).The substrate that applies at room temperature stops the blink in 90 seconds.Spray once conventional silver metal aqueous basecoat (coming from PPG such as NHWB-300146) then.The silver-colored priming coat thickness that obtains is 0.35mils (9 microns).After the coating, silver-colored priming coat was descended dry 10 minutes at 176 ℉ (80 ℃).On the silver-colored priming coat of drying, spray transparent coating composition (coming from PPG Industries, Inc. such as TKU-1050AR) then.The clear coat thickness that obtains is 1.97mils (50 microns).After applying clear coating composition, the substrate of coating at room temperature stops 10 minutes blink, heats 30 minutes under the temperature of 285 ℉ (140 ℃) then.

Multi-layer composite coatings by method for preparing detects by the following method.The 20 ° of gloss meters of NOVO GLOSS statistics that use GARDCO to produce detect 20 ° of bright lusters of the multi-layer composite coatings that obtains.The gloss result is with the numeric representation of 0 to 100 scope, and the high more expression gloss of numerical value is high more.

Use is decided Dorigon image definition (Dorigon Distinctness of Image) (" DOI ") by the DORIGON II instrumentation that Hunter Lab produces.The high more expression of numerical value DOI is good more.Long wave and shortwave value are coating surfaces, that is: surface configuration, smoothness measures.The BYK ripple scan values of listing below is to use BYK-Gardner ripple scanning meter to detect.The low more presentation surface of numerical value is smooth more.

Film hardness uses the Fischerscope H100 microhardness detection system of being produced by Fischer to detect.Use DIN 50359 standard methods to obtain detecting numerical value.Hardness number is with Newtons/mm ²Unit representation.The high more expression film of numerical value is hard more.Use is measured the aluminum slice orientation by the ALCOPE LMR-200 Laser Multiple Reflectometer that Alesco produces, and reflection changes with visual angle change.The high more expression aluminum slice orientation of " FF " value of report is good more.

Testing result is listed in the following table 1.

Table 1

^*: control methods.

Above the method for the data declaration formation multi-layer composite coatings of the present invention listed in the table 1 provide and had the multi-layer composite coatings that equates or improved the aluminum slice orientation at least.

The transmittance of two multi-layer composite coatings separately that formed by control methods 1 and method of the present invention (method 2) compares by following method.Use method separately to prepare free film (not having steel/electro-deposition coated substrate).Application system (as following description) is coated in the TEDLAR substrate (the Electrical Insulation Suppliers ofAtlanta that comes from Georgia).Peel off free film from the TEDLAR substrate then, and measure the light percent transmission by free film.Use with ASTM E 903-82 " is used to use the standard detecting method of day light absorption, reflection and the transmission of gamut material " and is consistent and have the mensuration that the FR Perkin Elmer of 150mmLabsphere Lambda 9 spectrophotometer meters carry out the percent transmission data.Use Perkin-Elmer UVWinLab software to carry out the collection of data.

Use the free film of control methods 1 preparation to contain the NHWB-300146 silver metal priming coat of 0.59mils (15 microns) and the TKU-1050AR clear coat of 2.0mils (51 microns).The free film of using method 2 preparations contains the ground coating composition of the embodiment A of 0.61mils (15 microns), the NHWB-300146 silver metal priming coat of 0.35mils (9 microns) and the TKU-1050AR clear coat of 1.98mils (50 microns).Priming coat and clear coating composition generally apply and operate according to described above.The light percent transmission of each multiple coating system that measures under different wave length can find in following table 2.

