GB2495776A - Plastisol composition for sealing and automotive coating - Google Patents

Plastisol composition for sealing and automotive coating Download PDF

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Publication number
GB2495776A
GB2495776A GB1118223.5A GB201118223A GB2495776A GB 2495776 A GB2495776 A GB 2495776A GB 201118223 A GB201118223 A GB 201118223A GB 2495776 A GB2495776 A GB 2495776A
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United Kingdom
Prior art keywords
text
plastisol
pvc
metal parts
citric acid
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GB1118223.5A
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GB2495776A8 (en
GB201118223D0 (en
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Humbert Vidal Codina
Santiago Jove Mayoral
Anton Leber
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of GB2495776A publication Critical patent/GB2495776A/en
Publication of GB2495776A8 publication Critical patent/GB2495776A8/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • 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
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/04—Coating compositions based on 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C09D127/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters

Abstract

A plastisol composition comprises (i) pulverulent polymer of polyvinyl chloride or polyacrylate (ii) a plasticizer of a citric acid ester of formula I, and (iii) amino- and/or amido-functional compounds and/or blocked polyurethanes as reactive additives. The citric acid esters act as a plasticizer and provide plastisols with moderate curing temperatures that confer good adhesion results when applied to organically coated metal substrates. The plastisol compositions of the underlying invention are especially useful for sealants and underbody coatings in the automotive industry. The preferred citrates are acetyl tri-butyl citrate or acetyl tri(2-ethylhexyl) citrate. The PVC may additionally contain a PVC copolymer formed with vinyl acetate, styrene or (alkyl)(meth)acrylates. Formula I: wherein R1 is H or C1-5, and R2-R4 are independently C2-9 alkyls.

Description

Plastisol composition for scam and underbody sealants The underlying invention relates to a plastisol compositions based on pulverulent polymers and amino-andior amido-frmnctional compounds and/or blocked polyurethanes as reactive additives wherein the plastisol additionally comprises citric acid esters. The citric acid esters act as a plasticizer and provide plastisols with moderate curing temperatures that confer good adhesion results when applied to organically coated metal substrates. The plastisol compositions of the underlying invention are especially usethl for seam and underbody sealants in the automotive industry.
Plastisols are generally known in the prior art to be dispersions of organic plastics in plasticizers that may additionally contain auxiliary substances like pigments, fillers, adhesion promoters and foaming aids. The plastisols have the property to gel on heating to higher temperature and thereafter to cure on cooling. The organic plastic is usually formulated as a pulverulent material to ease the dispersion ofthe polymer in the presence of the liquid plasticizer. Due to their gelling and curing properties plastisols are widely used as sealing compositions, e.g. for seam seals on metal construction parts or as a flange seam adhesive in the metal industry, as corrosion protection coatings for metals, e.g. underseals for motor vehicles, for impregnating and coating substrates oftextile materials, e.g. as a coating for carpet backing. The desired sealing properties are conferred mainly due to the physical barrier properties and the flexible mechanical properties ofthe cured plastisol but as well due to their unique flow properties that ensure the almost unlimited applicability of plastisols, e.g. by spray coating or by foaming.
Nevertheless, it is a prerequisite for the performance that good adhesion of the cured plastisol to the substrate is provided, especially on metal substrates. Therefore, adhesion promoters are often added to the plastisols in order to effect long-term adhesion of the plastisols on steel, aluminum or galvanized and/or electrodipcoated or otherwise organically pretreated metal sheets. In this respect polyaminoamides are used as an additive for plastisols based on PVC-type and/or acrylate-type ofresins.
GB-A-1193896 thus describes aPVC plastisol which comprises an epoxy resin and dicyandiamide as well as a-benzyldimethyldiamine as adhesion-promoting substances.
