CA2013678A1 - Paint composites - Google Patents

Abstract

PAINT COMPOSITES
Abstract A paint composite article comprising a thermally deformable carrier film having an adhesive layer on one surface. A paint layer is positioned on the opposed side of the carrier film and a tiecoat is interposed between the carrier film and the paint layer to promote adhesion of the paint layer. The tiecoat is preferably a mixture of an acrylic polymer and polyurethane. The paint layer includes a pigmented basecoat layer adhered to the thermally deformable carrier film through the tiecoat layer and a transparent topcoat layer superimposed over the basecoat layer. The tiecoat may also include an aminoplast and an alkylbenzene.

Description

2 ~ J '~ $

PAINT COM~POSIT~S

Fleld of the Invention Thi~ invention relates to paint compo~ites which may be used to apply a coating to a substrate, e.g., to the surface of a component such as the exterior surface o~ an automobile body panel.
Back~round of the Invention Automotive body panels are traditionally made of sheet metal or plastic material painted with layers of pigmented paints.
The painting procedure for these panels reguires elaborate 20 facilities, and conseguently involves heavy expense~. For instance, a large area o$~floor space must be maintained in a clean room environment for the spraying of paint and for the baking and curing of such paint on the body panels. The paint may include both a pigmented basecoat and tran~parent clear coat. Moreover, 25 soIvent-based paint~ have come to be considered undesirable in recent ~; years due to environmental concerns. As a consequence, the evaporation of such solvents must be strictly controlled.
The present invention is concerned with a method of making paint composites for the painting of automobile body panels which may 30 permit elimination of the entire painting procedure presently utilized in automobile assembly plants.
A variety of paint composites often referred to as laminates have previously been described. Typically, such composites or laminates have included a paint layerJ an adhesive layer ad~acent 35 to the paint layer and a carrier film ad~acent to the paint layer.
The composite i9 applied to a substrate with the adhesive against the substrate's surface and the carrier layer on the exterior of the ~ - 2 ~

composite. Subsequently, the carrier layer may be generally removed or may remain as a protective layer. Patents utilizing such laminate arraneements include European Patent Application 230,364 and U.S.
Patents 3,640,791; 4,101,698; 4,275,a99; 4,330,352; and 4,451,522.

Summary of the Inventio~i Thie present invention rel~ites to a paint compo~ite ar~icle. Thie article comprlses:
ta) a thermally deformable carrier film having first and second ma~or surface~, (b) an adhesive superimpo8ed on the first surface of the thermally deformable carrier film, (c) an adhesion promoting tiecoat layer superimposed on the second surface of the carrier film, (d) a paint layer superimposed on said tiecoat layer.
Thie paint layer comprises (i) a pigmented basecoat adhered to the thermally deformable carrier film through said tiecoat layer; and - -(ii) a transparent topcoat layer superimposed on the basecoat layer.
The above-described paint composite can be applied to 20 automobile body panels. By the use of the pre~ent invention, prepainted carrier films can be applied to vehicle body panels 8uch that all the body panels mounted on an automobile will have the desired decorative effect.

Brief Descri~tion of the Drawin~s The present invention is further described with reference to the accompanying drawings in which:
FiBS 1-4 are various vertical cross sectional views, in fragment, showing various embodiments of paint compo~ite articles 30 described herein.

netailed Descri~tion Referring to Fig. 1, the paint composite ar~icle includes a carrier film 10. On one surface of the carrier film, there is an 35 adhesiive layer 12. Superimposed on the other surface of the carrier film there i9 a paint layer shown generally at numeral 14. The paint -~

2~3~ 7~

layer ~ made up of a pigmented layer 16 and a clear coat layer 18.
A temporary support film 20 may also be positioned beneath the adhe~ive layer.
Carrier film 10 can typically be a polymeric ilm, such as 5 polyurethane, a polye~ter, e.g., polyethylene terephthalate, or a blend of such polymeric materials. The carrier film ~hould preferably have a low enough Tg to allow for its deformatlon at application temperature and a high enough T8 to allow for using pain~
ma~eriAls in the composite. FurtherJ carr~er film 10 ~hould have a 10 high tensil~ ~trength and elongation to allow for stretching around corners and edges of a substrate such as an automobile body part.
Typically, the carrier film will have a th~cknes~ of 5 to 10 mils. A
suitable carrier film i8 that available from ~astman Kodak Company as PMB 10231.
The prepainted carrier film is generally applied and adhered to an automobile body part by a vacuum forming procedure involving the use of heat to render the film sufficiently pliable for application. One preferred means of carrying out this procedure i8 described in European Patent Application No. 251,561, filed June 16, 20 1987 and published July 1, 1988.
The adhesive material which i~ optionally applied to the surface of thermally deformed carrier film 10 opposite the paint layer can generally be an adhesive such a~ a pre~sure-sensitive adhe3ive or a heat-activated adhesive. The adhesive may be either 25 solvent or waterborne, preferably waterborne. The aahesive should provide good bond strength to the coated article under a ~ariety of environmental condition~. Adhesive layer 12 i8 ~enerally from about 1 to 6 mils, preferably from about 2 to 4 mils thick upon carrler film 10.
Preferred adhesive compositions for adherin8 the carrier film to the automobile part are based on aryli~ latex polymers prepared predominantIy from aliphatic acrylate monomer having pendant carbon chain lengths of from 3 to 5 carbon atoms with minor amountQ of a hydroxyalkyl acrylate monomer and acrylic acid. One 35 particularly prefered latex is prepared at about 55 percent solids in water from about 59 percent of isobutyl acrylate, 31 percent butyl _, ~ , . ., ~ ., .

~ ~ ~ 3 ~ 7 ~

acrylate, 7 percent me~hyl methacrylate and 1 percent each of styrene, hydroxypropyl acrylate and acrylic acld. The composition also con~ains a defoamer, fungicide, and a polyacrylate thickener.
Other conventional additives and filler~ can be utilized if desired.
The adhesive composition can be applied to the bottom surface o~ the carrier film by such convent~onal techniques as spray or roll coatlng. The adhesiv2 composition may be activated by the heat applied during the vacuum forming of t~e part.
The pigmented ba~ecoat layer 16 portion of the paint layer 10 14 can be ~ormed from ~olvent or aqueou~-ba~ed film-forming composition~ which generally include as an e~sential ingredient a thermoplastic polyurethane binder. ~uch a polyurethane can be prepared by reacting an organic polyi~ocyanate with an active hydrogen-containing material such as a polyol and/or a pslyamine to `~
15 form a polyurethAne, polyurea or mixed poly(urethane-urea). In the present invention where the term "polyurethane" i8 used, not only polyurethanes from the reaction of polyi~ocyanates and polyols are intended, but also mixed poly(urethane-ureas) and polyureas are intended. Also, reaction products obtained from the reaction of 20 polyisothiocyanates with active hydrogen-containing compounds are intended.
To achieve the best blend of propertie~ in basecoat layer 16, e.g., flexibility, elongation, and adhesivenes~, the organic polyisocyanate i3 reacted with the polymeric active 25 hydrogen-containing compound and preferably with a short chain active -hydrogen-containing compound. ~ -The organic polyisocyanate which is used can be an aliphatic including cycloaliphatic or aromatic polyisocyanate or a mixture of the two. Diisocyanates are preferred although higher 30 polyisocyanates can be used in place of or in combination with diisocyanates. Examples of suitable polyisocyanates are 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-methylene-bi3(cyclohexylisocyanate), trimethylhexamethylene 35 diisocyanate and 1,2,4-benzene trii~ocyanate. Isothiocyanates corresponding to the above-described isocyanates (where they exist) .. , ; , ~ . ,, , . . ~

