IT1111007B

In mould coating of moulded articles

Abstract

Articles made by molding sheet molding compound are coated by injecting into the sealed mold liquid compositions comprising (1) a vinyl ester resin formed by reaction of a poly epoxide resin and an unsaturated monocarboxylic acid, (2) a low shrink additive and (3) a silicate filler having a sheet-like structure such as a talc or a mica. These compositions are used to smooth surfaces, fill porosity and other voids and to eliminate or reduce sink marks. Coatings typically are cured in less than two minutes and appear able to provide many features of normal painting without paint facilities except possibly those needed for touch-up. They have good cross-hatch adhesion, and can adhere to an uncleaned SMC molding.

IT1111007B, drawing sheet 1 — Sheet 1 of 14

Term

No projected expiry on record.

4 claims: 2 independent, 2 dependent

1
CLAIMS * · * <«'». ** KU u WW | KW'N · '' '«V * *« fi » RIVENDICAZIONI *·*<«' ». ** KU u W W| KW'N·' ' '« V* * «fi» 1. Method for coating a molded piece produced from mass by molding by sheet forming after the piece has been formed and hardened to a fairly rigid state because1 the piece is not deformed by the injection of the coating composition within a space formed by separation of the two half-molds, while maintaining the mold in a tight condition, said method being characterized in that it involves the improvement consisting in injecting a Composition of coating comprising a mixture of a low shrinkage additive, a silicate filler having a lamellar structure and a vinyl ester resin formed by the reaction of a polyepoxide resin with an unsaturated monocarboxylic acid. 1. Metodo per rivestire un pezzo stampato prodottp da massa da stampaggio per formatura in foglio dopo che il pezzo e’ stato formato e fatto indurire sino ad uno stato abbastanza rigido perche1 il pezzo non venga deformato dalla iniezione della composizione di rivestimento entro uno spazio formato mediante separazione dei due semi-stampi, pur mantenendo lo stampo in una condizione di tenuta, detto metodo essendo caratterizzato dal fatto che comporta il perfezionamento consistente nell*iniettare una Composizione di rivestimento comprendente una miscela di un additivo per basso ritiro, un riempitivo a cara· tere di silicato avente una struttura lamellare ed una resina di vinilestere formata dalla reazione di una resina poliepossidica con un acido monocarbossi^ lico insaturo.
4
4 ·** * • ’ 4 4 4 4 4 4 ·** * • ’ 4 4 4 4 4 ..... ..... 4 4 Λ * 0 4 4 * · «I» · • · tt * · . * · · . .* .... 4 4 Λ * 0 4 4 *· «I» · • · tt * · . * · · . .* .... •.. » » •.. » » *. * · ·· · . ···· ». · ... *. * · ·· · . ···· ». · ... • . »... •.... • . »... •.... . . ····. ····. 4 4 4 4 * 4 4 4 4 * -43e 0,4 nm. -43e 0.4 nm. Milan, 19 January 1979 - Milano,19 Gennaio 1979 - 0* · 0* · 4 »» 1 * ή>> «·>» * »« «0 ì4 ili ,,. ♦ · * »« · 0 • · · · «• 4 • · 4 • ri 4 0> 4 0» 4 » » 1 * ή > > « · > » * » « « 0 ì4 ili,, . ♦· * » « · 0 • · · · « • 4 • · 4 • ri 4 0 > 4 0 » *0* *0*

Independent claims2

942 paragraphs in 43 sections, as filed

TITLE

PRIORITY

THE i GENERAI TIRE. 6 RUBBER CO. ~

AKRONì OHIO UiS.Ai *

IN-MOLD COATING; DI-PIECES. PRINTED THROUGH? FORMING IN DI-MASSEDAiSTAMPAGGIO.'j; SA · DOM. BREVI - No. 89 7,980 OF · 20 APRIL 1978

ί. $ ΛΑ ΐ!; / / '

CDIccb -Tlvc'i

4/62566 VC.

...........

| Protocol No. ______ 1? 17LA / _ 79_, MINISTRY OF INDUSTRY OF TRADE AND CRAFTS

Provincial Office for Commerce, Trade and Crafts in Milan

You/

COPY OF THE MINUTES Ol DEPOSIT FOR INDVSTRIAL INVENTION

The year 1975 II day nineteen of the month of

JANUARY at 12 o'clock and zero minutes one

THE GENERAL TIRE & RUBBER COMPANY coti s & do of US nationality In ron Akron, Ohio 44329 - USA, Via a'mezzo attorney International Patent Office Ine. C. GREGORJ and electively domiciliat a eoi * effects of law in Milan - Vìa Dogana ι at the authorized representative itself - presented to me, signed:

- Stamp application for the granting of a PATENT FOR INDUSTRIAL INVENTION

MAIN having TITLE ·

MOLD COVERING OF PIECES PRINTED BY SHEET FORMING

OF MOLDS FROM MOLDING

Inventor designat

Priority of patent application

USA,

No.

897,980 of 20 April 1978 supplementary to patent no. (question no.

dep. the granted accompanied by:

- Description In duplo di ri. 43 pages of writing.

- ^ Letter of appointment - Priority document and Italian translation (reserve)

- Authorization or transfer deed. (reserve)

- Certificate of payment on postal account n. 00668004 Made payable to the Registry Office for taxes and concessions

Rome of L.112,500 issued by the Office Postal of Milan 32 II 19-1.79 n. 603

- Stamp duty from 1.2.000. The application, descriptions and drawings listed above have been signed by the applicant and countersigned and stamped by me with the official stamp

THE DEPOSIT,

For certified copy of the original

THE OFFICIAL OFFICER

...........

p, the Director tóSssteri'K ”Itemsfr (Salvatore Ravalli)

THE DOI CHIEF

......... "(Dr ... fied

PATENTS J data) ..............

On.le MINISTRY OF INDUSTRY, TRADE AND CRAFTS

Central Patent Office - ROME 1 a firm

4/62566 ve.

19411A / 7

AW 'vi ·' ί ι

T1IK GENERAI ·, TIRE & RUBBER COMPANY (company organized and existing according to the Laws of the State of Ohio - USA) - with headquarters in:

One General Street, Akron, Ohio 44329 - USA of American nationality through an agent and domiciliary agent PATENT OFFICE ING. C. GREGORJ, Milan, Via Dogana 1 - apply for a patent certificate for industrial invention with the title! "

MOLD COVERING OF PIECES PRINTED THROUGH

SHEET FORMING OF MOLDS FOR MOLDING

PATENT APPLICATION PRIORITY IN - U*.SA. No. 897.980 of 20 April 1978 the following documents are attached:

1. - Description in duplo.

3. - Letter of assignment. IWsÌ.TpX'VX

4. - Att / of day vers. in o / o I ". plus one of L. 2,000.

