WO2004018543A2 - Promoteurs d'adhesion ameliorant la rheologie pour plastisols pvc - Google Patents

Promoteurs d'adhesion ameliorant la rheologie pour plastisols pvc Download PDF

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Publication number
WO2004018543A2
WO2004018543A2 PCT/EP2003/050381 EP0350381W WO2004018543A2 WO 2004018543 A2 WO2004018543 A2 WO 2004018543A2 EP 0350381 W EP0350381 W EP 0350381W WO 2004018543 A2 WO2004018543 A2 WO 2004018543A2
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WO
WIPO (PCT)
Prior art keywords
adhesion promoter
plastisols
adhesion
acid
adhesion promoters
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2003/050381
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English (en)
Other versions
WO2004018543A3 (fr
Inventor
Jörg Volle
Christa Broll
Alfred Kruse
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huntsman Advanced Materials Switzerland GmbH
Original Assignee
Huntsman Advanced Materials Switzerland GmbH
Vantico GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huntsman Advanced Materials Switzerland GmbH, Vantico GmbH filed Critical Huntsman Advanced Materials Switzerland GmbH
Priority to AU2003268943A priority Critical patent/AU2003268943A1/en
Publication of WO2004018543A2 publication Critical patent/WO2004018543A2/fr
Publication of WO2004018543A3 publication Critical patent/WO2004018543A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/34—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids using polymerised unsaturated fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2477/00—Presence of polyamide

