BE622370A - - Google Patents

Description

       

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  Coating material,
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 The invention relates to n <i'uveatua6 Po1Y'ltèr. aoide ma ,, què glycol whose hardening is not entt'Ivê or e1t1p'Ch6 by air t which can be a..uen4J! of the stall i14ü1u ;; 'eJ' iu, i: -: 6là '' * ilrt3i'e ', in the state of dandruff or ii11: 1'tJ'il.'i, I8!', yiui ' , hr '; soli. '101i Eï particular, linvenion ana d c'. ";, i.,",.,., ē - .. tk; '1 "leu: L'3 soîutiotta, the polyesters were I", 15, i .F; .



  1 i -; 1; ... ':. f ,. I. {, "0¯. B ... d, t from a) a maleic arlde or a.nhyd.4e ti! Li1ê! Qu and /, oU to '* ixa empty 1'lW181'lcue, b) dloyclopenta d.1! - and 6) dithyl glycol, alone or in admixture with up to 50% d / jSSëffcfi & s t - .. oIC, ... AL ........ A- .... v..A '""' 7 '".....'" ", other glycols, an adduct possibly. 'Z9, tf" e "tia 5, t' âia fortaë in situ during the preparation Ûu PÓ11t.,: 'o:

  ur t '.. 1ne and for coating, these polyesters can be dl / il $ I,) 1. \ I! Í aènS .detJ, Í1l0 "" \ ,,

 <Desc / Clms Page number 2>

 
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 unsaturated copoly, mer1sable mothers. in inert vox-w tils solvents and / or in mixtures of solvents and monomers
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 We have known for a long time that he is. It is necessary to use special mixtures of unsaturated polyesters if one is to avoid the formation in contact with air of insufficiently hardened surfaces on the masses and films "¯r = 5 'without resorting to means preventing the access of the air.

   (.: t ". 1t this free of masses or films during the curing adornment. 111 .. To methods have been used so far for this tinr f1 '" example the free surface is covered with a impermeable film which can then be removed, such as cellophane film or other synthetic material, or else the
 EMI2.3
 polyester or the mixture of polyester-monomer with certain * # * '# or other materials which separate at the start of the curing of the polyester and form on its free surface a fine film: 1.cùJ:' which prevents the access of the polyester. 'air.

   The solutions of soft-polyesters ::. M; '1' .2 described in US Pat. No. 2.8S2.4! 7 constitute special products for which the use of measures and (.1.1 .'- agents preventing access air is unnecessary.



  It has now been found that polyesters n;: 1.d, ï HL '1J.'ltUt-diethylene glycol-dicyclopentadiene and certain products k.1 or derived by modification, having an acid number less than fi, about 50 and preferably 40, air dry and / or can
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 being dissolved in inert monomers and / or solvents, (, \ :. 1 makes it possible to obtain solutions for coating and for pe1mî: 'cj bzz in the case of which the reactions of hardening of surfaces exposed to air are not hampered by the action of air or
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 oxygen.

   The products according to the invention can t, xw <'4taln. # Nt cured in any desired masses or films without hearth
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 tacky, have poor resistance to solvents or have other known signs of insufficient curing of the free U4raCft as a result of the action of air.



   The invention relates to coating materials containing

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 nant unsaturated polyesters and / or solutions of polyesters the hardening of which is not prevented or impeded by the action of
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 l) & 1r. unsaturated pe-lyeatepa beds according to the invention oont pre. prepared from malish resolves or maldic anhydride and / or tumor aclde, dtoyolopentadibne and more. awte of d1 & thyln.

   glycol and they can be dissolved in copolymerizable mjJnOra8 and / or inert solvents, resulting in solutions whose hardening at room temperature and accelerated hardening at higher temperatures and / or at firing temperatures is not hindered or prevented by action
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 air. lias mssses and films formed from one or more of the above polyesters solutions are perfectly hardened to
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 1ur8 surfaces exposed to air.



   The polyesters and polyester solutions according to the invention are prepared from the following constituents
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 Constituents maleic anhydride and / or maleic acid or fumaric acids; 1 mole Total constituents 0.90 to 1.05 moles of diethylene glycol
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 diols or mixtures of diethylene glycol (54,100 mole%) with 0 to 50 mole% of other glycols of 2 to 6 carbon atoms
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 Dicyclopentad1ene: 85 to 100% purity, 0.1 to 0.85 mole: lice for coating or for painting, preferably 0.1 to 0.5 mole.



   US Patent No. 2,671,070 discloses polyesters prepared from maleic anhydride (1 mole) of dicyclopenta-
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 diene (1 ;, at 0.4 moles) and ethylene glycol (about 1.05 moles). By examining the data specified therein, however, it has been established that the hardening of all polyesters and any solutions of polyesters and monomers mentioned therein is impaired or
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 prevented by the attraction of air to surfaces exposed to air. f, i during the Applicant's research, it was established in or
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 as data on the possibility of using adûi products.

    lion maleic acid-dicyclopentadiene having reacted beforehand, are: also valid for the adducts of the invention (1I.d. 1 3szt3ennnent of dïcyelopentadiene. In other words, the research of the Applicant has established that these products addition formed at

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 prerequisite cannot be used and only the inventive purposes
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 can only be realized $ if the products of r4sQtiQn deg "" unsaturated and (Su d: J.cyo2.GPentadS.'nt are formed during t. * n * "training. No explanation fttiafaisftntft of eu compn-aat r . 'can be given *, ruais 4th .... a1' compared have t.Á; \ fji-, iS? pao the same results with back product of condensation * ov <44 * # * prior and with the products of reaction J. '(,; 1'UI.6a pendent If: .. ". Training.

   Comparative tests have furthermore shown ".. (1 which * 1 $ Juc.-se- ment solutions of polyester and otyrene m of 8ty.rèn #t :: - ': triallyl cyanurate which are described in Io treve , is prevented by Inaction of the air until the gljoSi: - contains are replaced by hand. 50% of the:

   Since the solubility of the invention in inexpensive monomers increases with dicyclopentadiene it is advantageous from a point of view of eoo.îfw - that to use at least 0.4 mol of dicyclopentadj en <1. 1. 101 ", from d1cyclopentad: 1àne meeting or exceeding this raimr also ri-ui-n the cost and increase the flexibility of the y-Asinaii &" ## -. r, ';

  -
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 In particular unfavorably, the other sought-after properties of hardened masses and films obtained in terms of both styrene and d1c'Yclopentl9.dine are less expensive than maleic anhydride and the key ', # />? *, col * so that it is economically advantageous to incorporate i as large quantities as possible of these {r'atiè'pes little & ïA? * Ai-, in the polyesters and solutions of polyesters according to l * in "/% t .. - the hardening of which is not impeded by the action of! * air.