5. - Priority document with Italian translation.

(reserve)

6 · - Deed of assignment (reserve)

Milan, 19 January 1979 UPfKW BKt VE ì M ind. C. òi -r\ '' GORJ

the Uffizi

GT-1181 4/62566 mb

Description of the invention having by title:

MOLD COVERING OF PIECES PRINTED THROUGH

SHEET FORMING OF MOLDS FOR MOLDING.

on behalf: THE GENERAL TIRE & RUBBER COMPANY in: One General Street, Akron, Ohio 44329 (US of US nationality and electively domici

Hata in Milan, Via Dogana 1, at the patent attorney Ing. C. Gregorj Filed on 1 0 Gfi'v5, N.

+1 + -H-4 + 4 +

The present invention relates to a mold coating process for applying layers of coating to molded parts formed by molding masses for sheet forming. SMC (molding masses for sheet forming) are widely used for molding operations. high volumes of large rigid parts.

Factors which favored this use were rapid hardening and easy sliding of the S {4C, high strength and rigidity, smoothness, low shrinkage, dimensional stability, and relatively low cost. However, an even further improvement in the quality of the surface for external automotive parts is of primary necessity.

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Sources of particular inconveniences are po.A.)

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in O> o 01 hi cn ir oO 9 Ó t tó • Sffl, rosity, the presence of undulations and cavities on the surface. None of these defects are effectively eliminated or masked through normal painting operations. Therefore, it is normal practice to examine all the parts (or pieces) and pass the defective ones again through the hand grouting, sandblasting, painting and examination stations, until an acceptable appearance is obtained / In the event that it cannot the presence of cavities being tolerated, it is common practice to form a separate part capable of acting with: τ; pll · '· ·' join to '-' / •• m. Harness; a: 1 with reinforcement and fixing rions.

Another method used has been that of forming a surface layer known as gelcoaf on parts so as to cover defects present on the substrate. In principle, this is done by coating the hot mold before a filler is subjected to a molding operation, see U.S. Pat. 3,940,468, - -.....-.....- · - «......, ~: and · * ·· • · ·· · '

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0 "or forming a gel-coat on a previously printed part, as can be seen from Japanese patent application No. 34210/62.

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None of the aforementioned methods of application of gel coat other than urethane seems to have received!

significant experimentation in the forming of SMC with hot metal mold and counter-mold, for a variety of reasons. Probably, the mag-! giore obstacle, from a technical point of view, was;

ì i

consisting of the lack of coating layers which adhere to the SMC if not through co-hardening. That is to say, if such coating layers are applied first, the coating must be hardened enough to resist tearing during the SMC flow , while still being fairly under-hardened by cross-linking with SMCs. Similarly, when SMCs are first formed, it is necessary to open the mold before the SMC is fully cured, which is generally inconvenient from a practical point of view, since thin sections of parts or pieces exhibit hardening much earlier. that sections of considerable thickness are adequately hardened.

One way to get around the above problems is to use resin impregnated sheets, instead of surface coatings like • · · »4 4 · * 4 4«

4*4« »4>4

4 ·· gel-coat. Another method has been the use of unimpregnated sheets capable of function4

1 »• W * Ζ]« Μ use a gel-coat as a bonding layer on the sides, first of which a gel-coat can cling, an advantage relative to both within which to oppose and subsequently

The striking methods is rappre »« «»

»» · W * »»

?. ·· * »» felt by the possibility of obtaining surfaces with printed configurations. However, the usefulness is limited by the fact that such sheets can present folds or tears on many non-planar parts.

Another method consisted of binding the mold coating material to the substrate through isocyanic reactivity, using a two component mold coating material. Two-component systems require mixing control, as can be seen from U.S. Pat. 4081.571.

The patent further describes the use of talc in the mold coating composition.

In consideration of the above difficulties, attempts were made to obtain liquid compositions which could be printed on, and to adhere to, the hardened SMC parts. As a result of this research, surface coatings capable of being applied by forming on parts of SMC were found.

The coating process used consists in the compression molding of. traditional type, of

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4 * 4. ··· • · • · · a part of SMC, separation of the half-mold, maintaining a seal between the cutting edge formed by the upper sides of the mold extending below the upper edge of the top of the lower half-mold. The mold coating material is then fed and the mold is closed so that the coating layer is distributed and hardened. 1 Injection coatings do not require mixing of reactive components upon, or immediately prior to, the injection (or injection). Coating operations!

according to the present invention they are also less expensive than those employing isocyanate, of the prior art. Such coatings can also be applied to hardened SMC parts with obtaining acceptable levels of. adhesion according to the tearing method on crossed incision.

In order to obtain coatings having the physical characteristics desired by car manufacturers, without the disadvantages relating to the prior art coating compositions, a mixture of 2 resinous components, monomer generally in a di / vinyl solvent, and a filler are used having a lamellar structure.

It was found unexpectedly,

4 4 4 4 • 4 · 4 · :·

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4 4 • 44 that a silicate-based filler having a lamellar structure provides an unexpected improvement in the adhesion evaluated according to the above-mentioned cross-etching tear method. With adhesion according to the tearing method on crossed incision yes. means that the coating resists on the substrate after a cross-etching pattern has been traced in the coating subsequently an adhesive tape has been applied to the etched surface and streaked away. If 80% of the coating remains on the substrate after this treatment, this coating is said to exhibit good adhesion to the cross-incision tear test. One of the theories is that the lamellar structure of the filler reduces the cohesion.

The end of the coating up to the point where the adhesion failure is secondary, furthermore the coating;

it has such a poor cohesion that it {ί

will break before. can be torn off in the form of a sheet. '

Silicate or silicate having a lamellar structure are described in Kirk-Othmer Ehcyclopedi ^ of Chemical Technology, Second Edition, Vol. 18, p ^ 49, Interscience Publishers, New York, NY (1969)

The filler having a lamellar structure can

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SHORT OFFICE 11 GFìfìGOR

-7• 44

4 »To be chosen from the silicate groups comprising talc and mica * The ratio between length and thickness has a minimum value of 4 and a maximum value of 10,000. This ratio is preferred between 10 and 1000. The particulate length of the fillers having a lamellar structure can1 vary between 0.001 mm and 0.4 min, preferably between 0.01 mm and 0.4 mm

Canadian talcs are the preferred talcs since they exhibit a lesser tendency to use the resinous component of the sheet molding mass. For a more rigid coating, mica fillers are preferred.