Definitions

  • the invention relates to specific polyaminoamide resins as adhesion promoters for plastisols, in particular PVC plastisols, to a process for the production of these adhesion promoters, to a process for improving the rheological properties of plastisols, characterized in that these adhesion promoters are used concomitantly, and to plastisols comprising these adhesion promoters.
  • Plastisols are widely used for protecting metallic surfaces from corrosion.
  • plastisols are used for the waterproofing, bonding and sealing of seams and joints, and for protecting external surfaces, such as underbodies and sills.
  • plastisols based on PVC polymers or on PVC copolymers.
  • These plastisols are composed of fine polymer particles which have been dispersed in a non-volatile plasticizer. At room temperature, the polymer particles are insoluble in the liquid phase. At a higher temperature (gelling temperature), the polymer particles dissolve in the plasticizer. On cooling, the homogeneous solution hardens to give a flexible or rigid coating.
  • the main methods used to apply these coatings to the materials to be protected are brushing, rolling, or spraying.
  • plasticized polyvinyl chloride coating compositions (plastisols), and their preparation and use is extensively described in: Kre eler / Wick, Kunststoff-Handbuch [Plastics Handbook] (1963), Volume II, Part 1 , pp. 396 ff.
  • a significant criterion for the quality of plastisols applied in this way is their adhesion to the coated material.
  • Relatively low adhesion of the protective layer increases the risk of penetration of aggressive fluids. For example, water can migrate under the coating and corrode the metal.
  • adhesion-improving additives to the plasticized polyvinyl chloride.
  • the function of the adhesion promoters is to bring about lasting adhesion to the surfaces of commonly encountered materials, such as non-degreased untreated steel, galvanised metal sheet or tin-coated metal sheet, electrocoated metal sheet, etc.
  • adhesion promoters which can give sufficiently good adhesion of the plastisol on the work piece to be coated.
  • adhesion promoters are polyamines, epoxy resins, capped isocyanates, organofunctional silanes, and esters of acrylic or methacrylic acid.
  • adhesion promoters are described by way of example in DE 26 54 871 A1 and DE 32 01 265 A1. These describe adhesion promoters based on polyaminoamides containing imidazoline groups, or, respectively, post- condensates of these polyaminoamides, which have to have a high proportion of trimeric fatty acids and of fatty acids with a higher degree of polymerization, and have to have a high imidazoline content, and are thus intended to give good adhesion results.
  • the imidazoline groups are formed here at relatively high temperatures of from about 160 to 280°C by intramolecular cyclization with elimination of water from the amide groups.
  • secondary adhesion promoters Although, when comparison is made with the conventional polyaminoamides, the addition of these secondary adhesion promoters somewhat reduces the impairment of rheology properties of the plastisol, adhesion falls markedly when the adhesion promoters are used in the amounts usual for plastisols, about 1%.
  • the present invention therefore provides the use of specific polyaminoamide resins which are obtainable via condensation of a1) polymerized fatty acids, where appropriate with concomitant use of a2) dicarboxylic acids, with b) polyalkylene polyamines, and c) amine compounds containing hydroxy groups, or else adducts of these condensation products with epoxy compounds, as adhesion promoters for plastisols.
  • polyaminoamides of the invention have comparatively low viscosity. There is very little discolouration of the plastisol during stoving.
  • polyaminoamides of the invention are obtainable from a1) polymerized fatty acids, and, where appropriate, a2) dicarboxylic acids, b) polyalkylene polyamines, and c) amine compounds containing hydroxy groups, by polycondensation, as described below.
  • the expression polymerized fatty acids encompasses polymerized fatty acids which are prepared from unsaturated, naturally occurring or synthetic, monobasic, aliphatic acids having from 12 to 22 carbon atoms, preferably 18 carbon atoms.
  • the fatty acids may be polymerized by a well-known process (see, for example, a process in DE 25 06 211 A1).
  • the condensation uses from 0.5 to 1.0 equivalent of a polymerized fatty acid a1), from 0.0 to 0.5 equivalent of a dicarboxylic acid a2), from 0.2 to 1 mol of a polyalkylene polyamine b), and from 0.05 to 0.8 mol of an amine compound c) containing hydroxy groups, the sum of the equivalents from a1) and a2) being one equivalent.
  • the equivalents of the polymerized acids or of the dicarboxylic acids here are the molecular weight equivalent to one acid group. In the case of a difunctional acid, this would be half of the molecular weight, and in the case of a trifunctional acid it would be one third of the molecular weight, etc.
  • Polymerized fatty acids a1) whose use is preferred are commercially available products which have approximately the following composition: monomeric acids: from 0.1 to 10%; dimeric acids: from 20 to 98%; trimeric acids and acids with a higher degree of polymerization: from 0.1 to 80%.