   H- apart from any consideration of the cost price, the qu -.t # *;. * Indicated from 0.1 to Oj.85 moles of, dicyclopentadiene give <# <*> * polyesters whose hardening is not impeded by 1. $ R (. 'i ..; air and which are still improved in other points <the e - oee The products of the invention are suitable for the cation -fptrt. of cast objects and die-cast, thus CU'1 \ '1' material permeation. The best proof of the fact that q-ie 3- ". #. i, w '

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 of the product of the invention is in no way impeded by the action of air (in particular for dicyclopenta- albïiji contents of 10 to 50 mole%) is illustrated by the use of these
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 to form thin films on the paper, which
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 P! H'J '/ l ;; t to obtain a water resistant and elastic resin coated paper.

   Films as thin as 2.5 miCyMtN will be successfully applied and cured on paper,
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 ordinary industrial machines and usual speeds, which makes it possible to obtain a varnished paper whose
 EMI5.5
 eàlvte2es couelies do not adhere when unrolled at the outlet of 1 coating machine. It is evident that an unscratched paper could not be obtained if the curing of the applied POY5cr film was hindered even to a small extent by air permeation.

   In addition, the fact that a film having 1; 10 / oaiss (> ur of only 2.5 microns does not adhere to the film).
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 ..:! the neighbor, is an indication that the hardening is not
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 .r.1'lpÍ} ohé HU "Inaction of the air, given that if there were any do yr:, H thus the resin film would remain sticky or aoIhiï i'ugueuaa throughout its thickness- The fact that the products' # "t1'ß '(tlttQ1t are suitable for the application of thin films:. on pûpldr ntn u, llet11lnt illustrates a possibility of use pr! JÍ11i t.'S. mis and \ co}.' demonstrates that the hardening is not prevented by the action of the air. Act examples below ... "; \. r'lÜ! 1flt dtJ $ siplannea typical which are used for bedding. # t-jt tXtpi as shown, on regular icachines which nt: ralnI.8B at the speed of the produced paper *.

   Now, it is known that the unsaturated polyesters of the endioyl type, r nu i aiip r hold the polyesters of the invention cured
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 a solid product by oxidation and / or by the mechanism of carbon-carbon addition This addition takes place between the doubles
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 bonds of motleic acid or endoyl residues and / or between these
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 double bonds and those of optional copolymerizable monomers
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 é <* 3 mixtures. By the use of dîeyclopentadiene in the

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 products of the invention, endioyie-type double bonds should *
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 always be consumed, and they are indeed consumed when
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 addition takes place.

   In theory, using 0.85 moles of dit-y-clopentadiene per mole of malec anhydride should consume 6% of the maldic double bonds when the dicyclopentadiene is added and it should consume 107 moles of double
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 maleic bonds when cyclopentadiene participates in the addition. In both cases, the adducts obtained should still contain, in the most favorable case, a few doubla
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 bonds usable for crosslinking. Research has always
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 However, it has been established that the crosslinking power (i.e.
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 reaction) of the polyesters of the invention apparently remains AX9vê per 0.85 & 1.0 moles of dicyclopentadiene.

   The fractional capacity of these polyesters is, in fact, significantly lower than that of a polyester prepared using 0.1. mole of dicyclopentadienp
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 but it still allows quantities of styrene to reach
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 35 - 40% can be effectively crosslinked with the product
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 final. It is therefore assumed that the dleyclopentadiene remains anywhere in the polyester in a state corresponding to a
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 addition only partial.

   No satisfactory explanation for
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 The precise state of dicycopentadiene in prepackaged liquid polyesters, in cured polyesters or in films of polyesters and monomers cannot be given at present, although it should be noted that polyesters of the invention shows good reactivity when the molar ratio dl.ayccp $ :: ts. diannei maleic anhydride reaches 1.00 1.00.
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 The reactivity attenuates polyesters of the invention for,
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 high levels of dicyclopentadiene can be used
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 successfully to prepare adhesives and sealants.

   For example,
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 it is possible to repair easily using the resins of the invention having a medium to high content of dicyclopentadiene and
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 presented in the form of pastes of resins and monomers,
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 boat hulls made of non-polyester. saturated and meio,% 4reo

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 reinforced with glass fibers; in fact, these pastes are easy to spread and level and have good adhesion while hardening.
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 slow enough and giving off sufficiently little heat of reaction for hardening to lead to a solid state! wanted without creating internal tensions.

   A durable, solid, well-adherent repair having good surface properties is thus obtained.



   It goes without saying that the Masses of the invention, in addition to the polyesters and / or their solutions may contain inhibitors, stabilizers, accelerators, pigments, fillers and
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 any other materials and can be hardened with the aid of catalysts which generate free radicals known for hardening.
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 Polyesters, such as peroxides, ozonides, etc. As with most solutions of unsaturated polyesters, with some combination of inhibitor,
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 dauct'.1v'rator and curing catalyst ditti results.
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 killed water from other systems.

   The specialist may, depending on the combination chosen, obtain the physical properties, the rate of cure, the degree of heat release best suited to the intended purposes. For most purposes, it is generally considered that a tuasse, layer or film is well cured when it can remain for a few minutes in con-
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 tact with a small amount of acetone or alcohol without any effect on the surface or without the mass becoming soft.

   The polyesters of the invention and their solutions harden over time (ambient H. * S, high cures moddr-4aent 4levies ($ 7-66 <') useful,' ocur accelerated hardening * and temperatures of firing Iii ,, t tiles (930C and above) in substances resistant 9. 1 * acetone, "presence of cobalt-based driers with or without catalyst
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 free radical generator. The hardening time is inversely proportional to the hardening temperature, ie the required hardening times are;> lua long at room temperature than at firing temperatures.

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   Since the polyesters of the invention and the solutions of the invention can cure at room temperature at accelerated cure temperatures and at baking temperatures, they are well suited as materials for painting and for coating paper, fabric, cloth, etc. wood, fiberboard. 4, metals, etc. that they protect in a remarkable way * The sa-
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 Any type of coating can be applied in any way, for example with a spray gun, brush, roller, etc.



    The remarkable adhesion of the products of the invention to metals and other supports is illustrated by the following examples.
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  For a more d7ta.7.l.e description of the additives cited; c '., nrs, reference should be made to US patents including NOs. are shown below
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 Inhibitors Accelerators Growth catalysts
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<tb> 2,646,416 <SEP> 2.846.411 <SEP> 2.632.751
<tb>
<tb> 2.593.787 <SEP> 2.822.343
<tb>
<tb> 2.815.333 <SEP> 2.822.344
<tb>
 
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 2,777,829 2,822 145
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<tb> 2.846.411 <SEP> 2.632.751
<tb>
<tb> 2.627.510
<tb>
 
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 Monoftlvasi..eioptfr | ymé, Pll? Ables '' ,,,, los
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<tb> 2. <SEP> 632.751 <SEP> 2.671.070
<tb>
<tb> 2.671.070
<tb>
 
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 .ËSMEMJL '"
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<tb> A <SEP> resin-monomer <SEP> solution? <SEP> is <SEP> prepared <SEP> to <SEP> from
<tb>
<tb> of the following <SEP> constituents <SEP> <SEP>:
<tb>
 
 EMI8.11
 Msl & S- <àSFs Resin (A.