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can be employed a~ well as mixed compounds containing both isocyanate and isothlocyanate groups.
The preferred active hydro;gen-containlng materials which are reacted with the polyisocyanates include materlals such as 5 amine~, amino alcohols, mercap~o-terminated derivati~es and polyols, which are preferred. The term "active hydrogen" reers to hydrogens which, because 0~ their position in the molecule, di~play reactivity according to the Zerewitinoff test. Preferred active hydrogens include hydrogen atoms attached to oxygen, nitrogen or sulfur and 10 thus useful compounds having at least two of the group~ from the group of hydroxyl, thiol, and primary or secondary amine~.
For the development of the best blend of properties such as good flexibility, elongation and adhesiveness, the active hydrogen-containing materials are preferably a mixture of both high 15 molecular weight actiYe hydrogen-containing materials, e.g., polymeric active hydrogen-containing compounds, and low molecular weight active hydrogen-containing materials, e.g., short chain active hydrogen-containing compounds. Example~ of ~uitable low molecular weight active hydrogen-containing materials are diols, triols, 20 diarnines and triamines having a molecular weight less than 300 and usually in the range of about 60 to 250. Such materials include aliphatic polyols, particularly alkylene polyols containing from about 2 to 18 carbon atoms such as ethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol and trimethylolpropane. Polyols 25 including acid groups such as dimethylolpropanoic acid can also be used as can polyamines such as ~thylene diamine and hydrazine.
Mixtures of such low molecular weight active hydrogen-containing materials may al~o be used.
Example3 of high molecular weight active 30 hydrogen-containlng material~ are polymeric polyols which have molecular weights of at least 400 and usually within the range of about 400 to 3000. The most suitable polymeric polyols include polyether polyols such as linear polyether diols, polyester polyols, including polyhydroxy polyesteramides, and hydroxyl-containing 35 polycaprolactones and hydroxyl-containing acrylic interpolymers including mixtures of polymeric polyols. Polyester polyols such as ~ 3 $ ~ ~

linear polyeister diol~ including hydroxy-containing polycaprolactones, particularly diol~, are preferred.
Example~ of polyether polyol~ are polyalkylene ether polyols which have the fol~owing structural formula:
Hf O - (CH)n~- OH
~ R J m where the substituted R is hydrogen, a lower alkyl, or mixtures thereof, n i~ typically from 2 to S, And m i3 from 2 to 100 or higher. Example~ are poly(oxytetrame!thylene) glycols and 10 poly(oxyethylene) glycols.
Examples of polyester polyol~ are those prepared by polyesterification of organic polycarboxylic acids or anhydride~
thereof with organic polyols. Polyols used in preparing the polyester include alkylene glycol~, such as ethylene glycol, 15 1,4-butanediol, neopentyl glycol, trimethylolpropane and the like including mixtures thereof.
The acid component of the polyester can be monomeric carboxylic acidq or anhydrides having about 2 to 36 carbon atoms per molecule. The acid may be acyclic or cyclic including cycloaliphatic 20 or aromatic polycarboxylic acids. Among the acids which can be used are phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, adipic acid, dimeryl diacid and maleic acid including mixtures of ~uch acids. Where acids are referred to above, it is understood that anhydrideQ of those acids which form anhydrides ci~n be u~ed in place 25 of the acid. Also, lower alkyl e~ters of diacid~, such as dimethyl esters, can be used. ~The preferred acid mixture employed in forming the polyester contains a C36 dicarboxylic acid product known as dimer acid. The processes for~forming this acid are well known and form the sub~ect of numerouis U.S. Patents including, for example, 30 2,482,761, 2,793,220, 27793,221, and 2,955,121. In carrying out such dimer-forming procedures, unsaturated fatty acidis such as oleic, linoleic and linolenic acid, or mixtures of such acids (all of essentially C18 chain length) are heated in the presence of water, or in the presence of both water and an actlve clay mineral, to induce 35 polymerization.

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Preferably, the relative amounts of organic polyisocyanate and active hydrogen-containing compound~ which are reaeted with one another are such that the resulting polymer will have a urethane content greater than 6, preferably at lea~t 8, more preferably about 5 8 to 25 percent by weight. The percentage by weight i8 based upon the weight of urethane linkago per total w2ight of polymer. By "urethane", it is meant to include not only the reactlon o~
isocyanate and hydroxy, i.e., -~(H)-C(0)-0- but al~o to lnclude the reaction o isocyanate and other active hydrogens 3uch as primary and 10 ~econdary amino and thiol.
With regard to the active hydrogen-containing materials which were used in preparing the polyurethane, the high mole~ular weight active hydrogen-containing material is preferably present in amounts of about 50 to 95, more preferably 60 to 85 percent by weight 15 based on the total weight of an active hydrogen-containing material with the remainder being the low molecular weight active hydrogen-containing material.
The organic polyisocyanate snd active hydrogen-containing materials can be reacted at temperatures of from about 20C to 200C
20 for about 0.1 to 4 hours and optionally in the presence of a catalyst such as an organo tin compound. The reactants and solvents used in the reaction preferably are dry. Polyurethanes can be prepared via so-called "one shot" techniques in whlch all of the active hydrogen-containing materials are reacted with the organic 25 polyisocyanate, or preferably by the prepolymer method in which only part of the active hydrogen-containing materials are reacted to form an isocyanate prepolymer followed by reacting the prepolymer with the remaining portion of active hydrogen-containing material~.
The polyurethanes for use in the practice of the present 30 invention ~ay be either water dilutable or solvent dilutable, i.e., they can be either aqueou~ polyurethane dispersions which are preferred or solvent solutions of polyurethanes.
Dispersion can be obtained by thinning the polyurethanes in a water-miscible solvent and dispersing the diluted polyurethanes 35 with water, optionally in the presence of an externally added surfactant. Preferably, however, the polyurethanes are prepared ~o :: -, ` . 2 ~ P~ ~

that they contain ionic ~alt group3 in the polymer backbone. Such ionically charged polymers can be dl3persed more readily in water and form more stable disper~ions. Examples of ionic group~ are anionic salt groups selected from the clasq consisting of -OS03-, -COO~, 5 -OP03=, -S020-, -POO~ and P03=, with C90~ being preferred. The polyurethane can be prepared with reac~ants containing an acid group which can be ~ubsequently neutralized before, after or during polyurethane formation. A portion of the acid groups can be iminated such a~ by reacting with hydroxyethyl ethyleneimine. Suitable 10 materials for introducing acid eroupa into the polyurethane are compounds which have two group~q which are reactive toward~ i~ocyanate groups and at leaqt one group which i8 capable of forming an anion.
Examples of such compound~ are hydroxy and mercapto carboxylic acids. Specific example~ include dimethylolpropionic acid, which is 15 preferred, glycolic acid and lactic acid. Other examples of compounds which contain active hydrogens and acid groups are amino carboxylic acids, amino hydroxy carboxyllc acids, sulfonic acids, ~-hydroxy sulfonic acld~ and amino sulfonic acidq. Examples include oxaluric acid, anilido acetic acid, glycine, 6-amino-caprylic acid, 20 reaction product of ethanolamine and acrylic acid, hydroxyethylpropionic acid, 2-hydroxy-ethane sulfonic acid and sulphanilic acid. Amino acids must be used in the presence of base uch as potassium hydroxide or a tertiary amine. Other examples include bi~-hydroxymethyl-phosphinic acid, trime~hylolpropane 25 monophosphate and monosulfate. Suitable salt-forming agents for acid group-containing compounds include inorganic and organic baseq such as ~odium hydroxide, potassium hydroxide, ammonia and tertiary amines. ~-Besides anionic salt groups which are preferred, the polyurethane can contain cationic salt groupc such as those sslected 30 from the clas~ consisting of:

- Il~ - _ p+ _ I +
~, '.

35 including mixed groups.
Preparation of polyurethanes with cationic group~ are described in U.S. Patent 4,147,679, column 12, line 12, to column 13, line 30, the portion~ of which are herein incorporated by refçrenca.