The first resinous component consists of a vinyl ester resin. Another component consisted of a material which is incompatible with the vinyl ester resin. Materials commonly used as low shrinkage additives meet this requirement. The low shrinkage additive is believed to cause a decrease in the tensile strength of the surface coating * so that it cannot be extracted in a single piece, nor transmit effort. Referring to 100 parts of resin from foreign wines, the low shrinkage additive is present in

- 4 »♦ 4·· »4 » 4

4 4 « 4 4 4 4 4 4 4 4 4 4 4

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4 4 ··*·. 4 4 4 « 1 a content level between 10 and 50 parts

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Φ »** •! Preferably between 20 and 40 parts by weight. Both the fine ester and the low shrinkage additive are normally dissolved in styrene. The additive for Lassò shrinkage reduces shrinkage than the coating in the mold

V undergoes during hardening.

Vinylester resins are generally prepared by reacting roughly equivalent proportions of a polyepoxide resin and an unsaturated monocarboxylic acid in which bonds of the type are formed

------------- <ÌoCH2CHCH2O ~ .......-

OH and the resin is on. many have polymerizable unsaturated end groups. For example, two methacrylic acid equivalents can be reacted with two equivalents of a polyepoxide resin to produce a vinyl ester resin.

The preferred vinylester resins are those which contain an average of carboxylic groups per mop.eί cola between 0 and 1. A free carboxyl group is

is a carboxylic acid radical or an ionized carboxyl group bearing a negative charge.

Vinylester resins are described in the patent

US No. 3,367,992 to Bearden in which he issued ~ •

4 4 • «

4 4

4*· 4 ·

4 4 b t.

there . f 'ί

-9 esters of carboxylic acids of hydroxyalkyl acres

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4 · «« »· * •« «» with 4 • 04 «· 4 4« sides or methacrylates are made to react with polyepoxide sins · Bowen, in the statutory patents tensions No. 3.066.112 and No. «5.179 * 623» describes the Preparation of vinyl ester resins from carboxylic acids, for example acrylic acid and methacrylic acid. Bowen further describes an alternative preparation method, in which a glycidyl methacrylate or acrylate is reacted with the sodium salt of a dioxyl phenol, for example Bisphenol A. Vinylester resins based on epoxy novolac resins are described in the patent.

Bekete et al.

Tunisian No. 3,301,743 to Bekete et al. / in addition, in the United States patent No. 3,256,226, vinylester resins in. whereby the molecular weight of the polyepoxide is increased by reacting a di-carboxy acid with the polyepoxide resin. lico, as well as acrylic acid, and so on. Other bifunctional compounds containing a group which is reactive with an epoxy group, for example a * amin, a mercaptan and the like, can be used [instead of dicarboxylic acid. All the resins described above that contain the characteristic king bonds · ··; * * * 4 single-row • ♦ • 00 • »'4

IMI •• —OOOHgCHOHgO— vPHGIO Bi ii Vt I

-10 and polymerizable unsaturated end groups are classified in the present context as vinyl ester resins. The preparation of vinyl ester resins is fully described in the aforementioned patents.

In addition, but not preferably, it is intended to include in the definition of vinyl ester resins those resins in which the secondary hydroosyl group formed by the interaction of an epoxy group with a carboxylic group has been difficult to react with a diearboxylic anhydride to produce hanging carboxylic groups . The preparation of these materials is described in U.S. Pat. No. 3,466,259 to Jernigan. A variety of saturated and unsaturated anhydrides similar to those described as usable in the preparation of the polyester resins can be used in proportions ranging from at least about 0.1 moles of anhydride per hydroxy group equivalent up to a quantity sufficient to react with each hydroxyl A reaction temperature between about 25 ° and 150 ° C is suitable and any of the well known vinyl polymerization inhibitors can be added in order to prevent polymerization

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- -11 IMìWi OFFICE

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In short, any of the known polyepoxides can be used in the preparation of the vinyl ester renders of the present invention. Glycidylpolyether and polyhydric alcohols as well as polyhydric phenols, epoxy resins suitable for retarding lf <are useful.

flame propagation based on tetrabromo-bisi ι

phenol A, novolaoche epoxy, epoxy oxidized fatty acids or acids of drying oils, epoxidized diolefins, epoxidized di-unsaturated acid esters, coime also epoxidized unsaturated polyesters, provided that it contains more than one oxiranic group per molecule. The polyepoxides can be of the monomeric type or the polymeric ones. !

Preferred polyepoxides are represented by (i

polyhydric alcohol glycidylpolyethers or polyhydric diphenyl alcohols having weights per epoxy group "

ranging from about 150 to 2000. These polyepoxides are ordinarily prepared by reacting at least about 2 moles of an epialogenohydrin or glioerol dialogenohydrina with one mole of the polyhydroxy alcohol of the polyhydroxy phenol, and one!

The amount of caustic alkali sufficient to combine with the halogen halogenhydrin. The products are --- zie.lln «nfificnza of a group

12w η / ψ ì f.

,····.

• is · Λ • 4 4 · • · · · ··· «4 4 4 epoxy per molecule, ie a degree of equivalence with respect to the 1,2-epoxy group greater than one.

Unsaturated monocarboseilic acids include acrylic acid, methacrylic acid, halogenated acrylic or methacrylic acids, cinnamic acid and the like and mixtures thereof, and hydroxyalkyl acrylic or methacrylic hemi-esters of thicarboxylic acids, as described in U.S. Pat. No. 5,567,992 wherein hydroxyalkyl group preferably has from to 6 carbon atoms.

Dicarboxylic acid anhydrides useful for modifying the vinyl ester resin include unsaturated anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, the various substituted maleic anhydrides and the like, as well as a variety of saturated anhydrides, for example phthalic anhydride, anoride , tetrabromophtallic anhydride and the like.

A variety of stable copolymer monomers are available and are suitable, and include alkenylaromatic monomers, alkyl ether of acrylic acid and methacrylic acid, vinyl acetate, acrylonitrile, diathylmaleate, diallyl phthalate, acid •

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«4 •••• ι 4» · · 'acrylic and methacrylic, and the like, as well as their mixtures.

-13 THE I ICIO SHORT 111

-NG. C. GREGORJ "· ·.

* « ···* valkenilaromaticl monomers such as for example styrene, alpha-methylstyrene, vinlltoluenf are preferred. substituted styrene alehyl, such as for example t-butyl styrene, and so on, halogen-substituted styrenes such as for example chlorostyrene, dicorostyrene and the like

The preferred low shrinkage additive or additive which causes a weakening of the film, and the polyvinyl acetate. Polyvinyl acetate copolymers can also be used.

The vinyl acetate thermoplastic polymers suitable for the purposes of the present invention contain an average variant between 0 and about 10, and preferably between 0 and about 3, of carboxyl groups per molecule. On a weight basis, suitable thermoplastic polymers contain from about 0 to about 5 / weight, preferably from about 0 to about 2% by weight, with a combined carboxylic place. These polymers can be prepared in various ways, as well known in the art, by means of!