Table 2

Transmitance under different wave length (nanometer) can %

Wavelength (nm)	300	350	400	450	500
Wavelength (nm)	300	350	400	450	500	Method 1 ^*	0	0	2.03	3.01	3.06
Method 2	0	0	0	0	0	Method 1 ^*	0	0	2.03	3.01	3.06

^*Contrast

Above in the table 2 listed data declaration use the multi-layer composite coatings of the inventive method preparation under the wavelength of all evaluations, all to show 0% transmitance energy, but in 400 to 500 nanometer wavelength range, show transmittance with the composite coating of control methods preparation.It will be appreciated by those skilled in the art that, low light transmission percentage can be relevant with the outside durability that improves, because the light that arrives at below the coating of multiple coating system is less,, thereby cause the coating degraded that produces as photooxidation as the relatively poor electrodeposited coating of durability.

Embodiment B-E

Following Embodiment B has been described the preparation of the medium grey ground coating composition of the polyurethane resin that contains different amounts to E.The composition of Embodiment B contains the polyurethane with solid weight meter 3.1%; The composition of Embodiment C contains the polyurethane with solid weight meter 10.6%; The composition of embodiment D contains the polyurethane with solid weight meter 18.1%; The composition of embodiment E contains the polyurethane with solid weight meter 33.1%.Each ground coating composition is prepared by concrete component is mixed under gentle agitation.

Embodiment B

Component:	Gross weight (gram)
Component:	Gross weight (gram)	N-butoxy propyl alcohol	15.00
The 1-octanol	5.00	N-butoxy propyl alcohol	15.00
The 1-octanol	5.00	CYMEL 327	22.22
The phosphorylation epoxy resin of embodiment A	1.63	CYMEL 327	22.22
The phosphorylation epoxy resin of embodiment A	1.63	TINUVIN 1130	3.00
The scentless petroleum solvent of embodiment A	8.00	TINUVIN 1130	3.00
The scentless petroleum solvent of embodiment A	8.00	Acrylic acid-the polyester latex of embodiment A	74.53
The polyurethane resin of embodiment A	0	Acrylic acid-the polyester latex of embodiment A	74.53
The polyurethane resin of embodiment A	0	The titania slurry of embodiment A	148.76
The carbon black slurry of embodiment A	25.60	The titania slurry of embodiment A	148.76
The carbon black slurry of embodiment A	25.60	SETALUX 6802 AQ-24	118.75
The dimethylethanolamine of embodiment A	3.46	SETALUX 6802 AQ-24	118.75
The dimethylethanolamine of embodiment A	3.46	Deionized water	63.51

The weight solid content of the ground coating composition of the Embodiment B for preparing is 39.96%; The ratio of pigment and adhesive is 0.92; PH is 8.69; The viscosity of #4DIN cup is 34.6 seconds under the room temperature.

Embodiment C

Component:	Gross weight (gram)
Component:	Gross weight (gram)	N-butoxy propyl alcohol	15.00
The 1-octanol	5.00	N-butoxy propyl alcohol	15.00
The 1-octanol	5.00	CYMEL 327	22.22
The phosphorylation epoxy resin of embodiment A	1.63	CYMEL 327	22.22
The phosphorylation epoxy resin of embodiment A	1.63	TINUVIN 1130	3.00
The scentless petroleum solvent of embodiment A	8.00	TINUVIN 1130	3.00
The scentless petroleum solvent of embodiment A	8.00	Acrylic acid-the polyester latex of embodiment A	57.87
The polyurethane resin of embodiment A	19.23	Acrylic acid-the polyester latex of embodiment A	57.87
The polyurethane resin of embodiment A	19.23	The titania slurry of embodiment A	148.76
The carbon black slurry of embodiment A	25.60	The titania slurry of embodiment A	148.76
The carbon black slurry of embodiment A	25.60	SETALUX 6802 AQ-24	118.75
The dimethylethanolamine of embodiment A	3.32	SETALUX 6802 AQ-24	118.75
The dimethylethanolamine of embodiment A	3.32	Deionized water	62.85

The weight solid content of the ground coating composition of the Embodiment C for preparing is 39.82%; The ratio of pigment and adhesive is 0.92; PH is 8.70; The viscosity of #4DIN cup is 33.5 seconds.