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Besides u~ing ionic solubiLizing groups as described above, nonionic solubilizing groups can be Incorporated into the polymer.
The nonionic water-solubilizing groups can be incorporated into the polymer through the isocyanate or through the active hydrogen 5 component of the polyurethane. Examples of nonionic water-solubilizing groups are ethylene oxide moieties which should constitute not more than 50 percent by weight of the prepolym0r and which can be incorporated into the prepolymer using polyethylene glycols.
The polyurethanes can be prepared as described above and dispersed directly in water. Examples of preparing the polyurethanes by thi~ t~chnique are shown in U.S. Patent 3,479,310 to Dieterich et al. Also, water-based polyurethanes can be prepared in accordance with Ex~nples 6 and 7 of U.S. Patent 3,954,899.
High molecular weight thermoplastic polyurethanes are preferred in the basecoat compositions because they provide for optimum metallic pigment orientation and prevent ~trike-in of the topcoat without the need for special addit1ves. Also, high molecular weight polyurethanes provide for optimum adhesiveness, elongation, 20 and flexibility in basecoat layer 16 making the ba~ecoat useful for stretch forming of the paint composite over and around automotive parts. Preferably, basecoat layer 16 based upon the polyurethane will have a tensile ~trength of greater than 2000 and usually within the range of 2500 ~o 10,000 psi and elongations of at least lOO and 25 more preferably from 150 to 250 as determined accordingly to ASTM D~639-72.
Basecoat layer 16 further contains color pigments and metallic P~8ments. Compositions including metalllc flake pigmentation provides for the production of so-called "glamour 30 metallic" finishes upon the surface of, 2.g., automobiles. Proper orientation of the metallic pigmen~s results in a lustrous shiny appearance with excellent flop, distinctne3s of image (DOI), and high gloss. By "flop" is meant the visual change in brightnes~ or lightness of a metallic coating with a change in viewing angle, i.e., 35 a change from 180 to 90. The Breater the change, i.e., from a light to dark appearance, the better the flop. Plop is important 2 g3 3L ~ ~ r7 ~
. ' .

because it accentuates the line~ of a curved surface such as an automobile body. Suitable metallic ~igments include, in particular, aluminum flake? copper bronze flake imd metal oxide coated mica.
Besides the metallic pigments, basecoat layer 16 may 5 include nonmetallic colored pigments conventionally used in surace coating compo~itions including inorg~nic pigment~ such a~ titanium dioxide, iron oxide, chromium oxide, lead chromate, carbon black and the like and organic pigments such as phthalocyanine blue and phthalocyanine green.
In general, pigment i8 incorporated into basecoat layer 16 composition in amounts of about 1 to 80 percent by weight based on weight of coating 301id~. Metallic pi8mentation i8 employed in amounts from about 0.5 to 35 percent by weight of the aforesaid aggregate weight. If desired, the composition for forming basecoat 15 layer 16 may additionally contain other ma~erials well known in the art of formulating ~urface coatings such as ~urfactants, flow control agent~, thixotropic agents, fillers, anti-gassing agents, organic co-solvents, catalysts and other similar auxiliary additives.
The metallic-pigmented basecoat composltion i~ applied to a 20 surface of carrier film 10 in a manner which provides a shearing force upon the metallic-pigmented basecoat composition. The shearing force should be sufficient to provide for metallic orientation within resultant metallic-pigmented basecoa~ layer 16. Various mean~ of applying a ~ufflcient shearing force are available and include roll 25 coating, i.e., coating with a knife o~er roll, or coating with an air knife over the roll coating to provide sufficient ~hear.
During application of the basecoat composition, a film of the ba3ecoat is formed on the carrier film. Typically, the thickness of basecoat layer 16 will be from about 0.1 to 3 mils. After 30 application of the ba~ecoat composition to carrier film 10, a basecoat layer film is formed by driving water or solvent out of the applied basecoat composition. This can be accomplished by heating or simply by air drying. Preferably, the heatin8 step will only be for a short period of time sufficient to en~ure that a ~ubsequently 35 applied tran~parent topcoat composition can be applied to basecoat layer 16 without any tendency of the former to mix or dissolve the ~,,.:, . . -2 ~ ~L 3 ~ r7 ~3 basecoat layer, i.e., "~triking in". Suitable drying conditions will depend on ehe ambient humidity and temperature but, in general, a drying tlme of from 1 to 60 minutes at a temperature of 160 to 200 Fahrenheit (F) (71C to 93C) will be adequate to ensure that 5 mixing of the two coating layers is E~revented. The temperature of drying should not degrade or deform the carrier film 10. At the ~ame time, basecnat layer 16 is adequately wetted by the transparent topcoat composition 80 that satisfact:ory intercoat adhesion is obtained. Also, more than one basecoat layer and multi~le clearcoat 10 layer~ may be applied to develop the optimum appearance. Usually, between coats, the previou~ly applied basecoat layer or topcoat layer is baked, i.e., exposed to ambient conditions~ for from about 1 to 60 minutes to form a dry/cured film.
The transparent topcoat layer 18 can include a film-forming 15 polymer and usually a diluent. Any suitable film-forming polymer may be used. The polymer may be either thermoplastic or thermosetting in nature. The polymer may be, e.g., an acryllc polymer which i~
particularly useful for automotive finishes. Such acrylic polymers are polymers or copolymers of one or more alkyl esters of acrylic 20 acid or methacrylic acid, optionally together with other ethylenically unsaturated monomers. Suitable acrylic esters include methyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate and the like. Suitable other copolyMerizable monomers include, e.g., styrene and acrylonitrile. Where the acrylic polymer is of the 25 thermoset~ing type, there should be suitable functional monomers present to result in crosslinking. Examples would include hydroxyl-containin~ acrylic monomerq such as hydroxyethyl methacrylate, hydroxypropyl methacrylate or the like and acid-containing acrylic monomers such as acrylic acid or methacrylic 30 acid. These materials can be crosslinked with a curing agent such as an aminoplast condensate or a polyisocyanate. Suitable aminoplasts include those previously described below.
Polyisocyanates and blocked isocyanates can also be u~ed a~
curing agents. Examples of suitable polyisocyanates include 35 monomeric polyi~ocyanates such as toluene diisocyanate, 4,4'-methy-lene-bis(cyclohexyl isocyanate), isophorone diisocyanate and isocyanate-prepolymers such as the reaction products o monomeric polyisocyanate, such a~ tho~e previously mentioned above, wlth polye~ter polyols or polyether polyols.
Besides the acrylic polymer~, polyesters can al90 be used 5 in the formulation of the ~ransparent topcoat. U~ually, the~e polyesters or polyester polyol~ are designed to be cured with a polyisocyanate or with an aminoplast resin. Polyesters can be ormed by ~he polyesterification of an organic polycarboxylic acld or its functional equivalent thereof, e.g., an anhydride thereof, with an 10 organic polyol. Among the acids which can be used are phthalic acid, terephthalic acld, tetrahydrophthalic acid, hexahydrophthalic acid, azelaic acid and dimerized fatty aclds including mi~tures thereof.
Example of suitable polyols are ethylene glycol, 1,4-butanediol, neopentyl glycol, trimethylpentanediol, trimethylolpropane and the 15 like, including mixtures thereof.
Polyurethanes may also be used as the film-forming polymer in the clearcoat layer 18. Particularly suitable are poly(ester-urethane) polyols which can be cured with an aminopla~t or polyisocyanate as described above. The polyester polyol is usually 20 first prepared and then reacted with the polyisocyanate. Polyesters which may be used include those previou~ly mentioned above. The polyisocyanate can be aromatic, aliphatic, and cycloaliphatic with - ~ -aliphatic and cycloaliphatic being preferred because o~ better U.V. ~-light stability. Examples of polyisocyanate~ are described above.
25 The polyurethane-based topcoating compositions are preferred.
Examples of such polyurethane-based coating composition3 are described in U.S. Patents 4,485,228 and 4,540,766, both to Chang et al, which are hereby incorporated by reference.
Topcoat compositions can be applied over baq coat layer 16 30 by any conventional technique such as brushing, ~praying, dipping, rolling or flowing, but it may be preferred that a roll-coat application be used where a roll-coat application is used to apply the basecoat composition.
After application of the topcoa~ compo~ition to basecoat 35 layer 16, the coated carrier film may be subJected to heating to con~ointly harden the coating layers. In the curing operation, 2 ~ 8 solvents and/or water are driven off and the film-forming material of topcoat layer 18 can be crosslinXed ~ith the aid of any crosslinking a8ents present. The heating or curing operation is carried out at a temperature which is not detrimental to carrier ~ilm 10, generally in 5 the range of from about 160F to 200~F (71C to 93C). Lower or higher temperatures may be used so long as the temperature does not degrade carrier film 10. The thicknle~s of topcoat layer 18 i~
generally from about 1 to 12 mils, preferably about 1.2 to 10 mils.
To provide for application of the composite paint article 10 of this invention, basecoat layer 16 and topcoat layer 18 must each be flexible and provide for elongation. The flexibility of the coatings can be determined by coat~ng an elastomeric substrate such as a 1/8" thick ~hermoplaQtic polyester urethane commercially available from Mobay Company as TEXI~ 3202 and bending the coated 15 substrate around the 1/4" diameter mandrel with the coating side outwardly facing. After bending, the coating is examined for breaks or cracks. Testing can be conducted at room temperature, i.e., 70F
to 75F or at low temperature, i.e., a cooled substrate at 0F before bending. The present coatings preferably exhibit no breaks or cracks 20 when tested at 32F in the above-described manner and more preferably exhibit no breaks or cracks at 0F.
The elongation of the present coatings can be determined by Instrom testing.
The hardness of the coatings can be determined by the Sward 25 method using a Sward rocker as described in ORGA~ilC COATINGS
TECHNOLOGY, Payne, Volume I, 1965, pages 642-643. Cured coatingq of the present paint compo-qite preferably have a Sward hardness within the range of 10 to 40, more preferably 10 to 24. Testing for Sward hardness i9 done on coatings having a thickne~s of about 2 to 3 mils 30 over steel panels.
Temporary protective cover 20 can be situated fld~acent adhesive layer 12 to enable the palnt composite article to be stored and rolled without adhesive layer 12 coming in contact with transparent coating layer 17. Temporary protective cover 20 should 35 be easily removable from the adhesive. For example, the temporary protective cover can be a paper or a polymeric material such as M~LAR
available from E. I. du Pont de Nemours and Co., Inc.