(1) Polymerization of vinyl acetate with a copolymerizable carboxylic acid to produce a copolymer having an average of at least one carboxyl group per molecule. Suitable copolymerizable carboxylic acids are the unsaturated polycarboxylic acids described above, as well as acids.

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4 4 4 · unsaturated nocarboxylic acids having the formula:

in which a represents an integer comprised between 5 and 10, preferably between 5 and 6. Examples of acids falling within the scope of the above are the following: acrylic acid, methacrylic acid, orotonic acid, ieocrotonic acid, vinylacetic acid, lime acid oo, hexenic acid, and yes.

(2) Reaction of poly (vinyl acetate) with a polymerizable carboxylic acid, as for example. acids described in (1) above, for formal a block copolymer or a graft copolymer.

of the

0) Partial hydroliases / polyvinyl acetate) generally up to a maximum value of 20 $ referred to the total number of ester groups! originally it presented and partial or total esterification of the hydroxyl groups with a polycarboxylic acid or a relative anhydride, according to what previously

described in this context. i, · ♦ »

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(4) More preferably, the vinyl acetate is a mopolymer. In the formulation of the compositions of the present invention, it is common practice to mix a polymerizable ethylenically unsaturated monomer with the polymers of vinyl acetate.

-15 OFFICE EFHVnII I! \ H, cross-link the vinylester resin until a thermoset product is obtained · Vinyl monomers have the formula:

CH? and CH-R wherein R represents a group having a carbon-carbon, carbon-oxygen or carbon nitrogen group in conjugation with the vinyl group. Groups having such unsaturation conjugated with the vinyl group are the aryl, ketonic, heterocyclic), ntryl, carbalkoxyl, carbonose and amide groups.

Specific vinyl monomers include the following:

wherein R represents aryl: styrene, halogenated styrenes such as for example chlorostyrene, p-iodostyrene, m-fluorostyrene, dichlorostyrene and the like? alebil-sosti styrenes. all such as p-methylstyrene »ρ-ethylstyrene, o-tert • butylstyrene and the like? alkoxy and aryloxy-substituted styrenes, such as for example petoxystyrene, p-propoxy styrene, p-phenoxy. styrene and the like?

in which. R is a ketone group? ethylvinyl ketone, n-propylvinylketone, phenylvinyl ketones * and the like?

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4> «· I 4 • 4 4 4 · •

• · v 4 • 44 «* in which. R is a heterocyclic group? vinylpyridine, vinylquinoline, vinylpyrrole, vinylcarbazole,

BRE.Vfc OFFICE: TH ING. C. X & frGORJ • 16vinyl thiophene and symili, wherein R is a nitrienic group; stellions tr 11 ^ and the like, where R is * a. amidic group; acrylamide, bicycloeptilacrylamide, dioetonacrylamide and the like, wherein Re * is a carboxyl group; acrylic acid and the like, wherein R is a carboxylic group; methyl-5 acrylate, butylacrylate, octylaorylate, laurylacrylate, cyclohexylacrylate, phenylacrylate, bendyl acrylate and the like.

Also suitable are diaphthalate and the like.

The amount of ethylenically unsaturated monomer used may vary within wide areas.

For example, the monomer can be used in amounts ranging from about 10 to about 60% by weight based on the added weight of the bromomer and the polyvinyl chloride.

acetate. It is preferable to employ from about 20 to about

THE

50% by weight of ethylenically unsaturated monomer, | referred to the added weight of the menomerò and of the polyvinyl

I acetate. The same unsaturated monomers can be used as solvents for the other low shrinkage additives and for the vinyl ester resin. The unsaturated monomer is normally present at a content level of between 50 and 400 parts © '_TO _ · ··,, ••4*4 « ·♦·.*·· :. : »*··. :;·· , ·· · \ · ... ·».· . ,· ···· . ···· • · · ...

• · · ·. · . *. * ·

-17UH JCK> FU J VI 11 11 ING, (AA GOKJ preferably between 100 and 200 parts referred to 100 parts of vinyl ester resin. Preferably there are from 1 to 3 equivalents of vinyl monomer for equivalent of unsaturation of vinyl ester.

Other preferred low shrinkage additives comprpn. polyhydric rubbers · In the term "polyhydric rubbers" we intend to include, in the present context, homopolymers or copolymers of conjugated alene monomers such as butadiene. It is also intended to include in the present definition polymers containing at least about 30% by weight of diene monomer , the complement 100 comprising at least one other copolymerizable monomer, such as for example styrene or acrylonitrile. It is also intended to include random, graft and block polymers, of which a wide variety is commercially available

I or is easily prepared by known κοίλοι!

of polymerization.

Although polyamide rubbers with only 30% by weight of a diene monomer provide improvements according to the invention, better characteristics in surface coatings are found when diene monomer forms at least about 40% by weight of the polymer and polymers. in correspondence or per day

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44 above this level are preferred for the present invention.

Conjugated dionomers, include butadiene, the various halogen- and lower alkyl-substituted derivatives thereof and monomers of a similar type. Mixtures of said diene monomers are often used to impart certain desired characteristics to polyhydric rubbers. Polybutadiene is a preferred polyamide.

Copolymerizable monomers which can be used with said alene monomers include nitriite monomers, such as for example acrylonitrile, methacrylonitrile and the like, and alkenylaromatic monomers such as for example styrene, a-methyl styrene, vinyltoluene, halogen- and alkyl-substituted styrenes, such as chlorostyrene or t butyl styrene. Preferred copolymers include styrene-butadiene copolymers and in particular block copolymers thereof. ii

The unsaturated polyhydric rubbers of the present invention can be prepared through a variety of well-known methods, and since

The present invention relates to the use of said rubbers and not to their preparation,

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* «· · • ·. * · * I • * »4» t *** ♦ · »♦ V / · * ·. . Testi · · ♦ · yes texts and numerous, patents that can be cor) sult in relation to said preparation methods, such as the chapter on butadiene polymers and copolymers, due to W. Saltman, in Enoyclopedia of Polymer Science and Technology '1,

Vol. 2, Interscience Publishers, 1965 * the preferred polyamide rubber has an inherent viscosity of between about 0.5 and 1.2 deci · liters / gram or a molecular weight of between at least about 15 * 000 and 20,000.

An improvement in the characteristics of the surface coatings seems to be related to the molecular position of the polyedienic rubber. That is to say polyamide rubbers with higher molecular weight, if used at the lowest concentration, show a greater improvement than when they are used at lower molecular weights. Accordingly, it is preferable to use polyide rubbers having a viscosity of at least about 0.5 declitres / gram.