   Diethyleneglycol 203 J H $ 3 Resin Di'thylene glycol ",, 05 11l1l) Resin B. Dicyclopentadiene * 0 $ 20 <4 (C. Maleic anhydride" so11de leoo J ± f <S>
 EMI8.12
 
<tb> "Solids" <SEP> introduced <SEP> 23571
<tb>
 
 EMI8.13
 Clear water,: 1-
 EMI8.14
 
<tb> <SEP> weight of <SEP> resin <SEP> 217.2
<tb> D. <SEP> Styrene <SEP> (25% <SEP> in <SEP> weight <SEP> on
<tb> the <SEP> 72.5
<tb>
 
 EMI8.15
 prepared -. (- w.¯¯w.n-1 ..... 2q to-

 <Desc / Clms Page number 9>

 
 EMI9.1
 Moles grVmme4 E. Xyln8 (4% by weight based on molta 9 4
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<tb> of <SEP> the <SEP> resin <SEP> used) <SEP> 9.5
<tb>
 
 EMI9.3
 F.

   Inhibitor - - (0010% by weight of
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<tb> the <SEP> base <SEP> of <SEP> the <SEP> solution <SEP> resin- <SEP> o
<tb>
 
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 monomer) O ,, ü29 * Purity 95 ,, the remainder is mainly methylcyclopentadi6nel
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<tb> ++ <SEP> P-quinone.
<tb>
 



  The resin is prepared as follows: we make
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 reacted? components 2. Bu and E, they are heated in a protective atmosphere 4th inert gas at 12 ° -138 ° C., the exothermic reaction is allowed to proceed freely at reflux for 30 minutes,
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 it is still heated to 210 ° 0 until the acid number is 15 to 17 and any remaining xylene is removed in vacuo.
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 The charge is cooled to 12700 µ, component F is added, cooled to 104 and styrene is added. The product is then withdrawn and
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 stored.



  The ready resin-monomer solution has a material content
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 non-volatile rot of 75 to 7? '; b by weight, a color index of about 5.a viscosity of about X (Gardner-Holdt at 25 *) and a specific weight of about 1.158 kg / liter . The solution is stable for.
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 about 10 days at 57 ° C and has a gel time of 3 minutes, .4 when catalyzed by 1% by weight of a 60% mthy.s3thyict peroxy solution and by bzz in weight of cobalt naphthenate (at 5% cobalt).

   The cured resin has a Barcol hardness of about 0; its hardening is not impeded by the action of the air, which is recognized by its remarkable resistance to acetone and its non-sticky surface. Results are also obtained!) One when the above maleic anhydride is replaced by 1 mole of maleic and / or fumaric diacid
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 PX & lPLff, 2% r
A solution of unsaturated polyester resin and monomer is prepared from the following constituents:

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 A. Diethylene glycol 1.00 lez B. Maleic anhydride 1.00 9 C.

   Dicyclopentadiene (95% purity) 0, X0 JLL & -
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<tb> "Solids" <SEP> introduced * <SEP> 217.2
<tb>
<tb> Water <SEP> released <SEP> -18.0
<tb> Weight <SEP> of <SEP> resin <SEP> (theoretical) <SEP> 199.2
<tb>
 
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 D. Styrene zozo by weight of the solution) .¯4 <j g # - #
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<tb> Solution <SEP> resin-monomer <SEP> 249.0
<tb>
<tb> E. <SEP> Xylene <SEP> (2% <SEP> on <SEP> the <SEP> base <SEP> of the <SEP> solids
<tb> introduced) <SEP> 4.3
<tb>
<tb> F. <SEP> Inhibitor <SEP> (p-quinone. <SEP> 0.005% <SEP> on <SEP> the <SEP>
<tb> - <SEP> base <SEP> of <SEP> the <SEP> solution <SEP> resin-monomer) <SEP> 0.012
<tb>
 
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 Po Solution, .nh.l.t, nâ:

  C'.Grti01 '' '0 # 254 of the resin-monomer solution 0.60 * Acetantidine hydrochloride. 2 kg
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<tb> Propylene <SEP> glycol <SEP> - <SEP> 8 <SEP> kg
<tb>
 
The constituents are heated until dissolved.



   The resin-monomer solution is prepared as follows: components A, B, C and E are reacted and left to react as in Example 1, with heating until
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 the acid number is from 20 to 22p is cooled to 127 *; add * components F and t3, cool to bzz and add component D.
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  The resulting solution has a glif.cation time of 4 minutes when catalyzed by 0.33 by weight of cobalt naphthenete (cobalt content z) and by zut by weight of a solution of methyl ethyl ethylene peroxide. at 60 / (6: of methyl ethyl ketone peroxide, bzz of dimethyl phthalate 1.088 kg / liter) In the absence of catalyst, the solution is stable at 57 for 4 days.



    EXAMPLE 3.
A solution of unsaturated polyester and monomer * and prepared from the following components?

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<tb> Mole? <SEP> Grams
<tb>
 
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 A. Diethylene glycol 1.00 106.0 B. Dicyclopentadine (95%) 0.40 vs C. Maleic anhydride le0o ¯98.2-
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<tb> "Solids" <SEP> totals <SEP> introduced <SEP> 256.8
<tb>
<tb> Water <SEP> released <SEP> -18.0
<tb>
<tb>
<tb> Weight <SEP> of <SEP> resin <SEP> (theoretical) <SEP> 238.8
<tb>
 
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 D. Styrene (30% based on solution) 102.
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<tb>



  Solution <SEP> resin-monomer, <SEP> to total <SEP> <SEP> 341.1
<tb>
<tb>
<tb> E. <SEP> Xylene <SEP> (4% <SEP> on <SEP> the <SEP>! base <SEP> of the <SEP> solids) <SEP> 10.2
<tb>
<tb>
<tb>
<tb>
<tb> F. <SEP> Inhibitor <SEP> (p-quinone <SEP> to <SEP> reason <SEP> of <SEP> 0.005%
<tb>
<tb> of <SEP> the <SEP> solution <SEP> resin-monomer) <SEP> 0.017
<tb>
<tb> S. <SEP> Inhibitor-accelerator <SEP> following <SEP> example
<tb>
<tb> 2 <SEP> (0.25 <SEP>%) <SEP> of <SEP> the <SEP> solution <SEP> resin-monomer) <SEP> 0.852
<tb>
 
The resin-monomer solution is prepared as follows * Components A, B, C and E are reacted, which are boiled as in Example 1 to achieve a viscosity
 EMI11.6
 of T-V (Gardner-Holdt at 21.

   , it is cooled to 2 'G, the components F and C are added then D. The solution prepared has a content of; solids 68.8% by weight, acid number (based on solids)
 EMI11.7
 of 21.0, a viscosity of Ut and a specific gravity of 1.125 lcr, t 'In the absence of catalysts, it is stable for 27 days at 57 ° C. If 0.33% of naphthenate is added. cobalt (6% by weight dw j cobalt) and 1% by weight of methyl ethyl peroxide solution having the above composition as a curing catalyst, the solution has a gel time of 3 minutes and reaches a Barcol hardness of o.

