BE579723A - - Google Patents

Description

       

   <Desc / Clms Page number 1>
 
 EMI1.1
 



  "Modified Alkyd Resin Compositions."
 EMI1.2
 The present invention relates to ciliated alkyl resin solvent soluble compounds of epoxy compounds derived from a fatty oil with oxygen containing oxirane in.,. Ene, precursors. its derivatives with these and from this; z..¯ here, and the manufacturing process of these products. more specifically, the invention relates to improved coozition3 of er.du.isa; I 3. resin-based.: 1. = - ¯ dc, l - "iere I
 EMI1.3
 al¯-Jae resin in combination with è a -, = # re epoxies. derivative;:;. 1 a fatty oil it el [:, î,: '. E 1 =:. = Ie or- -0' :::: '¯i:;. ::: p8.I:

   

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 EMI2.1
 ? this last, the process for the production of the latter - "" "1 (" 'k. 1h.' {"," "," 6 ', in an organic solvent system and the products derived from these. last.



   Industrial baking paints and enamels and
 EMI2.2
 Common pour-atitoaobiles are acceptable when they exhibit the following properties: excellent color
 EMI2.3
 and good color retention, a good bri1J.ê ..!. t, fast casing, immediate hardness, low viscosity to high solids, wide compatibility,
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 and good stability with other resinous materials, and easy handling. Some basic resins which satisfy these conditions are constituted by various systems of soluble alkyl resins in a bolvnt modified by resins either based on urea or based on urea.
 EMI2.5
 aélaaime.

   However, flexibility is sacrificed for the calf. hardness with other color retention problems, and resistance to solvents and alkalis.



   Consequently, the present invention proposes in particular to provide:
 EMI2.6
 - a resin aU :: yc1e diluted in an orca.niq solvunt, ue and epoxidized materials derived from a gra.sne oil presenting oxygen to internal oxirane, 3. be again useful adhesive, plastic and
 EMI2.7
 vehicles which are broadly compatible with the - ,. ures i- substances soluble in a solvent, and -L'or - slow xes C 0 = p1e :: e Molecular with high resistance - chemical and pliable state to varying degrees of hardness;

   - coating vehicles pī.;, ir.t4s of ::: - '; sine alyc òài + iGe and oo.nposi tions' oil ..¯ō ;; s donations ï4 organic solvent systems -, u4- donr.t: nt Durable and tough flexible films at high levels-¯-u1 of.> x = t4, excellent resistance to water, alkaline and acid ¯tiers, excellent tenacity and resistance

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   to the. weathering and abrasion, excellent resistance to cold, and exhibiting excellent resistance to yellowing. excellent color retention when
 EMI3.1
 the are pigmented, and excellent adhesion to. glass, at. metal, to other resinous surfaces;

   
 EMI3.2
 - aompositions soluble in a solvent of aatières of .nodifiëe alkyl resin and of 6pOYY compounds having internal oxirane oxygen, for ..: .. o.nt vehicles which have good stability with ij- aents qtti cook quickly with an almost inEiedia Hot re tG. suck, low visco # 1 = ty with high solids content, and force peiicles with excellent color and gloss characteristics;

   
 EMI3.3
 - A Yernis soluble in a solvent orLw-.i ;;. ue, paint and enamel vehicles comprising -.éj-ar.jes of a.,. tières resinous for-iant a reactive film and epoxy compounds long-chain reagents derived from a fatty oil source, vehicles which are capable of being
 EMI3.4
 cured by baking to give finishes exhibiting excellent gloss, excellent resistance to water, alkalis and chemicals, as well as good adhesion, flexibility, tenacity, and retention colored;

   - vehicles of varnishes, paints and equals containing epoxy compounds of 8 to 28 carbon atoms
 EMI3.5
 in the aliquot chain portion containing no terminal oxirane oxygen, and an alkyd ester material, with or without further modification by other resinous compositions and forming a film; - plastic binding and encapsulating compositions
 EMI3.6
 duisage of alky2.e esters coded for a st鯯rj-11- compound

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 than epoxidized with or. without additional modifying component, and the method of preparation and application thereof.



   In order to achieve the aforementioned aims, the present invention then comprises the particularities described more fully below, and which will emerge from the description which follows of certain embodiments given by way of illustration but not limiting the latter.



  To obtain the epoxidized oil-coded alkyd resins and the compositions against described above, the process has two parts as indicated below:
Part 1: In this part of the process, a modified alkyd ester (resin) is formed which is the reaction product of a monobasic acid, a polybasic acid, or an anhydride, and a polyol. A second polybasic anhydride is reacted with the ester of monobasic acid, polybasic acid, and polyol previously prepared to obtain a half ester of modified alkyd resin. These complexes all have an acid number (IA) of between 80 and 120 approximately, after the final reaction, in which the carboxyl group (s) react with the epoxy compounds.



   This alkyd resin is a special resin made by reacting a fatty aciae or other monobasic acid material, a polyol material, and a suitable aibasic acid or anhydride such as phthalic anhydride between 182 and 204 C. to a particular aciae number (45-90), and added thereto a sufficient amount of an appropriate second dibasic anhydride, such as phthalic anhydride, monochlorophthalic anhydride, tetrachlorophthalic anhydride, chlorendic anhydride, etc., and cooking only for a sufficient period of time between 182 and 193 ° C. to form the half ester of the second ¯ ¯ ¯.

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 anhydride.

   This resin is then cooled, and it can be diluted or not using an appropriate solvent, for example xylene or a mixture of xylene and butanol (95 parts of xylene, 5 parts of butanol), or equivalent product. .



   Part 2: In this part of the process, the complex of the modified half-alkyl ester of part 1 is cooled to at least 149 ° C., and diluted, preferably with an aromatic type solvent such as indicated, and with or without a second solvent, which can help achieve solution clarity and viscosity control. After cooling to about 43 ° C. or less, an epoxy compound having internal oxirane oxygen is added with or without the prior, subsequent, or simultaneous addition of a neutralization inhibitor or stabilizer.