Advantageously, it has been found that the viscosity range can extend in the direction of an increase of up to about 2 deciliters / gram if the system also contains at least about 1 * 4 * 4

· ... ·. ··,. · „» ··· »<* 4 4 4 • · 4 4 · -« · • »r *« -:

I · k · parts of an inert filler, such as ar-20Uf HCiO B, m, 'VfF 'II

ING ',, GGt; J • 0 «Μ *

0 * '> 0 0 0 0 ♦ · * * · · 0 • «· · 0 0 gilla and the like, per 100 parts of resin and rubber · This' f · *« e1 particularly significant for the fact that • 0 thermosetting resin systems are ordered formally filling fillers in the corner-f / .J j · * · · * cial use, in order to give certain characters ·····

I [

rietics, such as resistance to atmospheric agents and so on, and for economic reasons

The inherent viscosity e1 defined as follows:

- (2.505 1ο6ιθηΓ) / (Ο) where:

ηΓ "(Η / ^) e (and time for the often e

A time for a solution of 0.15 g of polymer / 100 ml of toluene

C and concentration.

viscosimetric units are expressed in deciliters / gram. !

the

Other low shrinkage additives that can be used include thenimetlimethacrylate, polyethylene and polystyrene.

In addition to the vinylester resin, an unsaturated polyester resin may optionally be present. The polyester resin is always at a level of between 0 and 100 parts of vinylester resin.

by weight

-21ΜΠΗΠΟ Γί / »· ·.

···* • · ·

99 9 9 * * * · • · · * · • Λ 4 · 9 4 4 ··.. .

4 * 4 4«· •44·· 4 4··· •••44

Generally, in the preparation of suitable polyesters, an ethylenically unsaturated dicarboxylic acid, such as, for example, maleic acid, fumic acid, itaconic acid, or the like, is interested in an alkylene glycol or polyalcbilen glycol having a molecular weight between cìrc ^

1000 and 8000 or similar. Often, dicarboxylic acids free of ethylene unsaturation, such as for example phthalic acid, isophthalic acid, tetrombromophthalic acid, chlorendic acid, oedipic acid, suceinic acid and the like, can be used within a molar range ranging from 0.25 to 15 moles for mole of dicarboxylic acid oc, β-unsaturated. It is understood that the appropriate acid anhydrides, when present, can be used, and are ordinarily preferred when available.

The polyester component of glycol or polyhydroxy alcohol is used normally in stoichiometric quantities or in light excess with respect to the sum of the acids. The excess of polyhydroxy alcohol will sometimes be $ 20-25 and ordinarily $ 2-10.

These unsaturated polyesters can be so prepared by heating a catalyzed mixture of the polyhydroxy alcohol with the carbonic acid. :

. . ...» * · . · ·

·..· · ,·

.. * · · · · • ·...

». * » » » • · · ·.. • · ·..

.....

♦ · · ♦ · * ar

UFUCIO Bi ll Vfc 1 1 1 ING \ C. ^ Rf GORJ

Bilico ο 1 * relative anhydride in the appropriate molar proportions »and high temperatures, normally at a temperature ranging from about 150 ° to 225 ° C, for a period of time varying from about 5 to 15 hours * Inhibitors can be added with advantage of polymerization, such as for example tbutiloatecolo.

It is also possible to prepare unsaturated polyesters directly from the appropriate oxide by copolymer

polymerization with an anhydride, for example propylene-oxide can be used in place of propylene glycol and copolymerized with maleic anhydride and phthalic anhydride. A further description of these well known resins is not necessary in the present context.

Normally, the composition to be applied is given as a gel-coat according to

the present invention is dissolved or suspended in i

a vinyl monomer, of the type described above with regard to the vinyl alcohol · The vinyl monomer can * be present at a level

The contents of between 10 and 200, and preferably between 50 and 150 parts, referring to 100 parts by weight of vinyl ester.

Ordinary agents may also be present. * ·

4 4 4 4 ···· ** · **•4 •

• 4 4 » 4 ··** ·· · *· *4 • 4 \ · •4 4 4

4 ’

4 4 4 4 ····. 4 4 4 4* • 4 4 4 4 » 4 4 4

4 4 4 4

4 • 4 4 • 4 4 4

?.:·

4 • 4 ·

4 4 « .··.·· • 4 4 4

4··»

4·

4 4 4

-23VA if , w«

/.'Λ, *** «• ··· · • * * · ·« · ··., · «· Emulsifiers, inhibitors and fillers; see, for a complete description of the above materials, the United States patents No.>. 466.259;

No.3.548.030; No.3.564 "074; No.3.674.893; No.3.83 ^ .600 and No.3.683.045. It is preferable, however, that the ordinary fillers make up less than 50% of the normal load of fillers and that the fillers of the present invention having a lamellar-like structure make up most or all of the filler content.

The preferred SMC type materials used in the practical implementation of the present invention as substrates for mold coating are those which are based on vinyl ester, isophthalic acid and propylene glycol fumarate based polyester systems. Molds with chromed cutting edges, suitable for. " * ···· ν? · * Ϊ · Ϊ ....

. · · ♦ » .*····

·. · ...

. * ·*··

*... » • ····

». · ...

• · ·. » · SMC compression molding, they are suitable for containing and releasing mold coated parts. Ordinarily, molds are used whose surfaces separate in a regular manner as the press is opened. Furthermore, it is necessary to observe |

that the thickness of the coating varies with the draft angle of the surface of the substrate; thicknesses typically vary between about 0f0l mm on low draft surfaces and θ, 07 nu »on high surfaces - 24— jl i ICIO BKEVt I II ing. cCòhraon, '»4 · ·« »·, *. *. »'' '• * * ·» * »• 4> · * · t draft · This * occurs due to the fact that the opening of the mold available for coating ^t if, determined perpendicularly to the surface of the part (or piece), the angle of the draft changes with the breast of the part.

According to what has been previously mentioned, the main method hitherto used for appli · |

Dear surface coating layers consists of slightly separating the half-molds, injecting the coating material into an area formed by a surface with a high draft angle on the SMC part and then closing the mold. This method allows you to design the cutting edges in order to obtain a seal, liquid at all times.

The best way to inject the coating material is to use an injection nozzle which has a pin extending through the opening in the nozzle!

In the closed position, the end of the pin formed a small portion of the inner surface of the mold. In the open position, the pin is pushed back from the mold and the nozzle opening, allowing coating material to be injected into the mold. The pin is stabilized against rotation so that it

V »*». . . • · · ·. · ·· »·· ·.

··.

... • * · · . · · · · ··.· · ,· · * « « ·· ». » . ··♦· • · · < · ·

». »...

• * ·. · * ». »Z and

king

Always form a uniform surface with the mold wall in the closed position, the nozzle is thermally insulated from the mold and is water cooled.

Have fillers been used such as to provide a coating layer of thickness up to 0.5 mm, but an average of 0.0? - 0.10 mm of coating layer was generally sufficient to provide both opacity and complete coverage. Since the normal SMC part has an average thickness of 2.5 mm, a typical surface coating layer required about 0, 03 - 0.05 g of coating per gram of SMC used, the simple deposition of a coating charge, often a "bubble" or strip formed by high pressure injection, ordinarily provided complete coverage.