Embodiment D

Component:	Gross weight (gram)
Component:	Gross weight (gram)	N-butoxy propyl alcohol	15.00
The 1-octanol	5.00	N-butoxy propyl alcohol	15.00
The 1-octanol	5.00	CYMEL 327	22.22
The phosphorylation epoxy resin of embodiment A	1.63	CYMEL 327	22.22
The phosphorylation epoxy resin of embodiment A	1.63	TINUVIN 1130	3.00
The scentless petroleum solvent of embodiment A	8.00	TINUVIN 1130	3.00
The scentless petroleum solvent of embodiment A	8.00	Acrylic acid-the polyester latex of embodiment A	41.20
The polyurethane resin of embodiment A	38.46	Acrylic acid-the polyester latex of embodiment A	41.20
The polyurethane resin of embodiment A	38.46	The titania slurry of embodiment A	148.76
The carbon black slurry of embodiment A	25.60	The titania slurry of embodiment A	148.76
The carbon black slurry of embodiment A	25.60	SETALUX 6802 AQ-24	118.75
The dimethylethanolamine of embodiment A	3.05	SETALUX 6802 AQ-24	118.75
The dimethylethanolamine of embodiment A	3.05	Deionized water	66.03

The weight solid content of the ground coating composition of the embodiment D for preparing is 39.38%; The ratio of pigment and adhesive is 0.92; PH is 8.71; The viscosity of #4DIN cup is 32.6 seconds.

Embodiment E

Component:	Gross weight (gram)
Component:	Gross weight (gram)	N-butoxy propyl alcohol	15.00
The 1-octanol	5.00	N-butoxy propyl alcohol	15.00
The 1-octanol	5.00	CYMEL 327	22.22
The phosphorylation epoxy resin of embodiment A	1.63	CYMEL 327	22.22
The phosphorylation epoxy resin of embodiment A	1.63	TINUVIN 1130	3.00
The scentless petroleum solvent of embodiment A	8.00	TINUVIN 1130	3.00
The scentless petroleum solvent of embodiment A	8.00	Acrylic acid-the polyester latex of embodiment A	7.87
The polyurethane resin of embodiment A	76.92	Acrylic acid-the polyester latex of embodiment A	7.87
The polyurethane resin of embodiment A	76.92	The titania slurry of embodiment A	148.76
The carbon black slurry of embodiment A	25.60	The titania slurry of embodiment A	148.76
The carbon black slurry of embodiment A	25.60	SETALUX 6802 AQ-24	118.75
The dimethylethanolamine of embodiment A	2.31	SETALUX 6802 AQ-24	118.75
The dimethylethanolamine of embodiment A	2.31	Deionized water	82.94

The weight solid content of the ground coating composition of the embodiment E for preparing is 37.76%; The ratio of pigment and adhesive is 0.92; PH is 8.67; The viscosity of #4DIN cup is 26.0 seconds.

Below the listed data representation ground coating composition prepared laminated coating measured physical property of top described Embodiment B of serving as reasons in the table 2 to E.The outward appearance that coating showed of all using method 2 preparations can be identical with the coating of using standard method 3 to make with cutting resistance.

Table 2

^aThe cold-rolled steel C710C18DI that applies with PPG ED 5000 electro-deposition that becomes that ACT provides except substrate and come from PPG Industries, outside the 1177225A ash color bottom paint surfacer of Inc., method #3 is consistent with method #1.

^bUse is by ERICHSEN GMBH ﹠amp; The Stone Hammer Blow TestingInstrument Model 508 that CO KG produces carries out cutting test.Steel bead in 500 gram fractures under the 2Bar pressure is used twice on each breadboard.Use is derived from the visual evaluation grade of DIN 55996-1 with the evaluation test plate.The Kennwert opinion rating is from 0.5 to 5, and the low more expression cutting resistance of numerical value can be good more.

Those skilled in the art can understand fully, are not departing under the wide in range notion of the present invention and can change the above-described specific embodiment.Therefore, be appreciated that the present invention is not limited to disclosed concrete embodiment, but as additional claims limited, cover variation within the spirit and scope of the present invention.