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, The paint composite article can be applled to automobile body parts in a fashion similar to that described in ~uropean Patent Application 251,546. Generally, temporary protectire cover 20 i8 removed from the paint composite article; adhesive layer 12 of the 5 paint composite article i~ positioned over the substrate to be coated; and the paint compo~ite art~cle may be heated to activate the adhesive and to thermally deform carrier fllm 10 whereby a vacuum can shape the paint composite article over the substrate to provide a painted automobile body part.
Referring to Fig. 2, the composite is slmilar to that of Fig. 1 in that it also includes a carrier film 110 with an adhesive layer 112 on one side and a paint layer 114 on its other side. The paint layer 114 similarly includes a pigmented basecoat layer 116 and a transparent topcoat layer 118. This composite may also include a 15 temporary protective cover 120. The above-described component~ have the same characterlstics as tho~e described above in connection with the corresponding components described above in connection with FiB.
1. The paint compo~its of FiB. 2 addit~onally9 however, includes a tiecoat layer 122 between the carrier film 110 and the paint layer 20 114. This tiecoat layer may consist of any suitable adhesion promoting material between the carrier film and the basecoat layer, but it i9 preferably a mixture of an acrylic polymer and a polyurethane. The tiecoat should be from about 0.01 mil to 1.0 mil and preferably 0.01 mil to 0.5 mil in thickness. The tiecoat may 25 also include an aminoplast in the amount of from l to 35 percent by weight and/or an alkylbenzene in the amount of 1 to 35 percent by weight of the tiecoat based, in both ca~es, on weight of ~esin sol1ds.
The acrylic polymers are copolymers of one or more alkyl esters of acrylic acid or methacrylic acid optionally together with 30 one or more other polymerizable ethylenically unsaturated monomers.
These polymers may be either of the thermoplastic type or thermosetting cros~linking type. Suitable alkyl esters of acrylic acid or methacrylic acid lnclude methyl methacrylate, e~hyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate and 35 2-ethylhexyl acrylate. Suitable other copolymerizable ethylenlcally unsaturated monomers include vinyl aromatic compounds such as styrene : - ~ , 3 ~,$7 ~, and viny} toluene; nitriles such as acrylonitrile and methacrylonitrile; vinyl and vinylidene halides ~uch as vinyl chloride and vinylidene fluoride and vinyl esters such as vinyl acetate.
Where the polymer 18 of the cros~linking type, suitable functional monomers may be u~ed in addition to the other acrylic monomers mentioned above and includs, for example, acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate. The coating 10 composltion in such cases contains a crosslinking agent ~uch as an aminoplast such as those described below, particularly a condensate of melamine and an aldehyde such as formaldehyde or a lower al~yl ether of such condensate in which the alkyl groups contain from 1 to 4 carbon atoms. Other crosslinking agents such as polyisocyanates 15 including blocked polyisocyanates may also be u~ed. Also, the acrylic polymer can be prepared with N-(alkoxymethyl)acrylamides and N-(alkoxymethyl)methacrylsmides which result in ~elf-crosslinking acrylic polymers. Aminoplasts are preferred curing agents and are present in amounts of from about 1 to 35 percent by wei~ht based on 20 weight of re~in 301ids in the tiecoat.
The acryIic polymer may be prepared by solution polymerization technigues in the presence of suitable catalyst~ such as orgsnic peroxides or azo compounds, for example, benzoyl peroxide ~;
or N,N!-azobis(i30butyronitrile). The polymerization can be carried 25 out in an organic solution in which the monomers are soluble.
Suitable solven~s are aromatic solvents such a~ xylene snd toluene and ketones such as methyI amyl ketone. Alternately, the acrylic polymer may be prepared by aqueous emulsion or dispersion polymerization techniques.
The polyurethane polymer useful in forming this tiecoat would be prepared in the manner described above in connection with ;
the paint layer. The acrylic and ~he polyurethane would be blended in a proportion of 90:10 to 10:90 by weight based on the weight of ~;
resin qolid~
Figs. 3 and 4 have the same elements as those which are included in Figs. 1 and 2. The palnt composite article of Fig. 3 :-.'`-,: ~

2 ~

includes a carrier film 210, having an adhesive layer 212 on its one side and a paint layer 214 made up of a pigment~d layer 216 and a tran~parent topcoat layer 218 on its other side. It may also optionally include a temporary protective cover 220. The paint 5 compoQite article of Fig. 4 includes a carrier film 310 with an adhe~ive layer on one side and a tiecoat layer 322 and a paint layer 314 on its other side. The paint layer would consi~t of a pigmented basecoat layer 316 and R transparent topcoat layer 318. It would alQo optionally include a temporary protective co~er 320. These 10 elements would be the ~ame as the corresponding elements tescribed above in connection with Figs. 1 and 2 except that the pigmented basecoat 216 or 316 would include an aminoplast in an amount sufficient to enhance thr adhesion of the basecoat to ~he thermally deformable carrier film but preferably in an amount insufficient to 15 cro~slink the thermoplastlc film-forming binder.
Aminoplaqt resins are aldehyde conden~ation products of melamine, urea, and similar compoundQ; products obtained from the reaction of formaldehyde wi~h melamine, urea or benzoguanamine are most common and are preferred herein. However, condensation products 20 of other a~ine~ and amides can also be employed, for example, aldehyde condensates of triazines, d~az~nes, triazole3, ~uanidines, guanamine~ and alkyl and aryl substituted derivatives of such compounds, including alkyl and aryl sub~tituted ureas and alkyl and ary~ ~ubstituted melamines. Some examples of such compounds are 25 N,N'-dimethylurea, benzourea, dicyandiamide, formoguanamine, acetoguanamine, ammeline, 2-chloro-4,6-diamino-1,3,5-triazine, 6-methyl-~,4-diamino-1,3,5-triazine, 3,5-diaminotriazole 9 triaminopyrimidine, 2-mercapto-4,6-diaminopyrimidine, 2,4,6-trimethyl triamino-1,3,5-triazine, and the like.
While the aldehyde employed i9 most often formaldehyde, other similar condensation product~ can be made from other aldehyde~, ~uch as acetaldehyde, crotonaldehyde acrolein, benzaldehyde, furfural, and others.
The amine-aldehyde conden~ation products contain methylol 35 or similar alkylol groupQ, and in mo~t instanceA at least a portion of these alkylol groups are etherified by a reaction with an alcohol ,~. , . . ... . . .. --'~- ,: ' :.
~, ~