Mold temperatures between 140 and 160 ° C have provided satisfactory coating layers,

A minimum hardening time of between 10 and 30 seconds, at 150 ° C, is used, and even slower curing speeds are sometimes required, to prevent too rapid gelling which would result in incomplete coverage,

Higher molding pressures, as expected, result in better coverage of 'a · · · · · · ·, ·. * ·. a »• · · · • ·· * a · * ...

• . ....

·♦··. 4 4 4 4 4

Uf 'ΛνΛ

-26»

«. · · · ·!· . . · · · · • · ·. · • ....

more inclined surfaces, and lower draft. However, the typical pressures required to form the patches! based on SMC are also re sul. generally suitable for providing a complete coating.

the main purpose of the gel-ooat coating was to fill voids, reduce cavities and act as a substitute for the primer layer - primer - sealant now commonly used by common SMC printers.

Mold coated parts have passed the proyes normally carried out on vehicles, except for some tests of resistance to humidity, immersion in water, adhesion and adhesion. gravaiometer, of i ί

painted panels * The tear tests on cross-etching according to the order method showed better results than similar compositions for coating in mold loaded with calcium-carbp born.

Although research has been directed, among other things, to replace a primer layer application operation (priming), in some cases said priming operation is still necessary to pass the required tests. Coatings have also been made which appear suitable as streps

*......

........

• * .... ..... .

...

··., : · . · · · . .····· • · * · · ···· · ,· · · · ·.

• 4 4 4 4 . · ·· · • · · ...

« » · * · ·

..... * . * * 1, Νβ· C\ 5? FGOfiJ «• MI» · ·

-27 pigmented finishes, estimate with regard to covering power, primlng, or painting *

Coating layers with good conductivity and adhesion were also prepared by inclusion of graphite having a lamellar structure, 4 4 4 4 4. · • ·. »· · ·» • · · · <· «···· ·.

y. · * · · · * * · · *. · · * ·: ·· ..

, ♦ ·, «· · · · • * · · * ·. ·, ·., * · · · · * 4 «» »• * · ·. · • · * · »· although the constancy of reproducibility is questionable. As can be seen, there is considerable flexibility in the choice of ingredients and in the resulting ethical characteristics in the coating layer. In the following examples, as well as elsewhere in the description and in the claims, all parts and percentages are by weight, unless otherwise specified.

EXAMPLE I

A panel with a grid opening of an Oldsmobile 1973 was molded using a standard type β massa unsaturated polyester sheet molding mass from Rohm and Haas.

The press, manufactured by Erie Press in Erie

THE

PA - USA - was used using a pressure of 68.95 kPa (1000 psi). All the presses produced by the various manufacturers have automatic vent control devices, or such devices can be added.

automatic press release cycle came

-deUH IU '. Η. ,,. 'AJ ι.

ING ,.

♦ tV .. · · * *. ··· * *. 0 "* 00 * * 0 * 0 •.

. · ... * • to . t. .....,, * * · «* · ......

activated to check. sequence necessary for molding the pieces, opening the mold to inject the coating material into the mold and re-closing at an appropriate pressure to coat the pieces. The pieces were printed and presented an excellent appearance. They were tested and passed all tests carried out. The coating was of such a high thickness that an adhesion test could not be carried out according to the tearing method on a cross incision. The coating had a thickness of 2.2 mm. The molding sequence was as follows.

All four timers on the press were used. The timer No. 1 (Tl.) Is the pre-curing timer and was set at a period of 2.5 minutes to print and harden the piece. When the hardening time has elapsed and the press discharges, the timer T-2 times the oil flow for the return of the piston (set at 1-11 / 12 seconds), and ole * causes the mold to open at 15 mm · Mold coating material was then injected into the mold, the timer relating to the injector being the T-3 timer which, in this case, was · * »0 • 4 ♦ • • 00

- * · · * 0 A 0 »« '· * * 0 0 * 0 0 0

0 « » 0 » • » 0 0 0 ·*.

0 0 «· set to 13 seconds · When the time pre-sets it

-29ΙΙΠ, '' ·:.Λ.

tri ·· ·· • »· · *

4» * • · · · · • ’ 4 · · * « * · · · · • ·

4 · »4 ••• 4 · 4 for the T-3 was spent, the press lowered * again and returned * under load and was maintained in such conditions for a time controlled by the teak pore T-4, until the layer hardened coating them.

This entire sequence presented an excellent operation for molded and coated parts and the press correctly repeated the same sequence every time, except for the operation of T-2, the action of which resulted in a displacement difference of 3 mm, from both sides once in a while This is understandable, since the required withdrawal force can fluctuate and fluctuate with variations in the weight of the filler and in the position of the filler when the cutting edges have an aperture as wide as this part*

With this system, the pre-hardening pressure and the hardening pressure were different, so as to eliminate cavities above ridges and ribs. The hardening pressure in the mold was reduced to 76.740 kg / area in the wing end!

Γ riore (100 tons / area in the front end) less than the pre-hardening load, to reduce the

tendency of pieces to crack · '·' · · 4 4

.........

* · 4 4 4 •• 4 4 4 «, ····::. : 4/4 4 4 4 * 4 4 »· * 444 4 / * · 4 # β · · · 4

4 * 4 4 4

4 4 4 4 4 * ·· *: 4 4 I · 'funf

TT »\ λλγτμγ, Το Λ4 4 fiVi-Pon · ί or« VAVAMÌ AH + .A <ì fi Φ — 2 VÌfiUfi

SHORT OFFICE hi INO. C ^ F.OORJ

-300 0 0 0 (used to activate the injector and another signal from the T-3 is used to deactivate it. This1 eliminates the need for a separate injector timer. Injection barring, sealing condition was maintained with the cutting edge of the mold. The following mold coating composition was the only one injected through a nozzle. cooled injection, positioned between the mold separation surfaces and so as to carry out the injection in the direction pa «*1 ** 00 «• ·, 4 4 · * 0 • 0 0 0 0 0 00 · 00, φ

........

• * · · t 0 «0» · • 0 0 0 0 0 0 slowdown with respect to the separation surfaces.