Claims

1. method that in substrate, forms multi-layer composite coatings, this method comprises:

Not necessarily, the substrate that applies is heated to uniform temperature and keeps certain sufficiently long time with the cured electrodeposition coating;

By at least a portion of electrodeposited coating, directly depositing the aqueous curable ground coating composition of the water-borne dispersions that contains polymer particles, on electrodeposited coating, form priming coat;

Not necessarily, dry this priming coat;

2. the method for claim 1 is characterized in that the film thickness after priming coat solidifies is the 1-50 micron.

3. the method for claim 1 is characterized in that ground coating composition comprises:

(i) contain the resinous binder compositions of polymer, polymer be selected from acrylate copolymer, polyester polymers, polyether polyols with reduced unsaturation, polyether polymer, polyepoxide polymer, silicon-containing polymer, its mixture, with and copolymer; And

(ii) be scattered in the color compositions that contains one or more colors enhancings and/or effect enhancing pigment in the resin binder (i).

4. method as claimed in claim 3, the ratio that it is characterized in that the pigment of ground coating composition and adhesive is less than 4.0.

5. the method for claim 1 is characterized in that electrodepositable coating composition contains the resin phase that is scattered in the aqueous medium, and described resin comprises mutually:

(1) resin one or more the non-gels of electrodepositable on negative electrode, that contain active hydrogen, cation amine salt group, described resin contain to derive from and have the cation amine salt group that following array structure (I) or side (II) are amino and/or end is amino

(I)

—NHR

Or

Wherein R represents H or C ₁To C ₁₈Alkyl;

R ¹, R ², R ³And R ⁴Identical or different, represent H or C respectively independently ₁To C ₄Alkyl; And

X and Y can be identical or different, represent hydroxyl or amino respectively independently; And

(2) one or more partially enclosed at least aliphatic polymeric isocyanate curing agent.

6. method as claimed in claim 5, the cation amine salt group that it is characterized in that resin (1) derives from have said structure one or more side amino of (II), therefore when electrodepositable coating composition during, have at least two electron withdraw groups to be bonded on the β position with respect to all nitrogen-atoms basically by electro-deposition and curing.

7. method as claimed in claim 6 is characterized in that electron withdraw group is selected from ester group, urea groups, carbamate groups and combination thereof.

8. method as claimed in claim 6, it is characterized in that resin (1) contains the cation amine salt group that derives from least a compound that is selected from the following material: ammonia, methylamine, diethanol amine, diisopropanolamine (DIPA), N-hydroxyethyl-ethylenediamine, diethylenetriamines, and composition thereof.

9. method as claimed in claim 6, the resin (1) that it is characterized in that containing active hydrogen, cation amine salt group contain be selected from polyepoxide polymer, acrylate copolymer, polyether polyols with reduced unsaturation, polyester polymers, its mixture, with and copolymer at least a polymer.

10. method as claimed in claim 6 is characterized in that the resin (1) that contains active hydrogen, cation amine salt group contains polyepoxide polymer and acrylate copolymer.

11. method as claimed in claim 5, it is characterized in that aliphatic polymeric isocyanate (2) is selected from 1 by at least a, 2-alkane diol, 1,3-alkane diol, benzylalcohol, allyl alcohol, caprolactam, dialkylamine, and composition thereof sealer partially enclosed at least.

12. the method for claim 1 is characterized in that the anti-slabbing grade of the multi-layer composite coatings measured according to ASTM D 3170-01 is 4-10.

13. a method that forms multi-layer composite coatings in substrate, this method comprises:

By at least a portion of electrodeposited coating, directly depositing aqueous curable first ground coating composition of the water-borne dispersions that contains polymer particles, on electrodeposited coating, form first priming coat;

Not necessarily, dry this first priming coat;

Not necessarily, dry this second priming coat;

14. method as claimed in claim 13 is characterized in that first ground coating composition further contains:

(i) first resin binder, and

(ii) be scattered in first color compositions that contains one or more pigment in first resin binder.