   Alternatively, the neutralization inhibitor and stabilizer, such as a suitable amine, preferably a tertiary amine or other suitable temporary inhibitor, can be added to the alkyd ester of Part 1 before; or together with the addition of an amount of epoxidized aliphatic base component of up to about 25%. If more than 25 to 30% by weight of the epoxy base component is added, a partial reaction between the formed alkyd resin half ester and the epoxy component is necessary to obtain optimum film properties.

   Further, in this part of the preparation of the vehicle, if the partial reaction is required, care should be taken not to allow the reaction between the alkyd resin half ester complex of part 1 and the epoxy compound to go so far. at completion.



  For this purpose, the addition of about 25% of an epoxidized oil-based material with the compositions of Part 1 allows baking to obtain very shiny tough films at baking temperatures of between

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 121 and 149 C. in less than about 30 minutes. Otherwise, when more than 25-30% of the epoxidized oil component is added to the alkyd resin half ester complex of the. Part 1, preferably a partial reaction is carried out to form an intermolecular complex soluble in a solvent having residual acidity which is neutralized before the end of the reaction. Softer films can be obtained by adding more than 30% epoxidized oil without partial reaction.



   The films formed from the compositions can be cured at temperatures ranging from 66 to 149 ° C. in 10 to 60 minutes or more. At lower temperatures, longer cooking times are required. A preferred baking program lasts approximately 3C minutes at 121 to 149 C. to achieve the baked films referred to as contemplated herein.



   As indicated above, the neutralization stabilizer is added in an amount at least chemically equivalent to the acidity of the composition of Part 1. This neutralization stabilizes the product during storage.



  Subsequently, upon application as a film by dipping or spraying, for example, the neutralizing and stabilizing agent evaporates allowing mutual reaction between the alkyd resin half ester and the epoxy compound. to obtain the formation of the desired film as an alkyd and epoxy resin co-iplex.



   As shown below, the constituent forint the base resin is an alkyd resin modified with dibasic acid. In order to obtain characteristics preventing yellowing, the alkyd resin is preferably prepared with saturated fatty acids. However, the alkyd resin can be further modified with a benzoic acid material.

 <Desc / Clms Page number 7>

 
 EMI7.1
 .., or: ma.tiera 'ana: rog.,' To '> fobtain hard dandruff,. : <. 4 ,,, ......., 1 ... .... '. "" "': High and very shiny, the epoxy component preferably contains 8% oxygen d internal oxirane or more.



   The following examples of compositions and products, as well as processes for their preparation providing film-forming compositions derived from the modified alkyd esters and chain fats.
 EMI7.2
 long epoxidized are given for illustrative purposes not limiting: of the invention: EXAMPLE I
 EMI7.3
 
<tb> Part <SEP> 1 <SEP>: <SEP> Partics <SEP> in <SEP> weight
<tb>
<tb> A. <SEP> <SEP> fatty acids <SEP> of <SEP> nuts <SEP> of <SEP> coconut <SEP> hydrogenated <SEP> 440
<tb>
 
 EMI7.4
 B. 2entaerythritol 412
 EMI7.5
 
<tb> C. <SEP> Phthalic anhydride <SEP> <SEP> 532
<tb>
 
 EMI7.6
 D.

   Anhydride a.Ie iqize 4
 EMI7.7
 
<tb> E. <SEP> Xylene <SEP> 80
<tb>
 
 EMI7.8
 The above components are mixed and reacted in a conventional alkyd resin esterification process, at a reflux temperature of between 182
 EMI7.9
 and 19300, until the acid number '-Uo:, ibe to 80, as determined by any conventional test method. The reaction mixture is then cooled to 135 ° C. or less,
 EMI7.10
 and 376 parts of tetrachloroph-alic anhydride are added, and the reaction mixture is maintained at 177 ° C. for at least 30 minutes. The solution is cooled to 149 ° C. and diluted with xylene to a solids content of 50%.



   Analysis of the solution gives: Gardner color 2+; Viscosisted 66 stokes; Acid number 106.9 (on the basis of solids).



  Part 2: A. Alkyd resin modified with a base of part 1 (50% in xylene) 2573 parts B. Triethylamine 251 "

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 C. Butanol 105 part s
D. Epoxidized linseed oil (8.3% oxirane) 261 "
The solution of the base modified alkyd resin of Part 1 is cooled to 27 ° C., to which triethylamine and butanol are added, and mixed until a homogeneous state is obtained. During mixing, the temperature increases to 43-49 C. The solution is then cooled below 43 C., and the epoxidized linseed oil is added with stirring until a sawing is obtained. homogeneous.



   Analysis of the product gives: Gardner color 2;
Viscosity 10 stokes; 49.1% non-volatile matter. The films of the solution force a hard, flexible, water resistant, and chemical resistant coating after baking at 121 ° C. for 30 minutes.



   The alkyd resin codified: by a base of the Part '
1 is also compatible with other fatty oil based epoxy materials as shown in the following:
Part 2a:
To 493 parts of the base modified alkyd resin of Part 1 are added 48 parts of triethylamine, 50 parts of epoxidized soybean oil (46.2% oxirane number) and 20 parts of butanol, they are mixed with a conventional paddle stirrer until a homogeneous solution is obtained. Analysis of the combined alkyd and epoxy resin solution gives: Gardner color 2;
Viscosity 10.7 stokes; and 49.1% non-volatile dobby.



   After baking for 30 minutes at 121 ° C., a tough and flexible film is obtained which is resistant to water and chemicals, and exhibiting a softer characteristic than that obtained with linseed oil epoxidized with an oxirane number. by 8%.