THE

The coating composition used had the following formulation ______)

Styrene vinyl ester resin (believed to be made up of 66% of copolymer of acrylic acid and bisphenol A diglycidyl ether in 44% of styrene) "200," J

40% of polyvinyl acetate, free from carbonyl groups, dissolved in 60% of styrene2^ 80

1) Bow XB 9013.02

2) Union Carbide BPg ©

Ιΐν, · (ν 1'Ηί Vi ·:! Ι

-31 (Continued)

Components

Styrene

Canadian talc, average particle length 0.03 mm

Set off

200 iNG „C, GRi: GObJ • · · · * * * * · ·> * * MI» • «» 4 · • MM • * »» * • * »· · * *» • 4 4 · * MM • · · »•• 44

4 » 4 · •444

♦ 4 ·

4 4 4 * * 4* • 4* *444 •4*·

4 4

4 4 4

Mica suz <rorite (phlogopite), average particle length 0.03 mm 140

Tertiary butyl benzoate 6

Saturated solution of parabenzoquinone in

Btyrene (inhibitor) 0.6

Piaichi! phosphate (mold release agent) 3.0

3) Belac ME Pu Pont them

A series of five formulations was prepared in order to determine physical laboratory characteristics. The formulations contained the same materials as in Example 1, with the difference that the quantities and types of fillers having a lamellar-like structure were varied.

ΙΑ %%

W vi

-52.

* -Ι ο

CM

Ol in O \ vo f »«

0Ί o

or "-Ί in ri

CO

CM in

co ri <CM

ΟΊ t— · o

CM in in

OR

Ιo vo

CO o

·—

Or if

in o

o rl

OR

- = r in

CO in ri

CO

P ri

V. **, · „· I., 4 4 j» '.

»4M« · * ·· * * * • »ύ -

in o

Ciri o

-T

OR ?

s tì in ri in r

4·^

Or in

H &

tì til o

tì ω

<td>or</td><td></td><td>you</td><td>Ρ-Ί</td><td>tìtSJ</td><td></td><td></td>

<td>& OR</td><td>• H you</td><td>•re +></td><td></td><td>• rlrj -little</td><td>V</td><td>re you</td>

tì o

• ri tì • E o

to tì ri tì h

oo • ri ri H 'ri

ti) <or • H «R -P • * -J i. «• · <» * ¥ • »m 4;is tì ci o

tì tì

IS1 * 4 * 4 β

* · ** '•, * «·. · Ν ·. * · I t ***** * * · * * * * 4 4 * ♦ · 4 «4 and · *« ¥ ··· '·.

• · · * · «

Π c

• rt

Ό tì tì o

• p

I

• g tì

-P

P tì fi • P

UH ΚΊ · ,. f ι Η: V: '/ -f

-33 The following are the process parameters and i |

The results of the tests relating to the formula "B" i

Molding temperature - 295 ° P / 3QO ° iL (146 / l49 ° C)

Hardening time of SMC Hardening time of the coating min »min · li 'F». · * • 4 · · • ·! · ·· * ·

4 • 4 4 » · • 44*4 *.··*·

Ϊ * • · 4 · · * •• 4 • 4 ***** •• 444

4·« • 4 4

14 4 time tote le

..... • «· · · min *

Coating thickness

Gravelometer

Hardness determined oon jnatItaWriting (Scribe X)

Adhesion according to the tearing method on crossed incision

0.23 mm

Difficult to determine ^

The kings on painted Noiji samples seem to be around 6

P

Good

- Good i

Adhesion to raw panel

Substrate and coating ΐ

do they appear to have a mechanical lock rather than a chemical bond?

when the coating is scraped from the substrate, the surface has a shiny appearance.

The superior a

The thickness of 0.23 mm was the minimum thickness that could be used with a still adequate coating of a 16-inch x 16-inch flat sheet

-34 (40.6 x 40.6 cm). Talc No. 5 contains a greater amount of calcium carbonate than Talc No. 505.

No .5. (CìANA3) BSN2,

Typical chemical analysis ai ii t-Si ur ~ 1 jn uer- «·. * · *» -R · χ. «· Τι .-», - »

SiOg silica

Calcium oxide CaO

Aluminum oxide Al ^ O ".

Magnesium oxide MgO Loss on burning pious

Typical ..characteristics. jT i ciche.

Dry shine

Specific weight

Density after slight shaking, pounds / plede ^ (kg / m ^)

Density in the unimpacted state, pounds / foot ^ (kg / m5) pounds / gallon (arid)

1 pound masses, gallons

Oil absorption

Hegman finesse - Percentage 16 - 25

- 30

- 4

- 28

- 20

9.5 - 10.5 P, 84 - 69 percent

2,80

ING. Ο., ΟΓΙΓΌΟΒ

4 * · 4 4 4 * * · ·. · ·· · • 4 »J • · · ·« • 4 4 44! · • * 4 4 4 · ♦ · J * • 44 • 4 · •• 44

4* • · 4 4 4.**

4 4

4 4 4 ····,

4 · 4 1

- 80 (1216 - 1280)

- 57 (7φ4 - 912)

23,32

0,0429

- 24

1-2 ^ assa through a 200 mesh sieve, 99%

Go through a 325 mesh dg sieve, / average particle length \ 0.03 mm.

-55TALCO No. 505 (CANADIAN)

Typical chemical analysis SiOg Silica

Calcium oxide CaO

Aluminum oxide A ^ O ^

Magnesium oxide WgO

Ferric oxide pe£°5

Combustion loss

percent

0 'i * .. «iq K« »· * ..» · .38-41

- 13

2-3

- 28

1-2

- 18

OFFICE i'I;! vr Hι

ING 0. G '/ iOG * · »·« »» * 0 · »»

0 »

0···· ···· · • # 0 0*0 ** ·· «

- - . · ♦ · · « *•00· « • _ * · « ♦ < · * < 0 0 ’·**· ·.♦, <·:

, ·. · * * 00 * · · * ζ · *Λ * · 4 ·

4 000

Λ0 * · «0 9 0 0 * * · «« «0 •: ·» 4 «•» · fe * • · J 4 · pH

Typical physical characteristics

M ·· »*» - * uà ** »» - ** · - ».» <'* !, h »'« * »- * '»' '»-1··1 ·»'«· ·*·« '

Dry shine ^ ex specific

Density after slight shaking, fog / foot ^ (kg / m ^)

Density in the unpumped state, pounds / foot ^ (kg / m ^) pounds / gallon (arid)

1 pound masses, gallons

Oil absorption

Pinesza Hegman

9-10

Percent «M« 'kH.-Ih. · <Γ

- 89

2,80

- 74

- 34

23,32

0,0429

- 24

3,5 - 5 (1088-1184) (448-544)

Go through a 200 mesh sieve, $

Go through a 325 mesh sieve, # average particle length 0.03 mm

-36 Ietic features,. Of ..mica .. ^ orlte _.in. ^ Flakes. ,,

Property

ΜΓ '** »·. * · Tl h, ^ R» - V · * ·· * »·

Color

Dorma

Nominal particle diameter

Particle thickness

Hardness (Mohs)

Specific weight

Refractive index pH (aqueous suspension) Solubility in water

Maximum temperature with little or no decomposition

Pile density (Scott voltmeter) as produced after transport, iClO BRt υι ·

ING. C. GREGOR

Value therej ·, J *. ... yt * '** - * - A - V' I »« · '»'

Amber-brown

Thin flakes

20 microJ to 0.25 inches (0.64 cm), depending on the type 0.5 to 10 microns depending on the type 2.5 to 3.0

2,9

1,598

7,5

Practically insoluble

2372 (1300

C)

- 17 there (0.14 - 0.2?