15. method as claimed in claim 14, it is characterized in that first resin binder contain be selected from acrylate copolymer, polyester polymers, polyether polyols with reduced unsaturation, polyether polymer, polyepoxide polymer, silicon-containing polymer, its mixture, with and the polymer of copolymer.

16. method as claimed in claim 14 is characterized in that first resin binder contains polyether polyols with reduced unsaturation.

17. method as claimed in claim 16 is characterized in that first color compositions contains one or more hyperchromic and/or synergy pigment.

18. method as claimed in claim 14, the ratio that it is characterized in that the pigment of first ground coating composition and adhesive is less than 4.0.

19. method as claimed in claim 14 is characterized in that the pigment of first ground coating composition and the ratio of adhesive are 0.1-4.0:1.

20. method as claimed in claim 14 is characterized in that first ground coating composition further contains the water-borne dispersions of polymer particles.

21. method as claimed in claim 14 is characterized in that the water-borne dispersions of described polymer particles contains crosslinked polymer particles.

22. method as claimed in claim 13 is characterized in that the thickness of first priming coat curing caudacoria is the 1-50 micron.

23. method as claimed in claim 13, the ratio that it is characterized in that the pigment of first ground coating composition and adhesive is less than 4.0.

24. method as claimed in claim 13 is characterized in that second ground coating composition is different from first ground coating composition.

25. method as claimed in claim 24 is characterized in that second ground coating composition contains:

(ii) be scattered in second color compositions identical or different in second resin binder with first color compositions.

26. method as claimed in claim 25, it is characterized in that first and second resin binders are identical or different, and contain respectively be selected from acrylate copolymer, polyester polymers, polyether polyols with reduced unsaturation, polyether polymer, polyepoxide polymer, silicon-containing polymer, its mixture, with and the polymer of copolymer.

27. method as claimed in claim 26 is characterized in that first and second resin binders contain identical or different polyether polyols with reduced unsaturation.

28. method as claimed in claim 27 is characterized in that it is 2,000 to 500,000 polyether polyols with reduced unsaturation that first resin binder contains number-average molecular weight.

29. method as claimed in claim 27 is characterized in that the content of the polyurethane in first ground coating composition is less than or equal to the content of the polyurethane in second ground coating composition, wherein content is in the total resin solid thing in the composition.

30. method as claimed in claim 25 is characterized in that second color compositions contains one or more and is scattered in hyperchromic and/or synergy pigment in second resin binder.

31. method as claimed in claim 25 is characterized in that first ground coating composition further contains a kind of composition, described composition contains second color compositions that is scattered in second resin binder.

32. method as claimed in claim 31 is characterized in that first and second priming coats are color coordinations.

33. method as claimed in claim 13 is characterized in that the thickness of second priming coat curing caudacoria is 50 microns or littler.

34. method as claimed in claim 13 is characterized in that electrodepositable coating composition contains the electrodepositable coating composition that comprises the resin phase that is scattered in the aqueous medium, described resin comprises mutually:

(I)

—NHR

Or

Wherein R represents H or C ₁To C ₁₈Alkyl;

35. method as claimed in claim 34, the cation amine salt group that it is characterized in that resin (1) derives from have said structure one or more side amino of (II), therefore when electrodepositable coating composition during, have at least two electron withdraw groups to be bonded on the β position with respect to all nitrogen-atoms basically by electro-deposition and curing.

36. the described method of claim 35 is characterized in that electron withdraw group is selected from ester group, urea groups, carbamate groups and combination thereof.

37. method as claimed in claim 35, it is characterized in that resin (1) contains the cation amine salt group that derives from least a compound that is selected from the following material: ammonia, methylamine, diethanol amine, diisopropanolamine (DIPA), N-hydroxyethyl-ethylenediamine, diethylenetriamines, and composition thereof.