DE-A-2642514 proposes the addition of Schiff's bases and/or enamines based on polyarninoamides and epoxy resins to PVC plastisols in order to improve the adhesion thereof to metallic substrates. A large number of patent applications furthermore describes the use of polyaminoamides and derivatives and reaction products thererof as adhesion promoters for plastisols, in particular PVC plastisols, and examples which may be mentionedare DE-A-2906134,DE-A-3l [1815, DE-A-3201265, EP-A-l7l85OorEP-A-263053.
US-B-7,163,976 discloses that the addition of pulverulent saccharides to a plastisol composition increases the adhesion to a large number of substrates employed in automobile construction. These plastisols are especially suitable for the sealing of metal parts that as well might have been organically precoated.
In spite of a large number of proposed solutions to achieve good adhesion ofplastisol compositions to the most diverse substrates, in particular metallic substrates, there still exists a sustained need for an improved adhesion ofplastisols on a large number of substrates, especially on organically coated metal parts, as well as for providing plastisols that can be cured at relatively low temperature without negatively affecting the adhesion of the cured plastisol to the substrate. With increasing energy costs it becomes more and more desirable to establish plastisols that gel and thereafter cure at relatively low temperatures in order to employ competitive sealing processes.
Surprisingly, it was found that for a specific range of plastisols the use of citric acid esters significantly promotes the adhesion while only moderate temperatures are necessary to gel and cure the plastisol.
The underlying invention therefore applies to a plastisol suitable for the sealing of metal parts comprising a) 20-60 wt.-% of a pulverulent resin selected from PVC and/or Poly(meth)acrylate resins; b) 10-50 wt.-% of one or more plasticizers, wherein at least 30 wt-% of the total amount of plasticizers is comprised of citric acid esters according to the following general formula (I): C(=O)0R2 R10 C(=O)0R3 C(=O)0R4 wherein Ri is selected from hydrogen, branched or linear alkyl group with not more than 5 carbon atoms or an acetyl group; it2, it3 and R4 are mutually independent from each other selected from a branched or linear alkyl group with at least 2, but not more than 9 carbon atoms; c) at least 0.5 wt.-%, but prefrrably not more than 5 wt.-% of reactive additives based on amino-and/or amido-functional compounds and/or blocked polyurethanes; d) optionally up to 40 wt.-% of inorganic particulate matter and pigments; e) optionally up to 10 wt.-% of organic solvents.
Plastisols according to the invention that have been applied to metal parts can already be cured at peak metal temperatures of 125°C while the peak metal temperature is the highest temperature the metal part reached during the curing process. Moreover, it was found that the use of citric acid esters according to fbnnula (1) provides superior adhesion of the sealing compared to plastisols wherein phthalates are the sole plasticizer.
With respect to the capability of the plastisol to confer a significant improvement of the adhesion, when applied and cured on organically coated metal parts, and to cure at comparably low curing temperatures it is mandatory that a minimum amount of at least wt.-% of the total amount of the plasticizer in the plastisol is comprised of citric acid esters according to the general formula (I).
The citric acid esters according to formula (1) do as well act as a conventional plasticizer and therefore might be present in an amount above 30 % with respect to the total amount of plasticizers. Moreover, the adhesion of the cured plastisol on organically coated metal parts further improves with an increased amount of the citric acid esters according to formula (1). Thus, in a preferred embodiment the citric acid esters according to formula (1) constitute at least 50 wt.-%, more preferably at least 80 wt.-% ofthe plasticizer of the plastisol of the underlying invention. Tn an especially preferred embodiment the plastisol does not comprise more than 1 wt.-% of plasticizers other than the citric acid esters according to formula (1).
It was found that those plastisols according to the invention give rise to significant improvement of the adhesion to orgaiically coated metal parts, especially to cathodically electrocoated metal parts, that comprise citric acid esters according to formula (I) wherein the residual Ri is an acetyl group and/or wherein at least one and preferably each of the residuals R2, R3 and R4 is selected from a linear alkyl group with not more than 7 carbon atoms, preferably not more than 5 carbon atoms. Within particularly preferred plastisols the citric acid esters according to formula (1) are selected from acetyl-tri-n- butyl citrate, tri-n-butyl citrate, acctyl-triethyl citrate, triethyl citrate and/or acetyl-2-ethylhexyl citratc, especially prefelTed is acetyl-tri-n-butyl citrate.