   The exposed surface of the resin over-
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 cie is not sticky and has a remarkable resistance to ac! -! ;
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 pXBMPM far A repair material in the form of a <* of a solutlonresin-monomer is prepared from the following components t

 <Desc / Clms Page number 12>

 
 EMI12.1
 jiolegr ffr.acynej
 EMI12.2
 
<tb> A. <SEP> Diethylene <SEP> glycol <SEP> 1.00 <SEP> 106.0
<tb> B. <SEP> Maleic anhydride <SEP> <SEP> 1.00 <SEP> 98.0
<tb>
 
 EMI12.3
 vs.

   Dîeyclopebtadiéne (technique,
 EMI12.4
 
<tb> quality <SEP>: <SEP> 90%) <SEP> 0.80 <SEP> 105.6 <SEP>:
<tb>
<tb> "Solids" <SEP> totals <SEP> introduced <SEP> 309.6
<tb>
<tb>
<tb>
<tb> Water <SEP> released <SEP> -18.0
<tb>
<tb>
<tb> Weight <SEP> of <SEP> resin <SEP> (theoretical) <SEP> 291.6
<tb>
 
 EMI12.5
 1) .. Styrene (30% of the solution) ISA
 EMI12.6
 
<tb> Solution <SEP> resin-monomer, <SEP> to total <SEP> <SEP> 416.5
<tb>
 
 EMI12.7
 2. Toluene (2) (solids) 6.0 F. Inhibitor (p-quinciie 0 035% of the
 EMI12.8
 
<tb> solution <SEP> resin-monomer) <SEP> Ci <SEP>, 020 <SEP>
<tb>
 
 EMI12.9
 .

   D1cyclopentad1.Î! Ne quality 90 (at least $ 8%); specific gravity Ct,? k., 9, normally 0.977; initial boiling point (A8TM standard distillation) at least 950 # normally 105 '; the other constituents are mainly dicyolopm, tadienes a7.yls lower.



   The resin-monomer solution is prepared as follows; the constituents A, B, '0-and E are reacted, which are boiled as in Example 1 to reach a viscosity of T-V
 EMI12.10
 (Qardner-Holdt 216) and an acid number of about 3 ...- 5, the feed is returned to 127 *, the component Bzz is added, the mixture is cooled to 104 * and the component D, La is added. resin-monomer solution obtained with a viscosity of W (Gardner-Holdt, 25 C)
The resin-monomer solution has the desired low reactivity and is easy to spread with a putty knife on a boat hull (or other body formed from a mass of unsalted polyester.
 EMI12.11
 turne and monomer).

   The solution can be used in a limpid state suitably peated or mixed with dyes and opacifiers, etc. Repairs made using the solution have good adhesion and remarkable strength and harden
 EMI12.12
 t ,,; 'd' 1.;.) 1;) lC'1t;:; ur tulle that no cracks and wrinkles are formed ci {ltl-d l '-':; .. 1:

  "t1CO to the repaired object is not detrimental selfwnt in-

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   funded. Repairs, after hardening, have a hardness
 EMI13.1
 Barcol of about 0 when curing at room temperature and their air exposed surfaces are very tacky which improves their adhesion to a subsequently applied surface layer.



  EXAMPLE 5.0
The example describes the preparation of a preferred resin mass according to the invention. It illustrates how such a resin can be used for painting or for coating in a variety of ways. The resin is prepared from the following constituents'
 EMI13.2
 
<tb>
<tb>
 
 EMI13.3
 D1 ethylene glycol 1.0 mole
 EMI13.4
 
<tb> Maleic anhydride <SEP> <SEP> acid
<tb>
 
 EMI13.5
 .Mal4ic and / or fumaric li, 0 mol Dicyclopentadiene (purity 97%) 0,

  4 mole
 EMI13.6
 
<tb> Xylene <SEP> in <SEP> quantity <SEP> of <SEP> 4% <SEP> in <SEP> weight <SEP> on
<tb>
<tb> the <SEP> base <SEP> of the <SEP> constituent <SEP> above
<tb>
 
 EMI13.7
 the resin is brought to the boil # as described in the example, until the acid number is about 20 after which the xylene is removed or left in the mass following.
 EMI13.8
 Whether or not a solvent is used in the coating materials described below.



  Part A.
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  Polyester / styrene coating consisting of up to $ 100 of reactive solids, serving as a coating for wood, paper, or basecoat. | e .tj.8s.ua ,, etc.



   The solvent-free resin is cooled from the reaction or distillation temperature to about 115 As a typical inhibitor, 0.015% by weight of p-quinone is added. The re-
 EMI13.10
 The sine is then cooled to about 104th and added with styrene-monomer. The viscosity depends on the amount of styrene added * The required styrene content is therefore determined by the use and the application process. For a styrene / resin ratio of 30/70
 EMI13.11
 a viscosity of about 1 to "W" is obtained (Gardner-Holdt at 250).

 <Desc / Clms Page number 14>

 



  At this viscosity, the resin is suitable for application with a doctor blade, for example on paper or fabric. For an atyrene resin ratio of 4.6 / 54, the viscosity is only about 21 seconds (Ford-Becher # 4). In this range of viscosities the resin is suitable for curtain application, casting application, etc.



   Coating hardens at 27-65,
Per liter, approximately 4 g of a cobalt salt such as cobalt naphthnate containing 12% by weight of cobalt and fulfilling two functions are added: a) activation of the added peroxide catalyst, b) drying of the surface of the film * The coating may be cured over an activated basecoat by the addition of methyl ethyl etone or other peroxide as a curing agent, or the methyl ethyl ketone or peroxide may be added immediately to the coating material. coating, at a rate of approximately 7.5 cm3 per liter (for example in 60% solution).

   When the peroxide is added directly to the coating material, the latter has a useful life which does not exceed a few minutes. Two-component catalyst guns should be used for coating coatings, film application using two-nozzle application machines and for squeegee application using mixing devices. improvised. In all of these cases, the required amount of peroxide is added to the resin-styrene mixture during spraying or application.

   The applied coating cures in 6-8 hours at 27 ° C or 30-60 minutes at 57-66 C, regardless of application process and viscosity, to a scratch and solvent resistant film. It goes without saying that the peroxide / cobalt ratio can vary within wide limits to suit the coating or paint system to a particular curing schedule. On paper, a film thickness of a few generally desired. microns, while the film on wood, metal or fabric can be 0.25 to 0.38 mm thick.

 <Desc / Clms Page number 15>

 



    Curing of coatings above 65
 EMI15.1
 Styrene and vinyltoluene in monomeric form are relatively volatile, so they can evaporate from the film before the onset of polymerization or co-polymerization.
 EMI15.2
 lymar1sat1on., If, however, short curing times are desired; for example in the coating of paper it is possible to use for a few seconds a curing temperature of 93 to 177 C if this gives the wet film a "standby time" at 27 to 66 C during which the copolymerization begins , after what
 EMI15.3
 the indicated elevated tamprutures can be applied.