38. method as claimed in claim 35, the resin (1) that it is characterized in that containing active hydrogen, cation amine salt group contain be selected from polyepoxide polymer, acrylate copolymer, polyether polyols with reduced unsaturation, polyester polymers, its mixture, with and copolymer at least a polymer.

39. method as claimed in claim 35 is characterized in that the resin (1) that contains active hydrogen, cation amine salt group contains polyepoxide polymer and acrylate copolymer.

40. method as claimed in claim 34, it is characterized in that aliphatic polymeric isocyanate (2) is selected from 1 by at least a, 2-alkane diol, 1,3-alkane diol, benzylalcohol, allyl alcohol, caprolactam, dialkylamine, and composition thereof sealer partially enclosed at least.

41. the method for claim 1 is characterized in that the anti-slabbing grade of the multi-layer composite coatings measured according to ASTM D 3170-01 is 6-1010.

42. method as claimed in claim 13 is characterized in that the anti-slabbing grade of the multi-layer composite coatings measured according to ASTM D 3170-01 is 4-10.

43. a method that forms multi-layer composite coatings in substrate, this method comprises:

First ground coating composition contains:

(i) water-borne dispersions of polymer particles,

(ii) first resin binder, and

(iii) be scattered in first color compositions that contains one or more pigment in first resin binder;

Not necessarily, dry this first priming coat;

Second ground coating composition contains:

Not necessarily, dry this second priming coat;

Wherein, the ratio of the pigment of second ground coating composition and adhesive is 0.1-4.0:1.

44. a method that forms multi-layer composite coatings in substrate, this method comprises:

First ground coating composition contains:

(i) water-borne dispersions of polymer particles,

(ii) first resin binder, and

Not necessarily, dry this first priming coat;

Second ground coating composition contains:

Not necessarily, dry this second priming coat;

Solidify this top coat, second priming coat, first priming coat simultaneously, and, not necessarily, while cured primer coating, and,

Wherein, the back light transmission that is 15 microns at film thickness, measures in 400 nanometers of first priming coat curing is 5% or littler.

45. a method that forms multi-layer composite coatings in substrate, this method comprises:

First ground coating composition contains:

(i) water-borne dispersions of polymer particles,

(ii) first resin binder, and

Not necessarily, dry this first priming coat;

Second ground coating composition contains:

Not necessarily, dry this second priming coat;

Wherein, the ratio of the pigment of second ground coating composition and adhesive is 0.1-4.0: 1

Wherein, first resin binder and second resin binder all contain identical or different polyether polyols with reduced unsaturation,

Wherein, the light transmission that it is 15 microns at film thickness that first priming coat solidifies the back, measure in 400 nanometers is 5% or littler, and

Wherein, first ground coating composition further contains a kind of composition, said composition contains second color compositions that is scattered in second resin binder, and before first ground coating composition directly was deposited on the electrodeposited coating, described composition mixed with first ground coating composition.

46. a method that forms multi-layer composite coatings in substrate, this method comprises:

First ground coating composition contains:

(i) water-borne dispersions of polymer particles,

(ii) first resin binder, and

Not necessarily, dry this first priming coat;

Second ground coating composition contains:

Not necessarily, dry this second priming coat;

Wherein, first ground coating composition further contains a kind of composition, and said composition contains second color compositions that is scattered in second resin binder,

Wherein, first resin binder and second resin binder all contain identical or different polyether polyols with reduced unsaturation, the content of the described polyether polyols with reduced unsaturation in first ground coating composition is equal to or less than the content of the polyether polyols with reduced unsaturation in second ground coating composition, and wherein content is in the total resin solid thing in first and second ground coating compositions.