  • fatty acids are obtainable from the company Unichema with the trade mark Pripol ® According to the invention, particular preference is given to polymeric fatty acids with a proportion of not more than 50% of trimeric acids and acids with a higher level of polymerization, examples being Pripol 1017, with the following composition: monomeric acids: not more than from 1 to 3%; dimeric acids: not less than from 75 to 82%; trimeric acids and acids with a higher degree of polymerization: not more than from 18 to 21 %.
  • Dicarboxylic acids a2) which may be used are: saturated or unsaturated, straight-chain or branched, aliphatic or cycloaliphatic acids which have not more than 20 carbon atoms, for example: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, primelic acid, suberic acid, azelaic acid, sebacic acid, trimethyladipic acid, maleic acid, and fumaric acid, hexahydrophthalic acid, tetrahydrophthalic acid; or aromatic dicarboxylic acids, for example phthalic acid, isophthalic acid, terephthalic acid. Preference is given to the use of aliphatic dicarboxylic acids.
  • the dicarboxylic acids may be used individually or in a mixture. These dicarboxylic acids a2) are preferably used in a mixture with the polymerized fatty acids a1) described above. It is also possible to add small amounts of tricarboxylic acids, e.g. trimesic acid.
  • the amine compounds c) containing hydroxy groups and used according to the invention are those which have at least one primary amino group for subsequent reaction with the acid groups of the carboxylic acids.
  • Examples which may be mentioned are: monoalkanolamines, e.g. ethanolamine, propanolamine etc.; mono,- di,- and polyalkanol polyamines e.g.
  • hydroxyethylethylenediamine (aminoethylethanolamine), hydroxypropylethylenediamine (aminoethylpropanolamine), hydroxyethyltriethylenetetramine, hydroxypropyltriethylenetetramine, di(hydroxyethyl)triethylenetetamine, di(hydroxypropyl)triethylenetetramine, etc.; glycolamines, e.g. diglycolamine.
  • monoalkanolamines in particular ethanolamine and hydroxyethyltriethylenediamine.
  • those amine compounds containing hydroxy groups listed in the previous paragraph are merely a small selection from the amine compounds which may be used according to the invention.
  • Preferred polyalkylene polyamines b) for preparing the polyaminoamides are polyethylene polyamines.
  • polyethylene polyamines having at least 4 nitrogen atoms in the molecule.
  • the polyaminoamides of the invention may also be subjected to a downstream addition reaction with epoxy compounds.
  • the invention therefore also provides adducts of the inventive polyaminoamides described above with epoxy compounds, obtainable by reacting a polyaminoamide of the invention with an epoxy compound.
  • any of the products having one or more than one epoxy group per molecule may be used as epoxy compound.
  • a comprehensive list of these epoxy compounds is found by way of example in the handbook “Epoxiditatien und Epoxidharze” [Expoxy Compounds and Epoxy Resins] by A.M. Paquin, Springer Verlag, Berlin, 1958 and in “Handbook of Epoxy Resins", 1967, Chapter 2, pp. 257-307.
  • a preferred epoxy compound is kresyl glycidyl ether.
  • the proportion of the epoxy component in the polyaminoamide adduct may, depending on the nature of the epoxy compound and on the desired product properties, be from 0.1 to 30%, preferably from 2 to 10% (by weight), so as to retain good processability of the polyaminoamide adduct used as adhesion promoter.
  • inventive polyaminoamides or their adducts may also be used after solution in plasticizers and/or solvents.
  • plasticizers/solvents which may be used are phthalic esters, e.g. dibutyl phthalate, dioctyl phthalate, diisononyl phthalate, and benzyl alcohol.
  • This invention also provides a process for preparing the adhesion promoters of the invention, characterized in that a polymerized fatty acid a1), and, where appropriate, a dicarboxylic acid a2), is added to an initial charge of a polyalkylene polyamine b) and to an amine compound c) containing hydroxy groups, and water is distilled off after heating at up to 230°C, where appropriate in vacuo.
  • adhesion promoters of the invention may also be obtained by multistage processes, for example those described in DE 694 02 959 T2.
  • the invention also provides the use of the adhesion promoters of the invention for plastisols, in particular PVC plastisols.
  • the invention therefore also provides a process for improving the rheological properties of plastisols, in particular of PVC plastisols, characterized in that use or concomitant use is made of an adhesion promoter of the invention, and a process for producing coatings and adhesive bonds for materials, by applying plastisols based on fine- particle polyvinyl chloride or, respectively, vinyl chloride copolymers, comprising conventional fillers, additives, plasticizers and adhesion promoters, characterized in that use is made of an adhesive promoter of the invention.
  • the adhesion promoters of the invention are added in proportions of from 0.3 to 5% by weight, preferably from 0.5 to 2% by weight, particularly preferably 1 % by weight based on the weight of the plastisol, and homogenized, and the plastisols thus prepared are stoved on the material at temperatures of at least 90°C, preferably from 120 to 160°C.
  • the invention also provides plastisols for the production of coatings on materials, comprising fine-particle polyvinyl chloride or, respectively, vinyl chloride copolymers, conventional plasticizers, fillers, additives and adhesion promoters, characterized in that an adhesion promoter of the invention is used.
  • Pripol 1017 1 equivalent is fed within about 30 min at from 60°C to 90°C into a mixture of 30.8 g (0.163 mol) of tetraethylenepentamine, 21 g of N-aminoethylpiperazine (0.163 mol), 48.8 g of ethyleneamine 100 * > (0.163 mol), and 33.8 g of aminoethylethanolamine (0.325 mol).