   He goes . of course that it is possible to obtain gels practically instantaneously starting from these resins by an appropriate choice of the content of inhibitor, of styrene, of optional monomers and of cobalt; and peroxide.
 EMI15.4
 



  Method to prevent pore formation, do crat ::: 'o: -er. (skin G'0: r {'., - u ±.) pt. {p1', e, s. , d, $ t: al \, t; t 9.liss .. dan jea j2ellleuleas .. 1- -
Polyester layers have, as is known, a tendency to form craters, pores and crevices. The use of thinning agents avoiding these drawbacks is indicated, but few of these agents are effective.

   In trying to find satisfactory thinning agents it has been established that they have nothing in common with the possible slowing down of drying by the active air. In the context of the invention, they are therefore indifferent to the formation of hard coatings resistant to scratching and salt.
 EMI15.5
 rrre itai .dc3 inert ons thjxotrop1 and "matAl:

  ,F H
The clear coating materials described can be pigmented or mixed with inert substances (by fillers), thixotropic agents and / or preservatives.
 EMI15.6
 conventional, to the extent of the needs of a PD.1't1 saloon application. All these additives are indifferent to the elimination of the slowing down effect from the air.

 <Desc / Clms Page number 16>

 
 EMI16.1
 part B Resin according to Example 5e in inert solvents or in solvent-monomer mixtures. ,,. ,,.,. ,,, ... # ,, i
Usual polyesters (as nominally sold commercially) are generally free from solvents.

   However, it is often advantageous to use inert solvents in
 EMI16.2
 quantities .rs. ias a) to adjust the viscosity, b) to adjust the flow p..3.as, e) to prevent the formation of ..sxas lo to the treated vertical surfaces * ta resistance of example-.tple 5 , which is self-oxidizing, can fertilize in all kinds of forms, for example a) as a non-s * 'cb <' resin, when dissolved in a single inert volatile solvent nm: r; .a :. ' : monomers, but with the addition of cobalt salts ser. vimt ùû s.aai .; ') cojiujie solution in a solvent retort under t) but pn using a peroxide which makes the film tenacious, in addition to the addition of cobalt salts;

   c) as a solution in a
 EMI16.3
 solvent cofuite 3vus a) with an addition of monomers in an amount of 2% on the basis of resinous solids, up to a resinous weight ratio of 40; 60, plus cobalt salts and peroxide. These modifications and variations and the choice of sol- and / or monomers for these variations lead to a large number of coating materials which are suitable for wood,
 EMI16.4
 paper, fiberboard, hardboard, metals, etc. As will be further indicated below, some of these combinations have a great power of adhesion on steel and other metals, which is an exceptional property in the case of polyesters.



   For combinations of resins with monomers and
 EMI16.5
 of the following inorts, use with particular advantage of unsaturated liquid under normal conditions and <i ..: LutiV # ttiMit low volatility, for example diallyl phthalate, dl ethylene glycol nethacrylate, butyl methacrylate , the ma- 3 (.te dirllyllque, etc, which evaporate appreciably more slowly, .ù thei 'Inertes used with them like the- toluene, the xy-

 <Desc / Clms Page number 17>

 lene, ketones, esters, mixtures of aromatic hydrocarbons and alcohols, etc. This does not, however, limit the use of volatile monomers, such as styrene, alone or in combination with higher boiling point monomers.



   It goes without saying that it is possible, for example when using diallyl phthalate as a monomer in a solution of the resin in a mixture of monomers and inert solvents, to apply the solution by spraying without danger of rapid evaporation of the monomers or of subjecting it to high drying temperatures (at which the styrene and vinyltoluene used eventually evaporate) or of hardening them at room temperature, while the monomers at the point of High boiling remain in the film during evaporation of the solvent.



  EXAMPLE 5-A Solution of the resin in an inert solvent, without addition of monomer or peroxide. ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
The resin of Example 5 not freed from solvent is diluted with a 90:10 mixture of xylene and isopropanol to a non-volatile content of 50%. The solution is added to the solution. tion 7.5 g per liter of cobalt octoate ($ 2.2 kg / liter).



   A film, applied to glass, dries at room temperature overnight and becomes tack free. Its tenacity is acceptable.



   A film, applied to glass, hardens in 1 hour at 57 C, is easy to sand and resistant to acetone and alcohol.



   A film, applied to phosphated steel, continued for 15 times at 121 ° C., gave exceptional adhesion and gave a crackle finish.



  EXAMPLE 5-B.



  Solution of the resin in a simple inert solvent, without the addition of ..monoplace but with the addition of cobalt and peroxide
The described methyl ketone peroxide solution is added at a rate of 7.5 car / liter to a 50% solution of the

 <Desc / Clms Page number 18>

 resin of Example 5-A. The films applied to glass and to metal generally have the same properties, moreover already described, but are appreciably more tenacious than those obtained using solutions free of peroxide.
 EMI18.1
 



  ± Y'-14PLg 5-C.



  Solution of the resin of Example 5 in a simple inert solvent sbtis aci8 t o dc ono de aba s
The resin of Example 5, without being freed from the solvent, is diluted with a mixture of 90 parts by weight of xylene and 10 parts by weight of isopropanol, to a non-volatile content. latiles of 505, no cobalt, monomer or peroxide are added.
 EMI18.2
 



  A film applied to glass is still ppisseuae after several jusrs at room temperature. A coating, baked at 121 ° C for 15 minutes over phosphated steel, dries to a film which is somewhat sensitive to acetone but hard enough to provide a satisfactory basecoat.
 EMI18.3
 BXRÎPLB 5-D.- Solution of the resin in mixtures of an inert solvent and ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ of a monomer
When using any monomer, cobalt and peroxide are essential.

   The amounts actually used vary essentially depending on the drying time desired. Amounts from 0.05 to 1% by weight can be used successfully., Based on the resin and monomer in the solutions.
 EMI18.4
 1, - The retina of 3.> exempl * $ * and diluted, without being damaged. rsased of the solvent, using a mixture of 90 parts by weight of xylene and 10 parts by weight disopropanol # with a volatile matter content of bzz. Allyl phthalate is then added in an amount of 5 to 30% by weight based on the resinous solids. To each solution, 3.8 g of an octot of bzz cobalt and 1% of a paste are added per liter. of 50! by weight of benzoyl peroxide, the remainder being triesilic phosphate.

   The solutions are then sprayed onto 2 'pickled steel the phosphated steel and then hardened at 121 for 15 minutes.