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 EMI9.1
 



  # àg ,,,,, ¯,., ¯ ¯, ¯,; =% Éj # ,, .i llÉl'I = 2fl) ± W; / =., $ àli) t. ,
 EMI9.2
 - \; Ji.j} 'i.i;!:,:. {- :::;' ;; if.;?;: '3- "' '' ':' -: ': ..; ..... /' / .. :::: ..; r'ri. .. <- .. <.. y - ## - '' Parts by weight v: Pe1argnic acid 400 B: Beataérytwitol 412 0 .. Talic anhydride. 5-7
 EMI9.3
 
<tb> D. <SEP> Maleic anhydride <SEP> <SEP> 4
<tb>
<tb> E. <SEP> xylene <SEP> 80
<tb>
 
 EMI9.4
 F. Tetrachlorophthalic anhydride 376 The above components are mixed and reacted as described for Part 1 of Example I, cooled and diluted to a solution containing 50% solids using xylene. Analysis of this basic alkyd ester gives: Gardner color 1+; Viscosity 10.5 stores (50% non-volatile product); Acid number 97.4 (based on solids).



  Part 2
 EMI9.5
 
<tb> A. <SEP> Resin <SEP> ester <SEP> of <SEP> base <SEP> of <SEP> the <SEP> Part <SEP> 1
<tb>
<tb> solution <SEP> to <SEP> 50 <SEP>% <SEP> in <SEP> the <SEP> xylene <SEP> 2607 <SEP> parts
<tb>
<tb> B. <SEP> Triethylamine <SEP> 229 <SEP> "
<tb>
<tb> C. <SEP> Butanol <SEP> 53 <SEP> "
<tb>
<tb> D. <SEP> Xylene <SEP> 42 <SEP> "
<tb>
<tb> E. <SEP> Epoxidized <SEP> flaxseed <SEP> oil <SEP> <SEP> (8.0 <SEP>% <SEP> of oxirane) <SEP> 262 <SEP> "
<tb>
 The components were combined as described in Example I. Analysis of the epoxy resin and alkyd ester composition gave: Gardner Color 1.5; Viscosity 8 stokes; and49.4% non-volatile products.



  EXAMPLE III
 EMI9.6
 
<tb> Part <SEP> 1
<tb>
<tb> A. <SEP> Soy <SEP> fatty acids <SEP> <SEP> <SEP> 500 <SEP> parts
<tb>
<tb> B. <SEP> Pentaerythritol <SEP> 412 <SEP> "
<tb>
<tb> C. <SEP> Anyride <SEP> phtaliqua <SEP> 570 <SEP> "
<tb>
 
 EMI9.7
 D. Zaleic anhydride 4 II E. Xylene 80 n F. Tetrachloropht anhydride, -mli-que 376 n

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 EMI10.1
 4F. "E .0w, jcet- ester àlk $ 1e and modify it as described in Example I.



   Analysis of the solution gives: Color Gardner
 EMI10.2
 4; Vïa 00 '3ité 350 Etolais; Acid number 93.5 (based on ± 15öliden) s 50% non-volatile product.



    Part 2
 EMI10.3
 the basic resin of part 1
 EMI10.4
 
<tb> (solution <SEP> to <SEP> 50% <SEP> of <SEP> produced <SEP> not <SEP> volatile
<tb>
<tb> in <SEP> of the <SEP> xylèrle) <SEP> 2688 <SEP> parts
<tb>
 
 EMI10.5
 8a 2riethylamine. 229 If ce mtaooi 175 'D. Epoxidized linseed oil (8.3xd'olir..ne) 276.
 EMI10.6
 



  We combine the components CO..h. :: b described above.



  Analysis of the product gives: Gardner color 3; iscc -.,:, bey stokes; ° 90 of non-volatile products.



  Tn? PLB 17 '
We. prepares a vehicle composition of the. manner described in Example III by substituting tall oil fatty acids for soy fatty acids. Analytical results for the base modified alkyd resin and modified alkyd resin solutions are substantially within the range given in Example III above. Films baked at 121 ° C for 30 minutes are tough, tough, and resistant to water and chemicals.



    EXAMPLE V
 EMI10.7
 
<tb> Part <SEP> 1
<tb>
<tb> A. <SEP> Acid <SEP> fatty <SEP> of <SEP> nuts <SEP> of <SEP> coconut <SEP> hydrogenated <SEP> 382 <SEP> parts
<tb>
<tb> B. <SEP> Trimethylol <SEP> ethane <SEP> 208 <SEP> "
<tb>
 
 EMI10.8
 0. Petaerythritol 236 n D. Anhydride phthalia-ue 572 "
 EMI10.9
 
<tb> B. <SEP> Xylene <SEP> 80
<tb>
 
 EMI10.10
 F.

   Zaleic anhydride 4- on
 EMI10.11
 The constituents of this 80osiion are reacted as described in Example I until - - ..

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   the acid number of the alkyd ester reaches 64 to 68. The composition of the reactants is cooled to 135 ° C.
 EMI11.1
 add 376 parts of tetrachloraphthalic anhydride during the final cooking, as described: in Example I. Analysis of the alkyd ester codified by a base gives: 5Os4 Ipe of non-volatile products; Gardner color 2, Viscosity 23.5 stokes; and Acid number 87.6 (based on solids).



  Part 2 :
To 2477 parts of a 50% solution of this modified alkyd ester in xylene solvent are added 216 parts.
 EMI11.2
 of tr14thy] minA, 275 parts of linseed oil 1 = o; .jée (8 "of oxirane), and 91 parts of butanol of the lesson described in Example I. Analysis of this cō c3iion of modified alkyd ester and epoxy resin gives: Cast Gardner 2; Viscosity 5.2 stokes; 4-9.1 of non-volatile products After baking at 121 * 0. will hang 0 .: linu. 1; es, on obtains a hard and flexible film comparable to that of Example I, Part 2.
 EMI11.3
 



  In addition, by way of illustration of: c chinai oon the modified alkyd ester of part 1 with an i-utre, .-: ire based on epoxidized oil, the following may be mentioned: Part 2a:
 EMI11.4
 To 505 parts of the alkali base of Example V, 39 parts of triethylate, 50 parts of epoxidized safflower (7.1 oxirane), and 17 parts of epoxy safflower are added to 505 parts.
 EMI11.5
 butanol, stirring them so as to obtain a homogeneous elaLe.