2 ~ 3 7 ~

to provide or~anic solvent-soluble resins. Any monohydric alcohol can be employed for thie purpose, including such alcohol~ as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol and others, as well as benzyl alcohol and other aromatlc alcohols, cyclic 5 alcohol such as cyclohexanol, monoethers of glycol~ such as ethylene glycol and diethylene glycol, and halogen-subst~tuted or other substituted alcohols, such as 3-chloropropanol. The preferred amine-aldehyde resin~ are etherified with methanol or butanol.
Preferably, the aminoplasts which are u~ed are melamine-, 10 urea-, or benzoguanamine-formaldehyde conden~ates etherlfied with an alcohol containing from about 1 to 4 carbon atom~ or mixtures thereof. When u~ed in the basecoat compositions, the aminoplast 1 generally present in amounts of about 1 to 35, usually 5 to 15 percent by weight, based on weight of resin ~olids.
The invention ia illustrated but is not limited by the following examples. In the~e examples and throughout the specification, parts and percentages are by weight unless otherwi~e specified.
:
ExamDle A
A water-diluted polyurethane binder was prepared from the following ingredients:
In~redientsParts bY Wei~ht ~pounds) N-methyl-2-pyrrolidone432.4 25 FORMREZ 55_561 315.0 ;
POLY~EG 20002 315.0 Dimethylolpropionic acid 129.0 DESMODUR W3 573.0 Neopentyl glycol 6.5 30 Deionized water 2348.0 Dimethylethanolamine82.3 Ethylenedlamine 43.7 lPoly(neopentyl adipate~ glycol having a molecular weight of 2000, available from Witco Company.
2Polytetramethylene glycol having a molecular weight of 2000, available from Quaker Oats Company.
,-- , ~.

2 ~

34,4'-methylene-bis(cyclohexyl isocyanate) avallable from Mobay Corporation.

The N-methyl-2-pyrrolidone, FORMR~Z 55-56, POLYMEG 2000, 5 dimethylolpropionic acld and 257 grams (g) of dibutyltln dilaurate and 2858 g of n-butanol were charged to a clean dry reactor set for total reflux, heated to 185F to 194F (85C to 90C) under a nitrogen blanket, and held for about 15 minutes until reaction mixture i9 homogeneous. The reaction mixture wa~ then cooled to 10 130F to 140F (54C to 60C) and the D$SMODUR W added, ~ollowed by the addition of the neopentyl glycol. The temperature of the reaction mixture wa~ ad~usted to 158F to 167F (70C to 75C) and held for about 15 minutes until the batch became homogeneous. The temperature of the reaction mixture was ad~usted to 185F to 194F
15 (85C to 90C) and dispersed by addlng to a mixture of the deionized water, dimethylethanolamine and ethylenediamine while maintaining temperature of the dispersion between 158F to 167F (70C to 75C).
The resulting dispersion was stirred for 30 minutes at 158F to 167F
(70C to 75C) and cooled to 86F to 95F (30C to 35C). The 20 dispersion had a ~olids content of 34.3 percent and a pH of 7.86.

Example B
An lmlnated water-diluted polyurethane binder was prepared from the following:
In~redient~ Parts bv WeiQht Polyurethane dispersion of Example A ~22.8 ~ydroxyethyl ethyleneimine 2.2 Deionized water 5.0 The polyurethane dispersion was charged to a reaction 30 vessel, the hydroxyethyl ethyleneimine slowly added over over several minutes and the mixture heated at about 70C for one hour. The mixture WaQ then diluted with the deionized water. The resulting disperslon had a sollds content of 3302 percent and a pR of 8.8.

~xample C
An acryllc resin was prepared from the followlng:

~ .,, , :
: ~ .

- . .

~ b~ ~
.
. ``

In~redients Part~ b~ eiRht Initial Char~e Deionized water 16.8 Feed A (described below) 342.5 Butyl CARBITOL ~monobutyl ether of diethylene glycol) 45.1 t-Butyl peracetate 4.55 Feed ~
Styrene 268.4 Butyl acrylate 259.6 Butyl methacrylate 165.7 Methyl methacrylate 40.2 ::~-Acrylic acid 75.2 ~ -Hydroxypropyl acrylate 84.6 Feed B
Butyl CARBITOL 112.5 ~:
Feed C
Butyl CARBITOL 105.4 -~
t-Butyl peracetate 10.6 - ~ :-Feed D
Butyl CARBITOL 22.5 :~
Deionized water 16.8 Feed E
Butyl CARBITOL 29.7 t-butyl perbenzoate 0.9 Feed F
Butyl CARBITOL 15.8 Feed G

Dimethylethanolamine 49.5 Feed H
Deionized water 2025.0 The initial charge was heated to reflux ~about 97C) in a properly equipped reaction vessel. The remainder of Feed A and -~
Feed C were then added over a three-hour period with continued :
35 refluxing. Feeds B and D were added after completion of the Feeds A
and C addition, followed by addition of Feed E over about an hour and .. ,,, .. , . .. , . ,.. ,.. ,, .. ,.. . ... ... ~ . , . , ., . , . , . , . ~ , . - , 2 ~ ~ $ ~

subsequent addition of Feed F. The re~ultant mixture wa~ refluxed for an additional hour, followed by addition of Feed G and sub~equen~
addition of Feed ~ over a quarter hour. The final mixture was cooled and analysis indicated a 301ids content at 150~C for one hour of 24.2 5 percent, a pH of 7.8 and a number average molecular weight of about 20,300 a~ measured by gel permeation chromatograp~y with a polystyrene standard.

ExamDle D
In a 22 liter round bottom 4-neck flask equipped with a metal stirrer, nitrogen gas inlet tube, thermometer and steam condenser with saddlepacked take off head, the followlng in8redients were charged:
InRredients Parts bY Wei~ht t~rams) Trimethylolpropane 900 Neopentyl glycol 5391 Adipic acid 1026 Tetrahydrophthalic anhydride 6420 Dibutyltin dilaurate tcatalyst) 28.2 - 20 The entire mixturejwas heated to 168C (head temperature 99C~. At this point 150 ml of distillate had been collected, most of which was water. After 6 hours the temperature had reached 221C
(head temperature 90C). 920 ml of distillate had been collected and the acid value was 25. After an additlonal 2 hours the acid value 25 had reached 18.5 and the batch was cooled overnight. Heating was resumed the next day, and in ~ hours the temperature had reached 222C at which time ~76 ml of distillate had been collected, and the acid value at that point was 13.6. The reaction was continued another 1.5 hours at 122C and a total d~stillate of 1,009 ml was 30 collected by that time. The acid value at that point ~as 9.13 and the resin vi~cosity, thinned to 70 percent by weight in methyl isobutyl ketone, was J on the Gardner scale. At this point the batch was cooled to 122C and a vacuum of 20 mm/Hg was applied for a period of 20 minutes. At a temperature of 114C a mixture of 512 g of 85 35 percent phosphoric acid and 488.8 g of a 70 percent~30 percent mixture by weight of xylene and methyl i~obutyl ke~one was added to ,, ., , . , ~ .. . ~ . . . .... . .. .

. .
~.. ,,,-;' , ~.-- .
.,, ,. ,: :, . . ... .
. . . .