 <Desc / Clms Page number 19>

 
 EMI19.1
 



  Catalyst 1.4 .. peroxide solutions have a pot life of several days at room temperature. Coatings dry to tough, shiny, scratch and acetone resistant films with high adhesion *
2. The resin is diluted as under 1) and mixed with monomers and cobalt, but the films are sprayed onto bowls pre-treated with a peroxide catalyzed filler containing methyl ethyl ketone peroxide. The films dried in air or by accelerated drying in 1.5 hours at 57 ° C. In all cases, coatings resistant to scratching and to solvents and having satisfactory to excellent tenacity were obtained.

   Excellent resistance is obtained when phthalate is used
 EMI19.2
 allyl and resin in proportions by weight of 15 <S5 to 30i70 and a drying temperature of 57 * 3. The procedure is as in 1, but use isophthalate dialll1, ethylene glycol 41raetha.cry1ate. , butyl methacrylate and alkyl maleate instead of dia., ylic phthalate. Practically the same results are obtained.



  4. The procedure is as in 1, but styrene and vinyl toluene are used and the coating materials are not plunged but spread over wood which, as in 2, has been treated with
 EMI19.3
 a catalyzed pore filler. Air dried films harden faster than solutions prepared with dlal1111q 'phthalate and the other high boiling point monomers mentioned. The pel-
 EMI19.4
 Licules which are cured in 1 hour at 57 ° C. are left for 1 hour at room temperature before the '# 1 -jie treatment.



  In this case also a hard, tenacious and
 EMI19.5
 sistancaux solvents.
 EMI19.6
 mPLE¯5-E
A pigmented solution of the resin in a mixture of an inert solvent and a non-volatile monomer suitable for application to metal and hardboard has, for example, the following weight composition:

 <Desc / Clms Page number 20>

 
 EMI20.1
 1000 part of the resin of Example 5 with 0.005% p-which contains 105 parts of diallyl phthalate 300 parts of xylene
 EMI20.2
 50 parts of ethylene glycol monobutyl ether 570 parts of titanium dioxide Viscosity 44 seconds at 21 Ford-Becher No. 4.

   We add, per liter,
 EMI20.3
 oye47 g of cobalt salt to lu and 1% of a paste t adorned with 50% benzoyl peroxide # the remainder being tricrdil111qu8 phosphate.



  The duration of use is 2 weeks. The material is applied *
 EMI20.4
 on phosphated steel and on filler boards After drying for 15 minutes at 121 C, tough coatings are obtained which are resistant to solvents and scratching.
 EMI20.5
 



  ? #aPF.-p '..



  If ethylene glycol (or propylene glycol) is used instead of all of the ethylene glycol in the resin of Example 5, the drying of the coating described in part A is hampered by the action. air. The films are more or less sticky, do not resist scratching or solvents, regardless
 EMI20.6
 whether dried at room temperature, at 570 or z 121.



  EK-y! 1P-'E 5-t. -.



  When dipropylene glycol or triethylene glycol are used instead of ethylene glycol, the same results are obtained in the former case as in Example 5-F. In the second case, very soft films are obtained which tend to form thin surface scales (i.e. they undergo oxidation) but are too soft to be useful as a protective coating or paint and they do not resist scratching or solvents.
 EMI20.7
 



  Z'1i "! PJIE 5-JI ..



     When 0.5 mole of ethylene glycol or propylene glycol is used instead of an equivalent amount of diethylene glycol in the resin of Example 5, the applied coatings dry with the water.
 EMI20.8
 4 ... p: wuro tabiante, without unfavorable action of the air, but more

 <Desc / Clms Page number 21>

 slowly than unmodified resins. This temperature can be considered as the limit of the suppression of the action of air. At 57, coatings require a longer drying time to achieve scratch and solvent resistance than coating materials prepared using diethylene glycol.



  At 121, the coatings cure as quickly and well as the unmodified resins, but with the great difference that the modified resins do not adhere to metals.
 EMI21.1
 



  7C1? TL '1, .... Lor81u'on uses 0.5 mol of d1proP11ene glycol instead of 0.5 mol of diethylene glycol in the resin of Example 5, a more malleable and rubbery film is obtained which can be considered as being at the limit of being able to dry at
 EMI21.2
 air at room temperature and at -1 ° C but fused, after drying at 121 ° C, remains hard and completes hardening sufficiently to provide permanent protection to the metals.

   
 EMI21.3
 mp ± .LE 5-K. - if one replaces, in the resin of Example 5, maleic acid in part by an equivalent amount of the so-called acids
 EMI21.4
 Saturated like isophthalic acid, again the ordinary type polyesters are obtained, the hardening of which is hampered by the action of air.

   In other words, the maximum insensitivity to air is obtained when the resin according to Example 5 consists exclusively of maleic and / or fumaric acid, however, amounts reaching 0.5 mol. a saturated acid, such as adipic acid, or an aromatic acid, such as isophthalic acid or phthalic acid, can be used instead of an equivalent amount of maleic acid when the coating is to be cured at high temperature, that is, about 93 C or more.



   In the case of the following resins, the dicyclopentadiene content of the resin according to Example 5 is changed from 0 to

 <Desc / Clms Page number 22>

   1-mole per mole of maleic anhydride.
 EMI22.1
 



  Dlylene gl1col 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Maleic hydride 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1 , 0 Dleyclopentadiene 0 0.1 0.3 0.4 0.5 0.6 Oog 1.0 The resins are fired as described in
 EMI22.2
 Example 1 up to the following acid numbers!
11.5 25 17 27 33 20 39 14 The xylene is then removed from the resins which are cooled.
 EMI22.3
 dies z 1150 and added 0 # 005% by weight of p-quinone as inhibitor and then cooled to 104.

   Some of the resins are then diluted with styrene, to a content of 70% by weight of
 EMI22.4
 resin and 30% by weight of styrene * The viscosities of the solutions are then measured at 250 (Gardner-Roldt) s W Z X U-V 1, T W Z-5
The gel times of the resins, measured in minutes, are as follows X:

   
 EMI22.5
 3.2 i 2 4 12 12 38 5.2 Gelation times (SPI), te # p. reaction temperature and the reaction temperature ... I below are established by standard methods SPI sx
 EMI22.6
 C611fiCation time, minutes 4.8 5.2 6 4 8.8 6 # 2 0 * 5 8.1 'fC :: 1PS reaction, min. 6.0 6.0 7.5 7 1502 16jO 2502 11.0 Reaction temperature miAx1mua, 00 240 209 214 189 129 100 91 92 To prepare coating materials, solutions of
 EMI22.7
 7th resin and 30% styrene are further diluted with ethylene as follows! 60/40 54/46 5-4 / 46 54/46 34/46 34/46 54/46 54/46
 EMI22.8
 To each solution we add, per liter, 3 days because d # ootoato

 <Desc / Clms Page number 23>

 
 EMI23.1
 cobalt (12% by weight of cobalt);

   ($ 1.0 kg / liter) e Films of the solutions are then poured onto wooden tablets previously treated with a nitrocellulose filler without planning, catalyzed by 30 car / liter of peroxide solution
 EMI23.2
 of 'thyetyorne.