  The mixed position forms a strong, flexible, water and chemical resistant film after being baked at 121 "C. For 30 minutes. 1;.;, Rt '; of the film is slightly less to the one done with

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   the oil, epoxidized linseed, but is sufficient for coating purposes. In addition, other epoxidized oils and other esters with slightly lower oxirane value, such as soybean oil (6.3% oxirane), epoxy stearyl acetate and other products. replacing the above safflower oil results in softer, more supple dandruff.



     EXAMPLE VI
 EMI12.1
 
<tb> Part <SEP> 1 <SEP>: <SEP>
<tb>
<tb> A. <SEP> Pelargonic <SEP> <SEP> 300 <SEP> parts
<tb>
<tb> B. <SEP> Trimethylol <SEP> ethane <SEP> 211 <SEP> parts
<tb>
<tb> C. <SEP> Pentaerythritol <SEP> 233 <SEP> parts
<tb>
<tb> D. <SEP> <SEP> phthalic anhydride <SEP> 556 <SEP> "
<tb>
<tb> E. <SEP> Maleic anhydride <SEP> <SEP> 4 <SEP> '
<tb>
<tb> F. <SEP> Xylene <SEP> 80 <SEP> "
<tb>
<tb> G. <SEP> Tetrachlorophthalic anhydride <SEP> <SEP> 372 <SEP> "
<tb>
 
The alkyd ester and the modified alkyd ester are prepared as described in Example V.



   Analysis of the modified alkyd ester composition gives: Gardner color 2-; Viscosity 17.8 stokes; Aid Index 93.9 (based on solids); 50.3% non-volatile products.



  Part 2 :
To 2517 parts of a 50% solution of the modified alkyd ester in xylene, 212 parts of triethylamine, 250 parts of epoxidized linseed oil (8.3% oxirane) and 70 parts of butanol as described in Example I, and analysis gives: Gardner Viscosity U +; Gardner color 2-; 49% of non-stolen products.



  EXAMPLE VII Part 1
An alkyd ester material prepared as described in Example V is formed which consists of: 1

 <Desc / Clms Page number 13>

 
 EMI13.1
 
<tb> A. <SEP> using <SEP> pelargonic <SEP> 800 <SEP> parts
<tb>
<tb> B. <SEP> Benzoic acid <SEP> industrial <SEP> <SEP> 168 <SEP> "
<tb>
<tb> 0. <SEP> pentaerythritol <SEP> 1030 <SEP> "
<tb>
<tb> D. <SEP> Phthalic anhydride <SEP> <SEP> 1280 <SEP> "
<tb>
<tb> E. <SEP> Maleic anhydride <SEP> <SEP> 10 <SEP> "
<tb>
<tb> F. <SEP> Xylene <SEP> 200 <SEP> "
<tb>
 
This alkyd ester preparation is then modified by adding 1180 parts of chlorendic anhydride, and the initial ester is modified as described.

   Analysis of this modified alkyd ester gives: 50.2% of non-volatile products; Viscosity 56.3 stokes; Gardner color 2; Aid index 92.6 (based on solids).



  Part 2 :
To 996 parts of a product of Part 1 are added 86 parts of diethanolamine (or 63 parts of triethylamine), 46 parts of butanol, 25 parts of xylene, and 1 5 parts of epoxidized linseed oil, and the mixture is stirred until it is homogeneous. Analysis of the composition gives: 4gtO% of non-volatile products; Viscosity 2.0 stokes; Gardner color 2-.



  EXAMPLE VIII Part 1:
This alkyd ester is predicted by mixing 231.4 parts of hydrogenated coconut fatty acids, 43.7 parts of resinous polyol, 223.3 parts of pentaerythritol, 328.6 parts of phthalic anhydride, 2.3 parts of maleic anhydride and 20 parts of xylene, baked at 121 ° C. for 30 minutes, but stopping the estrification of the initial alkyd resin when the acid number reaches 76 to 82, to add 217 5 parts of tetrachlorophthalic anhydride as the acid modifier for the initial alkyd resin esterification material.

   Analysis of the modified alkyd ester gives

 <Desc / Clms Page number 14>

 
 EMI14.1
 51 ,? % of non-volatile products; Viscosity 128 stokes; Gardner 2+ color; Acid indioe 97.8 (on the basis of solids).



  Part 2
Add to 771 parts of the ester solution
 EMI14.2
 modified alkyd of part 1, 70 parts of sorted 1: ..: ne, 48 parts of butanol, 13 parts of xylene and 99 parts of epoxidized linseed oil (8.3% oxirane). We mix these
 EMI14.3
 contents up to g. what we get a hoo3èr.e solution.



  Analysis of the solution gives: 49.5% of non
 EMI14.4
 volatile; 6 stokes viscostity; Gardner color 2.



  CONSTITUENTS of Part 1: In the preparation of the composition of modified alkyd resin ester, the fatty acids indicated are given by way of illustration of saturated and unsaturated fatty acids derived from fatty oils of vegetable, animal and nostril origin. , containing 6 to 26 and preferably 8 to 20 carbon atoms in the fatty chain. Instead of fatty acids, glyceride oils can be used to prepare the alkyd ester by alcoholysis, preferably
 EMI14.5
 in the presence of a catalyst, with a polyfunctional alcohol before adding dibasic acid, usually anhydride
 EMI14.6
 phthalic.