·· · · « 4 4 ’· ·4 4 • « 4 * « • » 4 · 4 : ·

4 4 4 4 ·:·:· • « · · ····: 4 4 · 4 1 / foot 'is / cm)

- 35 lbs / foot '(0.32 - 0.56 À / cn?) • 44 • 44., It (' .. ·! · '

ΠΆ, 0. CA 'vr i (a. Iii

-yt Characteristics of mica Suaorite flakes

I «,. MJ »- * ·» * W- »· *» · »1 '·»' «· ί · Mi. '»'1 «> * Ι» - H .Ι. * '.Tt. <«Ut i tt 1'. · -« ,! »'J ·,., ^ 1 aa' * H

Value property

Sand content * 4 0 «• 004 -», *** •

»» * Ί.

4 0 * 0 *·« « 0 « · 0*4

Modulus of elasticity ^ existence under traction (calculated) *

Thermal conductivity *1 (perpendicular to the flaking plane)

Go through a * 325 mesh ASTM D-607-42

25xl06 psi (172 léa) 125xlO3 psi (862 MPa)

4,6 (K factor) setac'I »0 ·» 4 * · 5 »* · * • 0 ty 0« «•

* > > 0 • 4 4 4 * ·

4 0 0 4 .·

4 0 to 0

Linear coefficient of thermal expansion (parallel to the flaking plane)

Average particle length

I 4. .tt '.H j. «. *« Tt- ii ^ hW * · ± J.Mater, Sci. 8, 1373 (1973)

7.2 x 10 ~6/ ° P (13 x lO *6/ OC)

0.03 mm US Bu jet. Mines Bull et ìn 647

-38u! f icm pnrvnn! r ....

• · · · · .·· • · * * ·

Chemical composition The chemical formula of Susorìte mica in flakes is the following!

Κ2Μβ4 > 32pel, 16A13,8 ^Yes5 » 75A12,25°20^ (0HV * 2 its chemical composition, by weight, is presented below.

·· · ♦ • «• · • * · · · e

· · · *. • ··· * »·· ee

Component the Si02

A120j

MgO k2°

FeO

T * V5 «2°

BaO Ke2°

TiO2

Cr202

MnO „^ .in _pe s o.

40.7

15.8 20,6

10,0

7,8

2,2

1,2

1.0 θ, 5

Traces

Panels prepared using the formulation "" B "of Example II were finished with three finishing treatments for vehicles comprising, or not, a base coat (primer) and were examined against the respective specifications for vehicles WG- <K> E00fi

4 4 4 4 . · · · · .··· · ’ 4 4 4 4 4 *•44 4

4 relating to finishing treatments.

1) Was one of the panels treated with a coat of funds? Sherwin-Williams Piane E67BB7 type was, ··, ·; '* ·' · baked in the oven for 30 minutes at 82 ° C (180 ° P),

2) One of the panels was not subjected to a primer treatment · Both of the above panels (1 and 2) were treated with PPG 871 * 571, then a final coat of lacquer was applied, wet-on-wet white 926-97686 from 3> u Pont

The panels were then pre-cooked for 10 minutes at 82 ° 0 (180 ° P), and then again passed for 30 minutes at 162 ° C (325 ° P).

Who / ysler

3) One of the panels was treated with Sherwin-Williams Piane E67BB7 primer and was fired for 10 minutes at 82 ° C (180 ° P).

4) One of the panels was not treated with primer. A final coat of tif enamel or Celanese 64-1170 HHA Enamel was then applied to both of the above panels (3 and 4) and the panels were baked in the oven for 30 minutes at 121 ° C (25O ° P).

the ord

5) One of the panels was treated with primer * 444. ··; · * ··., · · I * · ♦ *. ····· • «· · · ··· · ·. · * · · »·. ·· type Mobil Taupe ESB-M6J-119B and baked in the oven

-40.

ufiicìc <* bfìfvf; III

ING. C:; & ft6ORJ ****** * ··· for 30 minutes at 163 ° C (325 ° F).

6) One of the panels was not treated with primer, A final coat of Ford M50J MAI) Bnarael type enamel was then applied to both the panels above (5 and 6) and the panels were baked in the oven for 16 minutes at 135 ° C (275 ° i ')

All panels were examined against their respective specifications. The test results are listed below.

· ♦ ··> 7 · ** ·· «·» M • 4 »» »• ·· '* · o

B • * '···· »*» 4 • »a · B» · · 4 * • «4 * ·

4 4 B 4 ··

4 4

4»· • * 4 4 4

CJ o

•re

M

Panel No co

VP

ΙΛ xr

<td>Ό</td><td>wounded</td><td></td><td></td><td></td><td>P <</td><td></td><td></td>

<td>there</td><td>OP</td><td></td><td> 1</td><td></td><td></td><td></td><td></td>

<td>or</td><td>Rites</td><td>U></td><td></td><td> * '</td><td> (0</td><td> •</td><td> •</td>

<td>THE</td><td>fetuses</td><td> |</td><td></td><td>us</td><td>t</td><td>To the</td><td>pt</td>

<td></td><td>• canals</td><td></td><td>•re</td><td>or</td><td></td><td>B</td><td>or</td>

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-42Ut I ICIO PATENTS INO. Q / t <the CORI

4 priority claims, no other members on record

This recordMember, by publication datePriority claim

Priority claims4

Priority claims
Document	Office	Kind	Date
89798078	United States of America	A	1978-04-20
89798078	United States of America	A	1978-04-20
897980	–	–	–
US19780897980	–	–	–

Abstract

Term

TITLE

PRIORITY

MOLD COVERING OF PIECES PRINTED BY SHEET FORMING

OF MOLDS FROM MOLDING

USA,

THE DEPOSIT,

THE OFFICIAL OFFICER

THE DOI CHIEF

19411A / 7

MOLD COVERING OF PIECES PRINTED THROUGH

SHEET FORMING OF MOLDS FOR MOLDING

MOLD COVERING OF PIECES PRINTED THROUGH

-13 THE I ICIO SHORT 111

THE

EXAMPLE I

THE

THE

CM

CM

CO

OR

OR

CO

-T

I

-P

P

ING. C. GREGOR

C)

M

VP

OR

P,

I

H

P,

OR

R

P

K

P

P

V

Priority claims4

Events

Numbers

Titles2

Classification