   The covered wooden shelves are then ooze for 1 hour in an oven with forced ventilation at 57 The scratch resistance and to solvents of the films obtained, hardened by peroxide and cobalt, is given below! Scratch resistance good good good good good medium bad bad! Resistance to solvents Minimal slight attack It has been established that the water resistance of films
 EMI23.3
 increases with dicyclopentadiene content up to about 0.5 mole and is still good at 0.6 mole.

   At this value the slowing down of hardening under the inaction of air begins to be felt. Its slowing down is quite noticeable for grades
 EMI23.4
 higher in dicyclopentadiene, but in ration materials according to Example 4 this is an interesting property since the tacky surface of the film improves
 EMI23.5
 the adhesion of a surface layer applied afterwards.



  <t Solution of 70 parts of resin, 30 parts of styrene catalyzed by a solution of methyl ethyl ketontf peroxide (7.5 g per liter) and cobalt ooate (7.3 g per liter, 12% cobalt in octoate).
 EMI23.6
 The SPI (Society of Plastics Industry) tests are carried out using benzoyl peroxide as a catalyst and in
 EMI23.7
 covering at a constant temperature at 82 ° C from the ai bath. submersion of samples.



  This resin is unusable at a higher dilution with styrene.

 <Desc / Clms Page number 24>

 
 EMI24.1
 pFMP.J, 6; 9 ... adhesion to metals in IM ela of an aoolication J.i.hJf1.t, tt.l ....



   Good adhesion to metals is an unexpected property of systems formed from unsaturated alkyl resins and
 EMI24.2
 monomers, when no toD4 layer is used. Dei tests have shown that this unexpected adhesion is obtained when the resin of 1- * Example 5 is essentially unmodified and / or contains
 EMI24.3
 5 to 30% dia11rlic phte1.te. the remainder being the resinous solid, which gives baked coatings of good quality, well flowable, and resistant to scratching and to solvents.

   Sheets coated in this way have good resistance to salt water (salt spray test) when the coating materials are modified with thinning agents which prevent the appearance of craters (orange peel). crevices, etc., that is, these sheets have good resistance to salt water when the cured film is continuous.

   
 EMI24.4
 fmssËs¯¯¯¯¯¯¯¯¯¯¯¯6 9
 EMI24.5
 
<tb> Resin <SEP> from <SEP> example <SEP> $ <SEP>
<tb>
<tb> 70% <SEP> of <SEP> constituents <SEP> not <SEP> volatile
<tb>
 
 EMI24.6
 in xylene 100 g 100 g 100 g 1Q0 g Phthalate diallyl1qu, (PDA) 0 5 z2 30
 EMI24.7
 
<tb> Xylene <SEP> 30 <SEP> 35 <SEP> 42 <SEP> 37
<tb>
<tb> Isopropanol <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 0
<tb>
 
 EMI24.8
 Set 6/1 to 12% cobalt (1.05kg / l) 1.9 1.9 109 1.9
 EMI24.9
 
<tb> Paste <SEP> to <SEP> 50% <SEP> of <SEP> peroxide <SEP> of <SEP> benzoyl
<tb>
<tb>
<tb>
<tb>
<tb> and <SEP> 50% <SEP> of <SEP> tricresyl phosphate <SEP> <SEP> 1% <SEP> on <SEP> the <SEP> base <SEP> of <SEP> the <SEP> solution
<tb>
<tb>
<tb>
<tb>
<tb> complete
<tb>
<tb>
<tb>
<tb> Viscosity,

   <SEP> Becher-Ford <SEP> n <SEP> 4 <SEP> 40 <SEP> 38 <SEP> 27 <SEP> 35 <SEP> se *. '
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Constituents <SEP> not <SEP> volatile <SEP> hardened
<tb>
<tb>
<tb>
<tb> sands <SEP> weight <SEP>% <SEP> 50 <SEP> 50 <SEP> 50 <SEP> 50
<tb>
 
 EMI24.10
 Resin / PDA ratio - 95/5 & 5/12 70/30
 EMI24.11
 
<tb> Adhesion <SEP> very <SEP> very <SEP> very <SEP> very
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> good <SEP> good <SEP> good <SEP> good
<tb>
 
 EMI24.12
 Tenacity and malleability # fi

 <Desc / Clms Page number 25>

 
 EMI25.1
 1 l. Some of the sheets are uncoated steel, others are phosphate steel.



  2. Curing is carried out for 15 Minutes at 121.



  3, As established in Example 5, Part B, coatings
 EMI25.2
 according to the system of Example 8 (d1allyl1que resin / phthalate -S, 15)! have a particularly poor adhesion to metals when one replaces Ot5 mole of diethylene glycol in the resin with Ox5 mole of ethylene glycol.



  4. In general, the fluidity of the spray applied film increases with the content of diallyl phthalate.
 EMI25.3
 as already indicated, but a modification of the solvent system by using solvents with slower evaporation can remedy this defect.
 EMI25.4
 11P. 1 :: wall p \> 1J '.-.



  The resin of Example 5 (0.4 mole of dio7clopentadiene) and a comparison resin containing 0.45 mole of 0.5 mole of di-eyelopentadiene are treated with 1% by weight of p-quinone as inhibitor. Each sample is diluted to 70% non-volatile material using styrene. Each of the three resins is then added with an accelerator, at aavi.r 7.5 OR3 per liter of cobalt naphthenate (cobalt) (0 # 958 kg / liter) and an eatft lyitor, namely 7.5 g per liter of ae solution of .4ethylethyl ketone peroxide.



   About 3.170 kg of each of the aforementioned resins are applied to a general purpose lithographic paper having a weight of 27.2 kg per ream in a film of about 5 adorons. The coated sheets are cured for 30 seconds at 149. Overall they have a high gloss and good resistance to solvents and rough treatment.

 <Desc / Clms Page number 26>

 
 EMI26.1
 



  .Ef <1.1P ': E ... \. "Pore strainer court the bowl a.



  70 parts by weight of the renin of the example are dissolved
 EMI26.2
 S in 30 parts by weight of a slow-acting solvent suitable for blockers, for example in ethylene glycol monoethyl ether acetate. The composition below is typical of a wood filler for walnut.
 EMI26.3
 
<tb>



  Solution <SEP> of <SEP> 70% <SEP> of <SEP> resin <SEP> and <SEP> of <SEP> 30% <SEP> of <SEP> solvent <SEP> 4.2 <SEP> kg
<tb>
<tb> Ethylene <SEP> Monomethyl ether <SEP> <SEP> <SEP> acetate <SEP> glycol
<tb>
 
 EMI26.4
 ccsjN.e additional solvent 1 * 8 kg
 EMI26.5
 
<tb> Solvesso <SEP> n <SEP> 3- <SEP> 1.0 <SEP> kg
<tb>
<tb> Aerosol <SEP> of <SEP> gel <SEP> of <SEP> silica <SEP> serving <SEP> of <SEP> pigment <SEP> 8,0 <SEP> kg
<tb>
 
 EMI26.6
 "Asbestine" 3.0 kg t <very burnt shade 0 #, 431 kg
 EMI26.7
 
<tb> Bone <SEP> black <SEP> 0.125 <SEP> kg
<tb>
<tb> Brown <SEP> van <SEP> Dyck <SEP> $ 0.12 <SEP> kg
<tb>
<tb> Earth <SEP> of <SEP> Siena <SEP> 0.125 <SEP> kg
<tb>
<tb> Earth <SEP> of <SEP> Siena <SEP> burnt <SEP> 0.015 <SEP> kg
<tb>
 
 EMI26.8
 Dn1té 1,624 kg / liter OeOI5 kg
 EMI26.9
 & Aromatic petroleum saphtha;

   shrinkage index at 20, 1.48) 0, index 1M 66-70; Initial boiling point 1779 50% boiling point 18'-193; final boiling point 203-218. J dJ1ntlam- point: matlon 544.