   As typical examples but not li: -c. If fatty substances and saturated or unsaturated oils, mention may be made of cottonseed, corn,
 EMI14.7
 rapeseed, soybean, safflower, castor, castor, flax, menhaden, sardine, whale, cod liver, tallow, bacon, etc.

   In addition, one can. ::. See recoure
 EMI14.8
 to monobasic acids obtained syn théti'o.ue.: J. {;!. L, of the type of 2-ethylhexolque acids, benzoic acid, p-butyl-tert. benzoic, pelargonic acid and acids derived from "oxo" products, As typical fatty acids contained in fatty oils used and derived from the latter,

 <Desc / Clms Page number 15>

 as single constituents, but generally in the form of mixtures, to prepare the alkyd ester base, mention may be made of caproic, caprylic, capric, lauric, myristic, palmitic, stearic, behenic, oleic, erucic, linoelic acids, linolenic, arachidonic and olupanodonic. Furthermore,

  The fatty acids can be used together with other benzoic acid material and other materials, and they can be modified by the latter.



   The amount of fatty oil or fatty acid and monobasic acid constituents used in the alkyd resin can be varied. In general, the alkyd resin is modified so that it contains between
10 to 40%, preferably 20 to 30% oil or comparable monobasic acid material.



   The polyol constituents can be, for example, pentaerythritol, trimer thylolethane, trimethylolpropane, sorbitol, diethylene glycol, propylene glycol, ethylene glycol, glycerol; copolymers
1,2,6-hexanetriol-1,2,6 of styrene and allyl alcohol (resinous polyol X-450 from Shell), and glycol etherified phenols such as the resinous polyols of the "Dow
Chemical Company "(Dow X2631, X2635, 622 and 565 which were used in Example VIII) etc. The amount of such polyols used is preferably an amount chemically equivalent to the total acidity of the composition, but it can be vary it from a shortfall of about 10% to a surplus of about 10%.

   Although excess acidity remains in the finished alkyd ester or resinous material, it is preferable to use the theoretical amount of polyol at least for the film forming compositions.



   The first dibasic acid component of the alkyd ester portion can be any of those known in the art. However, although it is preferred either

 <Desc / Clms Page number 16>

 
 EMI16.1
 -. =: 1 '% ahfl¯j ± dē.mtalic; tetr4 Irt c or "'' ràDiiYdrldè> '1iéi3.hydràmtaliciue; 16n may have recourse to other dibasic acids such as isophthalic acids, terehtalic acid, tetrachlorophthalic llanhydride, salt anhydride, acid adipic, fumaric acid, ohlorendic anhydride, succinic anhydride, etc. In the foregoing examples, preferred dibasic acid materials are exemplified.

   In addition, we can add
 EMI16.2
 the initial dibasic oonstituent in UJJ.fhuaI1ti t in excess to maintain the acid number. In the preferred process, the second dibasic component should be in the anhydride form, and tetrachlorophta- anhydrides are preferred.
 EMI16.3
 lic, mono-chlorophthalic, chlorendic., phthalic, tetrahy.rophthalic, hexahydrophthalic, etc.

   The addition of the leic acid material can be eliminated as an auxiliary component, but it is preferable to do so.
 EMI16.4
 to have recourse as it favors the obz # ntion of the colors in solution, in particular with unsaturated fatty acids used in the preparation of the codified alkyd resin.
 EMI16.5
 We can also use the above dibasic acid cosipones used in Part 1 of the above. The supposedly indicated as anhydride to modify aavan-
 EMI16.6
 tage the drest1ye mass after the first. ox. =% zie main of the esterification reaction of the alkyd resin is completed.

   These anhydrides are believed to provide the reaction and coupling bond between the modified alkyd resin partial ester material and the epoxidized oil component. We prefer to have recourse
 EMI16.7
 with tetrachlorophthalicoid anhydride to obtain optisusi hardness and flexibility.

   Other dibasic materials can be su.osti.l ',, 1 to form comparable and softer films and plastics,
 EMI16.8
 depending on the content of fatty oak and oxirane per-cyclic

 <Desc / Clms Page number 17>

 
 EMI17.1
 : ') jJ # :: j} ² # jf.9.1t'ét-d1re that the carboxyl groups ¯? fi, J;) fj &' fiÉ [.éÙÀ ± j $) à3 $$ Q) É / # E [ 3iJf:. <,, '"- *,', <: 'vrJ} ß;:. = è t -', ';.': ï.,; k¯¯ - '. -: -.':; librês' ôurn1: s!: <a.àîiS1.it base -are essentially: f:; i; 1: t; t: J:?; i ± .1 '' '"' -. J: - - '' ' ..,: ±. :.: r - :; 'y.; -: - - -. . The oxirane oxygen reactive agent of the epoxidized oil component of Part 2. Therefore, the alkyd resin is changed in the content of oxirane in a functional relationship.

   To obtain optimum film hardness and mass, the oxirane equivalent of the epoxy component is preferably in excess over the free carboxyl groups of the alkyd resin half ester base.



   For a chemical equivalence based on the acidity of the alkyd resin, the amount of epoxidized linseed oil (8.0% to 9.5% oxirane) is between 15 and 20% approximately, and for soybean oil (5.0 to 6.7% oxirane) the amount added is between 20 and 25% based on the total weight of the alkyd ester and the epoxy component to obtain properties optimum dandruff. By using an excess amount of oil, the hardness is maintained with higher oxirane numbers.



   As indicated in the examples above, xylene is the preferred solvent used to form the partial or modified alkyd ester. Other organic solvents such as toluene or the like can be used. In addition, another solvent of the type of butanol, ethylene mono- and dibutyl ethers and diethylene glycols of ethylene mono- and diethyl ether and diethylene glycol, etc., in the proportion of 1 to 5 % approximately, is often advantageous. The additional solvent increases the clarity of the solution and provides viscosity control.