~ ~ ~ ..?.~ ~3t f7 85 the reaction mixture. The equipment was then modiied by replacing the steam condenser with a Dean-Stark trap with a cold water condenser. The reactlon mixture wa~ heated to 151C at which point 16 ml of distillate was collected and the acid value was 45. Over 5 the next 2.5 hours, the temperature was increased to 184C with 160 ml of d~stillate being collected and the acid value being 30.6.
Heating wa~ continued for an additional hour at which point the temperature was 190C with 180 ml o~ di~tillate being collected and the acid value being 27.S. A vacuum of 20 mm/Hg was applied to ~he 10 reaction mixture for 27 minutes. The reaction mixture was cooled to 140C and thinned with butyl CARBITOL to approximately 60 percent solids. The final product had a measured solids content of 60.5 percent by weight, an acid value of 1809, a viscosity of 16.7 poise and a hydroxyl number of 150. -Basecoats ExamDle ~
A silver metallic basecoat composition including a water dilutable polyurethane was prepared from the following~
In~redients Parts bY Weight Monohexylether of ethylene glycol 95.4 Butyl CARBITOL 30.3 IRopropanol 13.0 Silicone surfactantl 17.3 Titanate solution2 8.67 Phosphatized polyes~er from ~xample D 27.7 U.V. absorber3 13.0 Aluminum pigment4 147.0 Polyurethane disper~ion of Example B 1250 Deionized water 217.0 Toluene 101.88 lA 25 percent by weight ~olution of L5310 silicone in monohexylether of ethylene glycol.
2A 0.76 percent by weight solution of di(dioctyl)phosphatoe-35 thylene titanate (a liquid material available from Kenrich Company)in monohexylether of ethylene glycol neutralized with dimethylethanolamine to a p~ of 7.5.

- ~2 - 4æ ~

3A liquid U.V. absorber of the hydroxyphenylbenzotriazole class, available from Ciba-Geigy Corporation a~ TINUVI~ 1130.
4Non-acid resistant pigment available as PA-8260 ~rom J. H.
Hinz.

A vessel was charged with the butyl CARBITOL, monoheYylether of ethylene glycol, ilopropanol, ~ilicone ~urfactant, titanate solution, phosphatized poly~ster and U.V. absorber. The aluminum pigment was then mixed with agitation until completely 10 dispersed. Deionized water and 217 parts of t~e polyurethane dispersion were premi~ed and then added to the vessel wi~h agitAtion. The remainder of the polyurethane dispersion was added to complete the admixture.

Example F
A black pigment paste was prepared from the following:
InRredients Parts bY Wei~ht Butyl CARBITOL 8.32 Deionized water 39.00 20 SURFYNOL TgI O.62 TAMAL 7312 1.38 Dimethylethanolamine 0.84 Polyurethane di~persion of Example B 35.30 Carbon hlack 4.32 lA pigment disperQing aid, available from Air Products and Chemicals, Inc.
2A pigment dispersing aid, available from Rohm and Haas Co.
,, ~
The above ingredients were ground ln a steel ball a~tritor 30 to a Hegman 8 grind, followed by addition of 14.2 parts of deionized water.

; Bxample G
A blue pigment wao prepared from the following:

-, ,;

,,: -:

~ 3 ~

InRredients Part~ b~ WeiRht Butyl CARBITOL 3.20 Deionized water 5.82 SURFYNOL Tgl 0.20 5 TAMAL 7312 0.60 Polyurethane dispersion of Example B 21.18 Blue pigment3 4.00 lAs in Example F.
2As in Example F.
10 3Available as Palamar Blue from Harmon Color Corporation.

The above ingredients were ground in A steel ball attri~or to a Hegman 7.5 grind, followed by addition of 5.0 parts deionized water.
Exam~le H --A basecoat composition including a water dilutable :~
polyurethane was prepared from the following~
In~redients Parts b~ Wei~ht 20Char~e 1 .
Black pigment paste from Example F 240.0 Blue pigment pas~e from Example G 9.06 Silicone surfactant solutionl 9.96 ~ ~
Metal coated mica2 2.29 :-~ .
-:
25 Monohexylether of ethylene glycol 3.43 : :
CharRe 2 ~-Polyurethane dispersion of Example B 6.87 :::
Deionized water 8.92 :~
' CharRe 3 30 Polyurethane disperslon of Example B 625.0 U.V. light absorber3 7.47 Isopropanol 7.47 Char~e 4 Monohexylether of ethylene glycol 49.8 :
: . :' 5.

~ ~ 3 ~ ~

har~e 5 Polyurethane dispersion of Example B 15.3 Deionized water 30.6 Silica4 5.11 lAs in Example E.
2Available a~ 139X Bright Mica from PI-CO~.
3As in Example E.
4Available from PPG Industries, Inc. a~ LOVEL 27.

The basecoat compo~ition was prepared from the above charges by sequentially premixing each charge and then adding each charge to a vessel.

Clear Coat Exam~le I
A polyester-urethane polyol wa~ prepared from reacting isophorone diisocyanate with a polye~ter diol prepared from dimerized fatty acids. The polyester wa~ prepared from the following in8redient~:
In~redient~ Part~ b~ WeiRht ENPOL 10101 1276.0 Cyclohexane dimethanol 378.0 Trimethylolpropane 139.0 ~eopentyl glycol 359,0 Butyl stannoic acid 0.93 Triphenyl phosphine 1.07 Xylene 107.0 ; , Deionized water 200.0 lDimerized fatty acid available from Emery Chemical Company.
The ingredients were charged to a reaction veq~el equipped for reflux and a nitrogen ~parge. The admixture was heaeed under nitrogen to reflux and then maintained at reflux until an acid value of about one was obtained. The resultant product had a solidA
35 content of about 95 percent, an acid Yalue of about 0.54 and a hydroxyl value of about 2.85.

"""'.".'"''- ~, .,: ' ~

2~3~V~
, .

The above prepared polyester wa~ subsequently reacted with a dii~ocyanate as follows:
In~redie~tsParts b~ We~ht ~ ~;
Polye~ter from above5103.6 Neopentyl glycol 1614.0 Isophorone diisocyanate4414.0 Dlbutyltin dilaurate 1.1 Toluene 6022.6 The polye~ter, neopentyl glycol, toluene and dibutyltln 10 laurat~ were charged to a reaction vessel equipped for reflux and a nitrogen sparee. The admixture was heated to 80C under nitrogen and the isophorone diisocyan~te wa9 added over about an hour, and an -~ -exothermic reaction ensued. After the exotherm be8an to subside, the reaction temperature wa~ maintained at about 80C until an IR
15 ~pectrum initiaked the disappearance of isocyanate groups. The reQultant product had a solids content at 110C of 64.3 percent, an acid value of 0.2, a hydroxyl value of 51.9 and a number average molecular weight of about 2100. ~

ExamDle J ~-A two-package clear coat composition including a polyurethane polyol in one package and a polyisocyanate in a second packa~e was prepared from the following:
Packa~e a In~redient~ ~Parts bv Wei~ht Polyurethane polyol o~ Example I 3280.3 Dibutyltin dilaurate 8.4 -~ -~
U.V. absorberl 80.5 ;~
U.V. stabilizer2 13.3 Surfactant3 4.2 Acetyl acetone 24.7 Toluene 202 lAs in Rxample E.
2A 50 percent by weight solution of a hindsred amine llght 35 stabili~er, available as TINUVIN 292.
3Available as SF-1023 silicone rom General Electric Company.
. .

.- , 2~3~

The above ingredients were charged with good agltation and in the order listed to a container to form the first pacXage.

Packa~!e b The second package t587.9 parts by weight) is a polyfunctional aliphat~c isocyanurate resin based on hexamethylene diisocyanate, available as DESMODUR N-3300 from Mobay Corporation.