47. a method that forms multi-layer composite coatings in substrate, this method comprises:

Aqueous curable first ground coating composition that contains the polymer particles water-borne dispersions by deposition at least a portion of substrate need not to insert priming paint surfacer layer, forms first priming coat in substrate;

Not necessarily, dry this first priming coat;

Not necessarily, dry this second priming coat;

48. method as claimed in claim 47 is characterized in that substrate is a metallic substrates.

49. method as claimed in claim 48 is characterized in that substrate is a non metallic substrate.

50. method as claimed in claim 48 is characterized in that first ground coating composition is coated on to be coated in advance on the suprabasil weldable primer coating.

51. method as claimed in claim 50 is characterized in that forming the weldable primer coating by deposition weldable primer coating composition in substrate, the weldable primer coating composition contains:

(A) resin binder, contain:

(1) at least a polymer that contains functional group and

(2) at least a curing agent that has with the functional group of the functional group reactions of (1); And

(B) at least a conducting pigment that is scattered in the resin binder (A).

52. a method that applies composite coating in the vehicle substrate comprises the following steps:

(a) at least a portion of vehicle substrate, apply electrodeposited coating;

(b) provide the water-borne dispersions that contains first resin binder, polymer particles and the first aqueous basecoat composition of first color compositions;

(c) provide the second aqueous basecoat composition that contains second resin binder and second color compositions, second color compositions is different with first color compositions;

(d) second ground coating composition is coated on the insertion portion of the inside of vehicle substrate;

(e) first ground coating composition is coated on the electrodeposited coating;

(f) bumping wet directly be coated on first ground coating composition and drying-free first ground coating composition with second ground coating composition is wet, having the compound priming coat of first priming coat and second priming coat with formation;

(g) on compound priming coat, apply top coat; And

(h) compound priming coat of heating and top coat are to solidify this compound priming coat and top coat simultaneously.

53. method as claimed in claim 52 is characterized in that step (e) is included in the vehicle substrate to apply before first ground coating composition a part of second ground coating composition added in first ground coating composition to form with the pigment that changes first ground coating composition.

54. method as claimed in claim 52 is included on the electrodeposited coating and applies first and second ground coating compositions and need not to insert priming paint surfacer layer.

55. method as claimed in claim 52 comprises that revolving a glass coater by at least one applies first ground coating composition.

56. method as claimed in claim 52 comprises by at least one spray gun applicator applying second ground coating composition.

57. method as claimed in claim 52 is included in and applies first and second ground coating compositions cured electrodeposition coating before.

58. method as claimed in claim 52 comprises that heating electrodeposited coating and compound priming coat are with while cured electrodeposition coating and compound priming coat.

59. in the motor vehicle substrate, form in the process of multi-layer composite coatings, comprise following continuous step:

(1) the motor vehicle conductive substrates is sent to the electrodeposition coating station that is positioned on the paint line;

(11) at least a portion of priming coat, directly apply the coating composition that is substantially free of pigment, to form layer of varnish thereon; And

(12) substrate that applies in the step (11) is transmitted by being positioned at the top coat curing station on the paint line, to solidify this priming coat and layer of varnish simultaneously.

Improvement comprises that the substrate with the coating in the step (3) directly is sent to the primary coat station that is positioned on the paint line,

Directly wetly successively at least a portion of electrodeposited coating bumping wet independent, the composite water soluble ground coating composition that applies, wherein said aqueous basecoat composition comprises one of at least the water-borne dispersions of polymer particles, not necessarily dry every layer of continuous priming coat of while, to form the multilayer priming coat thereon, and need not between electrodeposited coating and multilayer priming coat to insert priming paint surfacer coating

The substrate that applies is sent to the varnish coated station that is positioned on the paint line,

On at least a portion of multilayer priming coat, directly apply the coating composition that is substantially free of pigment, forming layer of varnish thereon, and

The top that the substrate that applies is transmitted by being positioned on the curing production line is coated with curing station, so that multilayer priming coat and layer of varnish solidify simultaneously.