  CONSTITUENTS of Part 2:
The volatile neutralizing and stabilizing agent or inhibitor is intended to stop and retard the reaction between the alkyd half ester and the epoxy component.

 <Desc / Clms Page number 18>

 
 EMI18.1
 \ '² (f1: t60, .iifJ'YO: ta.; T'1 -' cba.sst1 by volatilization during f: '.-- :. 7' {. Q'f.- ï - ..;. :. v, .. ¯ -H. << = ¯ ..-.- r <.; ..: - <- <there ui.ssori of. fagorr to allow the residual acidity of the half-alkyd-ester to react with the component epoy, CO, x: the 'indicated the tertiary amines are preferred.

   However, other similar volatile amines and other volatile alkyd amines such as dimeric acid may be used.
 EMI18.2
 thyl formamife, efi, other temporary reaction inhibitors of the type of weak organic bases in the corresponding and necessary amounts, as required, and with or. without. mix them to obtain neutralization.



  However, in some cases other less favorable inhibitors can be used, for example ammonia,
 EMI18.3
 dimethylethanol! '1mi nA, monoethanolanine, ditho.nolamine, dipropylamine, diisopropylamine, and elan
 EMI18.4
 Management thereof, in correspondingly equivalent s-toichiometric and necessary amounts, as indicated.



   The epoxy oils and epoxy compounds useful in the present invention are, for example, those of the type described and prepared by the methods of United States Patent Nos. 2,485,160, dated October 18, 1949 .......
 EMI18.5
 in the name of rlied..rhauser; End of 2 813 878 of January 26, 1353 ..... in the name of Wahlroos; or as described by the patents of
United States of America No. 2771,972 of November 20, 1956 ..... in the name of Ritter Jr, et al, and No. 2,569,502 of October 2, 1951 .... on behalf of Swern. These oils are essentially those containing an unsaturation conne mentioned in the base oils for alkyd resins, or alkyd esters of Part 1, examples.

   These unsaturated oils, or their fatty acids, can be converted first into other esters by alcoholysis or. by est-
 EMI18.6
 rification with saturated and unsubstituted, substituted and unsubstituted e-arotic aliphatic mono- and po13-alcohols before or after the EDO == J-dation- In addition, one can

 <Desc / Clms Page number 19>

 also use epoxidized long chain fatty esters or. to epoxidized dimeric and trimeric polymers thereof;

   for example mono- and polyepoxy compounds such as epoxy stearyl acetate, epoxy stearyl epoxy stearate, butyl epoxy stearate, octyl epoxy behenate, diepoxy Methyl stearate, di- (epoxy-laury @@) adipate, propyl triepoxy-sterate, allyl epoxy sterata, etc., which contain about 4 to 12% oxygen. of oxirane.



   More particularly, the oxirane compounds which may be used are epoxidized glyceride oils containing from 5 to 12% oxirane oxygen. Preferably, in this group, it has been found that a selective oil-based material containing 8-9.5% oxirane is particularly applicable for film-forming properties. Therefore, for epoxidation, the base oil should preferably have an iodine number of at least 150. Typical examples of this class include linseed, deposited soybean, safflower, and other oils. of fish. However, epoxidized linseed oil is preferred as indicated for pigmented paint and enamel compositions.



   Although the epoxy oils and esters mentioned above are original. animal, plant and marine, the use of epoxy compounds from synthetic sources and petroleum-based is not excluded.



   In general, the oxirane compounds useful in the present invention are compounds derived from substantially substituted and unsubstituted long chain fatty substances containing from 6 to 26 carbon atoms in the fatty chain portion having at least one oxygen. internal oxirane, and preferably several internal oxirane groups per chain.

 <Desc / Clms Page number 20>

 



   The end applications and properties of the end products of the present invention are determined by several factors, including:
1) The degree of modification by a monobasic acid (oil concentration and modification by an oil) of the modified alkyd ester of Part 1 of the Examples;
2) The weight ratio of alkyd resin to epoxidized oil component of Part 2 of the Examples;
3) The oxirane content and structure of the epoxidized oil component of Part 2 of the Examples.



   The hardness of the film and the overall quality of the baked films of the final products increase as the oxirane content of the epoxy oil component increases when the amount and type of the alkyd ester is kept constant. Conversely, hard to soft, plastic to tacky films can be obtained when the preferred oxirane number of 8 to 8.5% decreases to about 4%. If the oxirane content of the epoxy oil is kept constant, the percentage of oil or monobasic change of the alkyd ester increases, and the films become softer.



  Thus, for a given combination of the desired final properties, the weight ratio of the acid alkyd ester base to epoxidized oil components, i.e. the modification by an alkyd resin and the oxirane content of the epoxy component, are important and mutually associated factors.



   In general, films can be obtained with essentially equivalent properties by combining: first two portions of a short chain alkyd resin of 20 to 25% modification by a monobasic acid with one portion of a linseed oil epoxidized (8 to 9.5% or more oxirane), second six parts

 <Desc / Clms Page number 21>

 
 EMI21.1
 The 25 to z monobasic acid modification of a longer chain with a portion of an epoxidized linseed oil (8 to 9.5% or more of oxirane). The above are within the preferred limits to achieve the desired film properties of the products described herein.

   Other ratios outside of those described, and certain change factors in the ratios, as indicated, serve to form a wider range of products varying from tacky and adhesive compositions to tenants to hard, friable and brittle.
Although composite mixtures, as described herein, can be used in the field of materials. plastics and the like, it is preferable to pigment them and use them as a baked coating. When used in this way, they provide a very tough film, adhering strongly to metal, glass, wood and resinous surfaces.

   The films are very glossy and exhibit good color retention, good resistance to water, acids and alkalis, and are not brittle and exhibit a high degree of flexibility.



   Soluble epoxy esters and alkyd esters are compatible with other soluble resinous materials.