  • the product mixture is heated to 220°C and stirred at this temperature for 2 hours, while the water produced in the reaction is distilled off.
  • the mixture is then cooled to 175°C, and a vacuum is applied (25 mbar) and maintained for 1 hour.
  • the product is then allowed to cool.
  • the adducts are prepared by using the polyaminoamide as initial charge and heating this at from about 70°C to 80°C, and adding an epoxy compound dropwise within about 60 min. Stirring is then continued for about 30 min until the reaction is complete.
  • 100 g of the polyaminoamide from example 2 are subjected to an addition reaction with 5 g of kresyl glycidyl ether.
  • Comparative example for example 2 the alkanolamine (0.3 mol) used in ex. 2 is replaced by ethyleneamine 100 (0.3 mol).
  • ethyleneamine 100 0.3 mol.
  • 290 g of Pripol 1017 (1 equivalent) and 240 g of ethyleneamine 100 are condensed. Distillate: 27 g.
  • Example 9 Comparative example: Euretek ® 563 (commercial adhesion promoter based on a polyaminoamide from the company Vantico GmbH).
  • PVC e.g.: Solvic ® 347 MB
  • 16.0% of coated chalk Socal ® 312
  • 16.5% of naturally occurring chalk Juraperle
  • 2.0% of CaO 0.2%
  • ZnO 0.2%
  • Exxsol ® 80 4.3%
  • adhesion promoters of the invention may be added to conventional plastisol formulations other than the formulations given above, in order to obtain the self-adhesive plastisols of the invention.
  • the adhesion achievable using the plastisols of the invention is determined manually. For this, use is made of Cathoguard 400 CEC sheets from the company BASF. Dimensions of adherends 25 x 100 mm.
  • a spatula is used to apply a strip of the PVC plastisol, about 1.5 cm width and about 5 cm in length, to the CEC strip, and a doctor is used to spread the plastisol to give a test strip of width 1.5 cm with a thickness of 1.5 mm.
  • the test specimen is placed in the temperature- controlled drying cabinet and stoved at 140°C for 30 minutes. After stoving, the test specimen is removed from the drying cabinet. After cooling (for at least 2 hours), the adhesion test can be carried out. For this, a knife is used to make an incision to a width of about 0.5 cm in both sides of the test strip. The test strip is then tested manually for peelability.
  • the following classification system is used for assessment:
  • the yield points (Pa) of the plastisols were determined to DIN 53019, using the Viscolab SM rotary viscosi meter with the Rheolab-Electronic MC 10, measurement system Z4, at a shear rate of up to 700/s. High yield points here mean advantageous run-off behaviour.
  • the characteristics of the polyaminoamides obtained and their adducts, and also the results, are listed in table 1 below.
  • Viscosities were determined using a VT 550 Haake rotary viscosimeter, and following the manufacturer's instructions. Interpretation of results:
  • the adhesion of the plastisols which comprise an adhesion promoter of the invention is very good.
  • the use of the adhesion promoters of the invention has markedly less effect on the rheology properties of the plastisol than is the case when the adhesion promoters of the comparative examples are used.
  • the effect of the adhesion promoters of the invention is in particular apparent on comparing examples 2, 8 and 10. Although the fall-off in yield point is not as marked as usual when using the adhesion promoter of example 10, where a free alkanolamine was added, there is nevertheless a significant reduction in the adhesion of the plastisol.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne des résines à base de polyaminoamides utilisées comme promoteurs d'adhésion pour des plastisols et, plus précisément, pour des plastisols PVC. Ces résines sont obtenues par condensation d'un acide gras polymérisé a1) et, si possible, d'un acide dicarboxylique a2), avec une polyalkylène polyamine b) et un composé aminé c) contenant des groupes hydroxy. L'invention concerne également un procédé destiné à la préparation de ces promoteurs d'adhésion, un procédé permettant d'améliorer les propriétés rhéologiques de plastisols faisant intervenir les promoteurs d'adhésion de l'invention, et, enfin, des plastisols comprenant les promoteurs d'adhésion de l'invention.
PCT/EP2003/050381 2002-08-21 2003-08-18 Promoteurs d'adhesion ameliorant la rheologie pour plastisols pvc Ceased WO2004018543A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003268943A AU2003268943A1 (en) 2002-08-21 2003-08-18 Rheology-improving adhesion promoters for pvc plastisols

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10238275.1 2002-08-21
DE10238275 2002-08-21

Publications (2)

Publication Number Publication Date
WO2004018543A2 true WO2004018543A2 (fr) 2004-03-04
WO2004018543A3 WO2004018543A3 (fr) 2004-04-22

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PCT/EP2003/050381 Ceased WO2004018543A2 (fr) 2002-08-21 2003-08-18 Promoteurs d'adhesion ameliorant la rheologie pour plastisols pvc

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AU (1) AU2003268943A1 (fr)
TW (1) TW200415179A (fr)
WO (1) WO2004018543A2 (fr)

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1076030A (en) * 1963-01-30 1967-07-19 Gen Mills Inc Improvements in or relating to copolyamides

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WO2004018543A3 (fr) 2004-04-22
AU2003268943A1 (en) 2004-03-11
TW200415179A (en) 2004-08-16

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