60. a paint line comprises:

The electrodeposition coating zone comprises at least one electrophoresis tank;

The primary coat zone, be positioned at the downstream in electrodeposition coating zone and close on the electrodeposition coating zone, the primary coat zone comprises inserts station, the first primary coat station and the second primary coat station, wherein the first primary coat station comprises that at least one revolves a glass coater, communicate with the first ground coating composition source flow that contains first resin binder and first color compositions, and described first ground coating composition comprises the water-borne dispersions of polymer particles; And

61. paint line as claimed in claim 60 is characterized in that inserting the upstream of erect-position in the first primary coat station, and the first primary coat erect-position is in the upstream at the second primary coat station.

62. paint line as claimed in claim 60, it is characterized in that the second primary coat station comprises at least one spray gun coater, communicate with the second ground coating composition source flow that contains second resin binder and second color compositions, second color compositions is different with first color compositions.

63. paint line as claimed in claim 62 is characterized in that inserting the coater that the station comprises that at least one communicates with the second coating composition source flow.

64. paint line as claimed in claim 62 is characterized in that inserting the mix source flow communication of standing with first and second ground coating compositions.

65. paint line as claimed in claim 60 is characterized in that the primary coat zone further comprises at least one drying oven.

66. paint line as claimed in claim 60 is characterized in that inserting the downstream of erect-position in the first primary coat station and/or the second primary coat station.

67. paint line as claimed in claim 60 is characterized in that not having drying device between the first and second primary coat stations.

68. a method that forms multi-layer composite coatings in substrate, this method comprises:

By at least a portion of electrodeposited coating, directly depositing aqueous curable first ground coating composition that contains the polymer particles water-borne dispersions, on electrodeposited coating, form first priming coat;

Not necessarily, dry this first priming coat;

Not necessarily, dry this second priming coat;

Wherein, first ground coating composition contains the water-borne dispersions by the polymer particles of the monomer mixture preparation that contains one or more monomers, and this monomer mixture contains one or more and has the monomer of the unsaturated point of two or more reactive olefinics and/or the combination with two kinds of different monomers of reacting to each other property group.

69. as the described method of claim 68, the amount of water-borne dispersions in first ground coating composition that it is characterized in that one or more polymer particles, in the resin solid thing gross weight in first ground coating composition, in the scope of 20wt% to 75wt%.

70. as the described method of claim 69, the amount of water-borne dispersions in first ground coating composition that it is characterized in that one or more polymer particles, in the resin solid thing gross weight in first ground coating composition, in the scope of 25wt% to 70wt%.

71. as the described method of claim 69, the amount of water-borne dispersions in first ground coating composition that it is characterized in that one or more polymer particles, in the resin solid thing gross weight in first ground coating composition, in the scope of 30wt% to 60wt%.

72. as the described method of claim 69, the amount of water-borne dispersions in first ground coating composition that it is characterized in that one or more polymer particles, in the resin solid thing gross weight in first ground coating composition, in the scope of 35wt% to 55wt%.

73. as the described method of claim 68, it is characterized in that first ground coating composition contains, in the resin solid thing gross weight in first ground coating composition, be less than one or more hybrid resin adhesives of 50wt% by one or more polymerizable ethylenically unsaturated monomers copolymerization in the presence of polyester polymers.

74. as the described method of claim 68, it is characterized in that first ground coating composition and second ground coating composition contain one or more polyurethane resins respectively, wherein the content of one or more polyurethane resins in first ground coating composition is less than or equal to the content of one or more polyurethane resins in second ground coating composition.

75. as the described method of claim 68, it is characterized in that first ground coating composition contains, in the resin solid thing gross weight in first ground coating composition, one or more hybrid resin adhesives that are less than 50wt% by one or more polymerizable ethylenically unsaturated monomers copolymerization in the presence of polyester polymers, and

First ground coating composition and second ground coating composition contain one or more polyurethane resins respectively, and the content of one or more polyurethane resins in first ground coating composition is less than or equal to the content of one or more polyurethane resins in second ground coating composition.