  In addition, the epoxy resin and alkyd ester mixtures can be dispersed in water, using an excess amount of amine neutralizer, and can be mixed with other soluble materials and substances. - liable to be dispersed in water. Therefore, their film-forming characteristics, and plastic properties can be further varied from a hard state to a soft state, and from a high gloss state to a dull state. Generally: 'less shine is obtained

 <Desc / Clms Page number 22>

 
 EMI22.1
 ->. '<i' "'' 'a"; ... ",; - .: h -; - :;' , -; "';:, - o -.' A and softness when the constituents are not fully and mutually compatible.



   The following table lists, by way of illustration, resinous materials soluble in an organic solvent, and capable of being dispersed in water, compatible with the mixtures of epoxy resin and alkyd ester described here:
 EMI22.2
 
<tb> Type <SEP> of <SEP> resin <SEP> Nargue <SEP> Manufacturer
<tb>
 
 EMI22.3
 Phenol formaldehyde at R0% EEHB 700 .rcher iels - ;. iâlanc
 EMI22.4
 
<tb> AROPHENE <SEP> 735
<tb>
<tb> AROPHENE <SEP> 753 <SEP> "<SEP>" <SEP> "
<tb>
 
 EMI22.5
 Butylated melamine nuesimeneu 875 Mansanto
 EMI22.6
 
<tb> "Resimene" <SEP> 876 <SEP> "
<tb>
<tb> "Resimene" <SEP> 879
<tb>
<tb> "Resimene" <SEP> 881
<tb>
 
 EMI22.7
 toÉ2lllBiOn acryl:

  ique nphoplexn P-85 Rohm & Eaas
The following example indicates other compositions which may be formed from the epoxy resin and alkyd ester mixtures described above with compatible materials having a resinous nature:

     EXAMPLE IX
 EMI22.8
 
<tb> Parts <SEP> in <SEP> poias
<tb>
<tb> A. <SEP> Mixture <SEP> of <SEP> resin <SEP> epoxy <SEP> and <SEP> of ester <SEP> alkyd
<tb>
<tb> soluble <SEP> in <SEP> a <SEP> solvent <SEP> like <SEP> described <SEP> in
<tb>
<tb> Example <SEP> I <SEP> (by <SEP> example) <SEP> 100
<tb>
<tb> B, <SEP> Soluble <SEP> matter <SEP> in <SEP> a <SEP> solvent, <SEP> by
<tb>
<tb> example <SEP> the <SEP> phenolformaldehyde
<tb>
<tb> ("Arophene <SEP> 700") <SEP> 2-30
<tb>
 
The mixture of epoxy resin and alkyd ester A, and a second soluble resin B, with or without the addition of a mutual solvent, are simply mixed at the desired concentration.



  The compositions form plastics, and may be pigmented and preferably used in the form of spray or ion coating materials, as described herein.

 <Desc / Clms Page number 23>

 



  - The addition, of the. The resinous material is intended to act as a modifying agent which modifies the film-forming and plastic properties of the epoxy alkyd resin complexes. For example, mixing any of the listed melanin resins and added in increasing amounts increases the hardness of the baked film. Surprisingly, by comparison with conventional resin systems, harder and softer resins can be obtained at equal melamine concentrations. The addition of about 2% or. the addition of the melamine resin material also increases the retention of color and gloss, and the chemical resistance of the epoxy resin and alkyd ester complexes.

   In addition, the alkyd esters codified in combination with the epoxy compounds having a lower oxirane number, that is to say between 4 and 6%, as defined above, form adhesive to soft plastic films which can be more codified by the addition of latex solutions and latex emulsions, rubbery: synthetic such as butadiene-styrene, and other analogous latexes such as polyvinyl acetate eulsions, acrylic exhaustions, emulsions of copolymer oils Known in the market, combinations which cure to give flexible rubbery plastic masses and films exhibiting an adhesive to tough condition.



   Normally, a slightly excess amount of the neutralizing material is added to the compositions.



  In some cases, it may be advantageous to prepare compositions strikes by adding an emulsifying material, for example an amount of tertiary amine neutralizer in excess of about 2%, such as triamine and water. However, the viscosity decreases very

 <Desc / Clms Page number 24>

   slightly when water is added, and such emulsion compositions are generally not suitable as water-diluted coating vehicles.

   However, for use in plastics and as an addition agent, they can be mixed with other water soluble materials, such as proteins, urea-formaldehyde and other resinous systems. soluble in water, and in a solvent, which are compatible with the modified epoxy resin and alkyd ester compositions. These modified epoxy resin and alkyd ester compositions are primarily useful for providing adhesive, plastic, and bonding compositions in the laminating and related fields.



   Preferred solvent compositions as shown by the examples are useful as vehicles in the paint and enamel industry.



   The vehicles can be pigmented in a manner analogous to other solvent-type vehicles in any conventional ball or stone roller mill. Pigmented compositions are very stable in storage. Preferably, vehicles are used to provide baked end products. The films thus forced, at a Sward hardness level of 30%, pass a G.E. impact test of 60%, and at a Sward hardness of 40% they pass a G.E. impact test of 40%. In comparison to conventional films currently known, a Sward hardness of 30-40% successfully undergoes only a G.E. impact test of 12-20%.



   A pigmented enamel composition prepared as a coating composition of the preferred type is illustrated by way of illustration of the film-forming compositions described herein as follows:

 <Desc / Clms Page number 25>

 
 EMI25.1
 :; g, = z, i;.; ¯ =; =. not a word;; . j; y; - <¯- - J "j鵯¯ ¯ ,, ¯ ¯, ¯ ¯ ¯ ¯ ¯] ¯) (?: j-µLj ± 1) µ; l ir] = .µIl]; Parts by weight Parts ¯weight µlf) h? ÉM $ µé3gµÔé $ iJilb (.li, ì? 1 "jflijÙ ': lsl" ..', ¯ ..