  Dilution for Use 1 kg of the sealer is diluted before the use of 10 * ido 1025 liter of a diluent having the following composition, which gives a sealer having a specific weight of 0.934 kg / liters
 EMI26.10
 41'tb11n monoethral ether glycol acetate. 70 parts by volume .va ne 39 25 Octoatt of cobalt (to bzz of cobalt) zip 6% zirconium zirconiumphthenate, 2t5 a
Application: the door filler is applied with a spray gun or brush on wood. It is then wiped in the usual way

 <Desc / Clms Page number 27>

 and quickly dried in 30 minutes at 57, or at room temperature in 2 to 4 hours. A filler varnish is then applied (for example an unplasticized nitrocellulose).

   This pore filler has good stability under protective layers of polyester resins, lacquers, varnishes etc.



   To illustrate the compatibility of the resin of Example 5 with nitrocellulose, the resin is dissolved in a good solvent for lacquers and varnishes, such as methyl ethyl ketone. The compatibility test with nitrocellulose is carried out at resin / nitrocellulose ratios of 95/5 to 5/95 (on a solids basis).



  Films of the mixtures, applied to glass, are perfectly clear and hard.



    TEMPLE 12.-
Rotten exterior paint building.



   Paints for the building comprising the air-drying polyester, alone or in the presence of diallyl phthalate as a film former, are prepared as follows!
 EMI27.1
 
<tb> <SEP> titanium dioxide <SEP> <SEP> 352 <SEP> g
<tb>
<tb>
<tb>
<tb> Magnesium <SEP> silicate <SEP> <SEP> 10 <SEP> g
<tb>
<tb>
<tb>
<tb>
<tb> Carbonate <SEP> of <SEP> calcum <SEP> 132 <SEP> g <SEP>. <SEP>
<tb>
<tb>
<tb>
<tb>
<tb>



  Clay <SEP> 100 <SEP> g
<tb>
<tb>
<tb>
<tb>
<tb> Aerosol <SEP> of <SEP> gel <SEP> of <SEP> leaves * <SEP> - (charge) <SEP> 100 <SEP> g
<tb>
<tb>
<tb>
<tb>
<tb> Polyester <SEP> maletic-dicyclopentadiene <SEP> acid
<tb>
<tb>
<tb> diethylene <SEP> glyool <SEP> of <SEP> example <SEP> 3 <SEP> to <SEP> 80% <SEP> of
<tb>
<tb>
<tb> solids <SEP> in <SEP> the <SEP> xylene <SEP> 1000 <SEP> g
<tb>
<tb>
<tb>
<tb> Xylene <SEP>. <SEP> 240 <SEP> g
<tb>
 
The aforementioned mixture is introduced into a silica slurry mill and ground for 12 to 14 hours.

   It is removed from bro @@ and mixed with the following constituents:
 EMI27.2
 
<tb> Polyester <SEP> of <SEP> example <SEP> 3 <SEP> to <SEP> 80% <SEP> of
<tb>
<tb>
<tb> solids <SEP> in <SEP> the <SEP> xylene <SEP> 400 <SEP> g
<tb>
<tb>
<tb>
<tb> Xylene <SEP> 304 <SEP> g
<tb>
<tb>
<tb>
<tb>
<tb> <SEP> ethyl alcohol <SEP> denatured <SEP> 111 <SEP> g
<tb>
 A further liter of the product obtained is added;

   

 <Desc / Clms Page number 28>

 
 EMI28.1
 
<tb> Octoate <SEP> of <SEP> cobalt <SEP> (12% <SEP> of <SEP> cobalt) <SEP> 3.8 <SEP> cm3
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Methyl ethyl ketoxime <SEP> (agent <SEP> against <SEP> on
<tb>
<tb>
<tb>
<tb>
<tb> lamination) <SEP> 1.9 <SEP> cm3
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Alkyd <SEP> from <SEP> coconut oil <SEP> <SEP> * <SEP>. <SEP> 3
<tb>
<tb>
<tb>
<tb>
<tb> 100% <SEP> of <SEP> solid <SEP> (fluidifying) <SEP> 15 <SEP> char
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 a Prepared according to Example 1 of US Patent No. 2,437,657 using all the acids in coconut oil instead of capric acid.



   The paint obtained can be used without further treatment as a white paint for buildings, it has good stability (for example to bad weather) when it is applied to wood, masonry, plaster, etc., over an approximate bottom coat. - requested. For example, an emulsion of a synthetic resin, for example a base coat based on commercial polyvinyl acetate emulsions, is used as a base coat.



   The above paint can also be modified into a varnish by adding polymerizable monomers in an amount up to 20% by weight based on the resinous solids of the paint. In this case, a peroxide is also added, for example the already mentioned solution of methyl ethyl ketone peroxide, at a rate of 7.5 cm 3 per liter.



   $ Modified * or unmodified paints harden overnight. Tests have shown that they have good resistance as exterior paint * for building * CLAIMS.

** ATTENTION ** end of DESC field can contain start of CLMS **.


    

Claims (1)

1. Coating material characterized in that it has a certain content of unsaturated air-drying polyesters which are obtained by hot reaction of a) maleic anhydride, maleic acid, fuma acid. 'ric or their mixture, b) of diethylene glycol or of mixtures of 50 to 100 mole% of diethylem glycol with 0 to 50 mole% of other glycols of 2 to <Desc / Clms Page number 29> 6 carbon atoms, c) of dicyclopentaldiene having a purity of 85 to 100% in an amount corresponding to molar ratios of 1: 0.0-1.05: 0.1-0k, 85, and whose index of acid does not exceed .. not 50. 2. Coating material according to claim 1. characterized in that the amounts of a), b) and c) correspond to molar ratios of 1: 0.90 - 1.05: 0.1-0.5. 3. Coating material according to claims 1 and 2, characterized in that it comprises a solution of the polyester in an inert solvent. 4. Coating material according to claims 1 to 3, characterized in that it comprises a solution of the polyester in an inert solvent or in a normally liquid unsaturated copolymerisable monomer, a dissolved cobalt salt and peroxide curing agents. dissolved organics.