The poly(meth)acrylate-type ofpulvcrulent resins is a polymeric resin that preferably comprises copolymers of styrene with (meth)acrylic acid, (meth)acrylamide andior alkyl (meth)acrylates or copolymers of methyl or ethyl methactylate with C-to Cg-alkyl (meth)acrylates or alkyl (meth)acrylate homopolymers or mixtures of the abovementioned polymers.
The PVC-type of pulverulent resins is a polymeric resin that preferably comprises a mixture of homopolymers of vinylchloride monomer (PVC homopolymer) and copolymers containing vinylchloride monomer units (PVC copolymers). The PVC copolymers are preferably selected from copolymers comprising vinyl acetate, styrene,
S
(meth)acrylates and/or alkyl(meth)acrylates, more preferably the PVC copolymers comprise vinyl acetate.
The preferred K-value of the PVC-type resins according to DIN EN ISO 1628-2 lies within the range of 62 to 72, more preferably within the range of 66 to 70. The K-value is related to the molecular weight of the PVC-type of pulverulent resin. The K-value impacts the thsion temperature and gellation rate of the Plastisol. The K-valuc also influences the melt viscosity of the plastisol composition and the rate at which the composition can be foamed. Typically the higher the K value the better the mechanical properties but the lower the flowability.
It was found that comparably low weight ratios of the PVC copolymer to the PVC homopolymer can be achieved when at least 30% of the plasticizers of the plastisol are citric acid esters according to formula (I) without significiantly deteriorating the adhesion of the cured plastisol. A decrease in the relative amount of PVC copolymers regularly gives rise to an improved viscosity stability of the plastisol. Therefore, in a preferred plastisol the weight ratio of PVC copolymers to PVC homopolymers lies within the range from 1.2 to 1.8, more preferably in the range from 1.2 to 1.6.
PVC-type of pulverulent resins arc generally preferred in plastisols according to the invention.
Amino-andIor amido-functional compounds and/or blocked polyurcthanes, individually or in combination, such as are known as adhesion promoters from PVC-type plastisol technology, are an essential reactive additive of the plastisols according to the invention, these having the effect of a considerable improvement in the adhesion properties in the presence of the citric acid esters according to formula (I).
A preferred reactive additive are the well-known polyaminoamides based on dimerized fatty acids and low molecular weight di-or polyamines, and/or amino-functional condensation products of epoxides based on the bisglycidyl ether ofbisphenol A with diamines or polyamines, such as ethylenediamine, propylenediamine, ctc.
In a specifically preferred plastisol the reactive additive is a polyaminoamide with an amine value of at least 100mg ICOH / g, but not more than 500 mg KOH / g. The amine value is a measure for the number of primary, secondary and tertiaiy amino-groups in the polymer and accords with the amount of KOH in milligrams which is stoichiometrically equivalent to the amount of amines per gram of the polymer. The amine value has to be determined according to DIN 53176.
Within the underlying invention the term "plasticizer" denotes organic ester compounds with a molecular weight below 1,000 g/mol that are selected from carboxylate esters, phosphate esters and sulfonate esters.
As a rule, suitable plasticizers are all the conventional plasticizers (in this context compare e.g. Paul E. Bruins, Plasticizer Technology [Reinhold PubI. Corp., New Yorki, vol. 1, p. 228-232). C4-to C16-alkyl phthalates, such as dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, benzyl butyl phthalate, dibenzyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate (DP) and diundecyl phthalate (DRiP) as well as the known plasticizers from the group consisting of organic phosphates, adipates and sebacates or also benzyl benzoate and other benzoate plasticizers, alkylsulfonic acid esters of phenol or cresol, dibenzyltoluene or di-phenyl ether are suitable. Furthermore, ester compounds of glycerols formed by esterification reaction of glycerols with carboxylic acids, such as acetic acid, propionic acid or butyric acid, can be used as plasticizers as well as citric acid esters.