Adhesives ExamDle R ;~An adhesive wa~ made from an acrylic latex, a defoamer which i9 commercially available as HODAG ANTIFOAM PX 13, a fungicide which i8 commercially avallable as AMOCO ~LOWABLEi ABG 8001 and a polyacrylate thickener which i9 commercially a~ailable from the Union 15 Chemicals Division of Union Oil Company as AUSCO R~S 6038. The acrylic latex had a solid~ content of 55 percent solids in water, a viscosity of 25 centipoises and a pH of 7.1 and was made from the following ingredients:
In~redientsParts BY WeiQht Isobutyl acrylate 59.4 Butyl acrylate 30.7 Methyl methacrylate 6.9 Styrene Hydroxypropyl acrylate Acrylic acid ExamDle L
; Another adhesive wa~ made from the following ingredient~:
In~redients Parts bY Wei~ht Initial Char~e Deionized water 742.1 Sodium bicarbonate 8.4 Feed A
Deionized water 740.7 Potassium persulfate 29.4 2~3~

Feed A-l Deioni~ed water 70,8 Feed B
Isobutyl acryl~te 3037.8 Butyl acrylate 1569.6 Methyl methacrylate 302.4 Acrylic acid ' 50.4 Styrene 50.4 Hydroxypropyl acrylate 52.2 -10 Phosphate ester surfactantl25.3 Feed B~
Feed B 70.8 Feed C -~
Delonized water 70.8 Feed D
Deionized water 221.0 lEMPHOS CS-136 a~allable from Witco Chemical Co.
:
The lnitial chargs was heated to 85~C then Feed A was added 20 over 10 minutes at the same temperature. Peed A-l wa then used to rinse Feed A. Feed B was then added and the mixture was held for 15 minutes at reaction temperature. Feed B-l was added over 5 hours and - -then the mixture was held at the snme temperature or 2 hours. Feed C and D were added and the reaction mixture waQ cooled. Experimental 25 solids were 60 percent, pH was 2.8, viscosity was 25 centipoiAes and particle size was 35 angstroms.
:
Tiecoats ExamPle M
30~ An adhesion promoter was prepared from the following:
InRredients ~ Parts bY Wei~ht ;
Polyurethane dispersion of Example B 822.1 ~;~
Acrylic re~in from Example C1118.0 Silicone surfactantl 5.6 -~
35 Deionized water 1621.0 lA silicone surfactant a~ailable as LS310 from Union Carbide Corporation.
::

2 ~

The polyurethane dispersion and acrylic resin were entered into a vessel. The silicone surfactant was added to the previous admixture with agitation. Deionized water was then slowly added with continued agltation. The resultant product had a sol$ds content of 5 15.7 percent.

~E~m~le N
Additional adhesion promoters were prepared in a similar fashion to Example M with the follo~ing:
Parts by Wei~Lht Ingredients l _ 2 3 Polyurethane dispersion of Example B4500.5822.1 690.6 Acrylic resin of Example C 4500.5822.11174.0 Silicone surfactantl 122.1 5.6 4.8 15 Deionized water 8876.11396.81116.0 Aminoplast resin2 -- 63.6 53.4 ToIuene -- 112.1 --lA silicone surfactant available a~ L5310 from Union Carbide Corporation.
2A partially methylated melamine-formaldehyde resin available a~ REiSIMEiNF 717 from Monsanto CompanyO
.:~
Example 0 An acrylic latex composition was prepared from the 25 following:
In~redien~s Parts bv Wei~ht (pounds) Feed 1 Deionized water 300 2~

Feed 2 Styrene 4620 N-butyl acrylate 2920 ~-butyl methacrylate 2860 Methyl methacrylate 2600 Hydroxypropyl acrylate 1520 Glacial acrylic acid 1262 ~ -Diethylene glycol monobutyl ether 2528 ~:
tert-dodecyl mercaptan 78 VAZ0 64 catalyst 134 Feed 3 Deionized water 266 Sulfonic acid functional acrylic monomerl 78 Dimethylethanolamine 30 Feed 4 Diethylene glycol monobutyl ether 199 Feed 5 Deionized water 83 Feed 6 Diethylene glycol monobutyl ether 254 tert-butyl perbenzoate 15.6 Feed 7 Diethylene glycol monobutyl ether 40 tert-butyl perbenzoate 8.4 Feed 8 Diethylene glycol monobutyl ether 32 ~
Feed 9 ~ ~;
Dimethylethanolamine 600 Diethylene 81YCol monobutyl ether 159 Feed lO
Deionized water 24240 Dimethylethanolamine 100 .
Feed 11 Deionized water 833 lAYailable under the trademark AMPS from Lubrizol Corporation. ;~
''' ' ':

'f~
2 ~

In a reactor set for total reflux, Feed 1 and 5960 parts of Feed 2 were added. A nitrogen atmosphere was used and the mlxture was heated to reflux and that heat was malntained. The remainder of Feed 2 and all of Feed 3 were then added to the reactor over a 5 three-hour period. Feeds 4 and 5 whlch were used, respectively, as tank rinses for the tanks containing Feed~ 2 and 3 were also added.
Feed 6 was then added over a two-hour period along with Feed 8 which was used as a tank rinse for the tank that contained Feed 6. The mixture was held at reflux for two hours after which lt was cooled to 10 215F. Feed 9 was then added after whlch the mixture was cooled to 210F and held for 40 minutes. Feed 11 which was a ~ank rlnse for the Feed 10 tank was also added. Feeds 10 and 11 had been heated to 175F before belng added.

Exam~les P-Q
Tiecoat compositions were made with the following ingredients:
Parts bY Wel~ht InRredient~ Exam~le PExamPle 0 Polyurethane disperslon of Example B 140.6 140.6 Acrylic latex of Example 0 132.3 132.3 Amlnoplast reslnl 11.9 Sillcone surfactant2 4.0 4.0 Toluene 10.0 Deionlzed water 295.3 295.3 lA partially methylolated melamine-formaldehye resin available as RESIMENE 717 from Monsanto Company.
2A silicone surfactant avallable as L5310 from Union Carbide Corporation.
The polyurethane dispersion and acrylic resin of 1 and 2 were weighed into a reaction vessel. The aminopla t res~n, silicone surfactant and toluene were added with agltation. Deionized water was then added with continued agitaton. Solids of Example P were 35 17.0 percent and Example Q were 15.7 percent.

- ~
, ~ ~ . . : :

~3~ ~8 Ba~ecoat With and Wlthout AminoDlasts Exam~le R
A titanium dloxide pigment paste was prepared rom the following ingredients:
InRredients Parts bY Wei8ht Butyl CARBITOLl 52.19 Hexyl C~LLOSOLVE2 52.19 Deionized water 550.54 Urethane resin from Example B 354.78 TiO2 plgment3 499.2 lAvallable from Union Carbide Corporation.
2Monohexyl ether of ethylene glycol available from Union Carbide Corporation.
3Available a~ R902 from E. I. du Pont de Nemours and Co.
After the solvents were premixed, the resins were added.
The TiO2 pigment was then added and di~persed to a Hegman reading of 7.5.
~ .
Exam~le S
; A white, aqueous-based, polyurethane basecoat wa3 prepared from the following in8redients~
In~redients Parts bv Weight Paste from Example R 602.3 Polyurethane dispersion of Example B 380.2 Toluene 19.6 U.V. absorberl 6.0 Silicone surfactant2 7.0 Aminoplast resin3 23.3 lA liquid U.V. absorber of the hydroxyphenylbenzotriazole class, available from Ciba-Geigy Corporation as TINUVI~ 1130.
2Silicone surfactant available as L5310 from Union Carbide Corporation.
3A methylolated melamine available as RESIME~E 717 from 35 Monsanto Corporation.

2~3~

The toluene, U.V. absorber, sllicone ~urfactant and aminoplast re3in were premixed. The paste and poly~rethane di~perslon were charged to a ves~el and mixed after which the premixed materials were added and mixed.