  {: ':,; 6o'! Ú.t1Ón "': a.ë -âiitë-epoxy and ester
 EMI25.2
 
<tb> alkyl <SEP> from <SEP> from <SEP> Example <SEP> I
<tb>
<tb> (by <SEP> example :) <SEP> 107
<tb>
<tb> B. <SEP> titanium <SEP> <SEP> <SEP> (RA) <SEP> 195
<tb>
<tb> C. <SEP> Xylene <SEP> 50
<tb>
<tb> D. <SEP> Ether <SEP> monobutyl <SEP> of <SEP> ethylene <SEP> glycol <SEP> 5
<tb>
 
The above components are charged to a conventional rock mill and crushed for 16 to 48 hours in a conventional manner.

   We. then add an additional 290 parts of the epoxy resin / alkyl ester mixture of Example I, and 76 parts of xylene while continuously stirring until a uniform mixture is obtained. The pigmented composition contains about :
Resin solids 26.9%
Pigment solids 26.9
Pigment volume concentration 19%
Ratio of pigment to binder 1
Viscosity in Ford N 4 cup 44.8 seconds
This composition is pulverized and baked at 121 ° C. for 30 minutes to form a very shiny, tenacious, hard enamel film. water and product resistant
 EMI25.3
 chemical.

   Additional films have been shown to cure at temperatures between 66 and 177 ° C. over a period of time of between approximately 10 minutes and 1 hour. Faster cooking is obtained at the higher temperature, and a longer period of time is required at a lower cooking temperature. Other conventional pigments in lieu of titanium dioxide can analogously be blended with the vehicles of the present application to obtain paint and primer compositions, and other conventional non-reactive pigments such as. black, chrome yellows, worms, etc.,
 EMI25.4
 calcium carbonate, baryLi-res, .. c.

 <Desc / Clms Page number 26>

 
 EMI26.1
 



  -: w,.;, - .: "i 'n, c.ç', .. rrtslq.:;r- v '> y" ..''-- "' ..-.



  , .. ït'ient3.cit.ri is not limited to =, .g; j, 1. (jj -.... ¯ j # ¯ig =;, =; = - =;, forms $ dg: realization described and shown, and is likely to receive various variants falling within the .frame and spirit of the invention.


    

Claims (1)

- R E S U M E - A - Resin composition characterized by the following points. 'separately we in combinations: 1 - It comprises a modified alkyd ester soluble in a solvent, exhibiting a residual acidity, a compound EMI26.2 laid epoxy having internal oxy-oxygen, and a neutralizing agent preventing the reaction between the acidity of the modified alkyd ester and the oxirane oxygen. composed of epoxy. 2 - The epoxy compound contains 6 to 26 atones of EMI26.3 carb # e in a fatty chain, and an iribitor is provided to stop the reaction between the residual acidity of the alkyd ester and the oxirane oxygen of the fatty chain, and an organic solvent. 3 - The inhibitor is a tertiary amine. 4 - The composition includes a pilent. 5 - It contains a modifying agent. EMI26.4 6 - The modifying agent is a r.tière rār. :: us soluble in a solvent. 7 - The modifying agent is a material of synthetic latex. EMI26.5 8 - Said coaposition includes an a.:;6\i ¯: alsi..n and water ... 9 - The neutralization agent is a -mine. EMI26.6 10 - The epoxy compound prér # nte 4 2. 12;:,. ::. 1 o :: y- oxirane gene. 11 - Said composition contains an oil compound EMI26.7 epoxy glyceride having 4 to 12% o.ene oxorane. <Desc / Clms Page number 27> 12 - The resin. alkyd contains 10 to 40% of a monobasic acid material, a chemically equivalent amount of polyol, and a dibasic anhydride modifying agent -contained in a solvent solution with the compound d epoxy glyceride oil containing 8 to 26 carbon atoms per acid radical. 13. The alkyd resin is coded as a dibasic anhydride with an acid number of between 80 and 120, and the epoxy glyceride oil compound is a glycerol ester of an epoxy stearic acid. 14 - As a composition for vehicles, it comprises an alkyd material modified with a dibasic acid anhydride and having a residual acid number of between 80 and 120, a neutralizing agent intended to prevent the chemical activity of said residual acidity, and an epoxy material having from 4 to 12% oxirane hydrogen, the composition being in solution in an organic solvent. The epoxy material is selected from the group consisting of a material of vegetable, mineral, synthetic, and petroleum-based origin, and has an oxirane number of between 5 and 12%. 16. The epoxy material is an epoxidized linseed oil material having 8.0 to 9.5% oxirane number. B - Process for the preparation of a vehicle composition of a modified alkyd resin and of an epoxy compound, process characterized by the following points separately or in combinations: 1 - It consists in mixing a fatty acid, a polyol, and a dibasic acid, in carrying out the esterification of the alkyd resin at a temperature between 182 and 204 C. until the acid number is between 70 and 90, cooling the reaction mixture to 135 ° C., adding a second dibasic acid anhydride and heating <Desc / Clms Page number 28> iron the alkyd resin at 121 C. for a period of time sufficient to allow a half ester to force itself, to cool and dilute the alkyd resin with an organic solvent, to add a neutralizing material and to agitate until A homogeneous mixture is obtained, upon further cooling the mixture, and adding and mixing an epoxy compound with the neutralized mixture. 2 - A portion of the neutralization material is mixed with the epoxy compound before it is added to the mixture. 3 - The esterification of an alkyd resin with an acid number of between 45 and 90 is carried out, the alkyd product is modified by a second dibasic anhydride with a residual acid number of between 80 and 120, the product is diluted. alkyd product using an organic solvent, and an epoxy compound and a neutralizing agent are added to retard the chemical reaction between the residual acidity and the epoxy compound.