Examl)le T
Another white, agueous-based, polyurethane basecoat was prepared from the following ingredien~s:
In~redients Parts bY Wei~ht Paste from Example R 928.0 Silicone surfactantl 2.95 Polyurethane dispersion of Example A 583.1 U.V. absorber2 7.4 Amlnoplast resln3 39.3 Toluene 33.0 Hexyl CELLOSOLVE 8.85 lTI~UVIN 1130.
2L5310 .
3RESIMENE 717.
The ingredient~? except for the paste and the polyurethane dispersion; were premixed. The paste and polyurethane disperslon were then mixed and the premixed ingredients w~re added.

Com~arative Exam~le U
Another whiSe, aqueous-based, polyurethane ba~ecoat wa3 prepared in a manner like Example ~ except that no aminoplast re3in was used.

Pa~nt Com~osites Example To a thermoplastic polye~ter film available a~ PMB 10231 from Eastman Rodak Company having a thicknes~ of about 7 mils a silver metallic basecoat composition is applied by roll coating at a 35 thickness of 1.5 mils. The ba~ecoat ic cured at 180F for 10 minutes. Metallic orientation was observed a~ shown by evaluating 2 ~

the flop. Two successive clearcoat layers, each 1.25 mil~ in thickness of the material described in ~xample J, ar~ spray applied and cured at 200F for 10 minutes. The adhesive from Rxample R is then applied at a thickness of about 3 mils to the polyester ilm on 5 the side opposite the paint layer.

Exam~le 2 A thermoplastic polyester film available as PMB 10231 ~rom Eastman Kodak Company having a thickness o about 7 mils and 10 containing a 3 mil layer of adhesive of Example L applied to one surface was coated on the opposed surface with the tlecoat of Example N to an average thickness of 0.02 mil by drawing down with a wire wound draw bar and dried at 180F for 10 minutes. The silver metallic basccoat compositlon o~ Example E was then applied over the 15 adhesion promoter by drawing down with a 6 inch Universal draw bar.
The basecoat, 1.5 mils in thickness, was cured by heating at 180F
for 10 minutes. Excellent metalIic orientation was ob~erved as shown by evaluatin& the flop. Successive clearcoat layers, each 1.25 mils in thickness of the material described in Example J, were applied by 20 drawing down with a 6 inch Universal draw bar and t~e coating cured at 180F for 10 minutes. The resultant free film was tested for solvent resistance by soaking the film under a watch glass with .
monohexyl ethyl of ethylene glycol and with toluene for a given time, followed by placing the film in a humidity cabinet at 100F and 100 25 percent relative humidity for 10 days. The results of the testing indicated an excellent overall solvent resistance by the film.
~,:
Exam~le 3 The thermoplastic polyester film precoated with adhesive as 30 described in Example 2 was coated on the side opposite the adhesive with the tiecoat of Example P by drawing down with a wire wound draw bar over about one-half of its surface to an average ehickness of 0.33 mil and dried for 10 minutes at 180F. The white basecoat of Example S was then applied at a thickness of 3.1 mils by drawing down 35 with a 6 inch Universal draw bar and cured by heating at 180F for 10 minutes. One clearcoat layer having a thickness of 2.5 mils of the 2~

material de~crlbed in Example J wa8 applied by drawing down with a 6 inch Univer~al draw bar and cured at 180F for 10 minutes.

ExamDle 4 A paint composite was made in the same way as 1s described in Example 3 except the tiecoat composition from Example Q WaQ u~ed lnstead of the composition from Example P.

Test l The paint composites made in Examples 3 and 4 were tested for adhesion by manually attempting to peel the paint layer ~combined basecoat and clearcoat layers) from the thermoplastic film. In the case of both composites, the paint layers were easily pulled from the film over those portions of the composite in which no tiecoat was 15 used between the thermoplast~c film and the paint layer. Over the portion of both composites where a tiecoat was applied between the paint layer and the thermoplastlc film, the palnt layer waR separated from the film only with difficulty.

ExamPle 5 The thermoplastic polyes~er film precoat~d with adhesive as described in Example 2 was coated on the side opposite the adhesive with the tiecoat of Example P as generally described in Example 2.
The white basecoat from Example T was then applied over th0 adhesion 25 promoter by drawing down with a 6 inch UniYersal draw bar at a thickness of 1.5 mils. The basecoat i~ cured at 180F for 10 minutes. A clearcoat layer of 2.5 mil~ in thicknesR of the ma~erial described in Example J was applied as described ln Example 3 and cured at 180F for 10 minutes.
Com~arative ExamPle 6 A paint composlte was made in the same way a~ Example 5 except that the white ba~ecoat was from Example U.

2~3~

Test 2 The paint composite~ from Example S and Comparative Example 6 were both vacuum formed over a steel panel. The~e panels were scribed from top to bottom and placed into a ~alt spray chamber for 5 14 days a~ter which the creepage from the ~cribe line was evaluated.
The panel having the paint composite from Example 5 showed no creepage indicating excellent adhesion of the paint composite to the substrate. The panel having the paint compo~lte from Example 6 eXhibited creepage, i.e., the paint layer shrunk back from the 10 carrier fllm ad~acent the scribe line.

~ ' ~

': ''~'~ '

Claims (22)

1. THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
   OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
   
   l. A paint composite article comprising:
   (a) a thermally deformable carrier film having first and second major surfaces, (b) an adhesive superimposed on the first surface of the thermally deformable carrier film, (c) an adhesion promoting tiecoat layer superimposed on the second surface of the carrier film, (d) a paint layer superimposed on said tiecoat layer, said paint layer comprising (i) a pigmented basecoat adhered to the thermally deformable carrier film through said tiecoat layer; and (ii) a transparent topcoat layer superimposed on the basecoat layer.
2. 2. The article of Claim 1 wherein the tiecoat layer comprises a mixture of an acrylic polymer and a polyurethane.
3. 3. The article of Claim 2 wherein the relative amount of acrylic polymer and polyurethane is in a proportion of from about 90 to 10 to about 10 to 90 based on the weight of resin solids in the tiecoat.
4. 4. The article of Claim 2 wherein the tiecoat layer contains an aminoplast.
5. 5. The article of Claim 4 wherein the aminoplast is present in an amount of from about 1 percent to about 35 percent by weight bayed on the weight of resin solids in the tiecoat.
6. 6. The article of Claim 4 wherein the aminoplast is a condensate of melamine and an aldehyde.
7. 7. The article of Claim 6 wherein the tiecoat layer contains a partially methylolated melamine-formaldehyde resin.
8. 8. The article of Claim 4 wherein the tiecoat layer includes an alkylbenzene.
9. 9. The article of Claim 8 wherein the alkylbenzene is present in an amount of from about 1 percent to about 35 percent by weight based on the weight of resin solids in the tiecoat.
10. 10. The article of Claim 8 wherein the alkylbenzene is toluene.
11. 11. The article of Claim 1 wherein the pigmented basecoat is derived from a thermoplastic polyurethane film-forming binder.
12. 12. The article of Claim 1 wherein the transparent topcoat is derived from a polyurethane polyol and a polyisocyanate curing agent.
13. 13. The article of Claim 11 wherein the basecoat layer has an elongation from about 150 percent to about 300 percent.
14. 14. The article of Claim 11 wherein the polyurethane in a polyester urethane.
15. 15. The article of Claim 1 wherein the adhesive is an acrylic latex polymer prepared from aliphatic acrylate monomers having pendant carbon chains of from about 3 to about 5 carbon atoms
16. 16. The article of Claim 12 wherein the polyurethane polyol is a polyester urethane polyol.
17. 17. The article of Claim l wherein a temporary protective cover is superimposed over the adhesive layer.
18. 18. The article of Claim 17 wherein the temporary protective cover consists of 8 material selected from paper and a polymeric material.
19. 19. The article of Claim 1 wherein the transparent clearcoat layer has an elongation of from about 150 percent to about 300 percent.
20. 20. The article of Claim l wherein the basecoat layer includes a metallic pigment applied with sufficient shear force to produce metallic orientation.
21. 21. The article of Claim 20 wherein the metallic pigment is selected from the group consisting of aluminum flake, copper bronze flake and metal oxide coated mica.
22. 22. The invention or inventions substantially as herein described and with reference to any of the preceding claims.