The choice criteria for the plasticizers preferably used depend on the one hand on the polymer composition and on the other hand on the viscosity, the gelling conditions of the plastisol and the desired physical properties of a plastisol coated metal part.
It is preferred for reasons of health safety that the plastisols according to the invention do not contain more than 1 wt.-% of phthalates, even more preferably the plastisols according to the invention do not contain any phthalates. Most of the phthalates that are commonly used as plasticizers are hazardous and prone to cause hormonal disbalance in human bodies. Even curedplastisols thatwere appliedin order to seal jointmetal parts of car bodies steadily outgas small amounts of volatile plasticizer compounds, which thereby might be temporarily trapped in the inside of the vehicle interior. Plastisol compositions suitable for the sealing ofjoint metal parts in car bodies are thus preferred that do not comprise more than I wt.-% of plasticizers other than those selected from citric acid esters, more preferably other than those selected from citric acid esters according to formula (I). In this context it is even more preferred that the citrate acid esters according to formula (1) constitute the sole type of plasticizer used in a plastisol according to the invention.
The plastisols according to the invention can moreover optionally comprise ifirther auxiliary substances and additives such as are conventional in plastisol technology. These include e.g. colored pigments, anti-ageing agents, rheology auxiliaries, such as e.g. pyrogcnic silicas, bentones, hydrocarbons and castor oil derivatives, and blowing agents for the preparation of foamed plastisols. These conventional additives include, for example, epoxide plasticizers, preferably epoxidized natural oils, such as epoxidized soya bean oil, epoxidized linseed oil or epoxidized tall oil. As is known, epoxidized plasticizers may be used in small amounts as heat stabilizers in PVC plastisols in particular.
A preferred plastisol composition does not comprise more than 50 wt.-% of auxiliary substances and additives, especially not more than 40 wt.-% of inorganic particular matterand pigments, e.g. bentones, pyrogenie silicas, titanium dioxide, and not more than wt.-% of organic solvents, e.g. hydrocarbons.
In an especially preferred embodiment of the invention the plastisol suitable for the sealing of metal parts comprises a) 20-60 wt.-% of a pulverulcnt PVC resin; b) 10-50 wt.-% of one or more plasticizers, wherein at least 30 wt-% of the total amount of plasticizers is comprised of citric acid esters according to the following general formula (U: flC(=O)0R2 R10 [C(=O)0R3 C(=O)0R4 wherein R1 is selected from hydrogen, branchcd or linear alkyl group with not more than 5 carbon atoms or an acetyl group, preferably an acetyl group; R2, R3 and R4 are mutually independent from each other selected from a linear ailcyl group with at least 2, but not more than 7 carbon atoms, preferably not more than 5 carbon atoms; c) at least 0.5 wt.-%, but preferably not more than 5 wt.-% of reactive additives based on amino-and/or amido-functional compounds, preferably based on polyaminoamides with an amine value of at least 100 mg ICOH / g, but not more than 500mg KOH / g; d) optionally up to 40 wt.-°A of inorganic particulate matter and pigments; c) optionally up to 10 wt.-°A of organic solvcnts.
The plastisols according to the invention are especially suitable to be applied and cured on organically coated metal parts. It was found that the adhesion of the cured plastisol on the metal part can be significantly improved when the metal parts bear an organic coating based on a thermosetting polymer composition comprising an epoxy and/or acrylic base resin and a polyamine and/or polyisocyanate crosslinker. Therefore, the plastisols according to the invention were found to be superior in adhesion when applied to cathodically clectrocoated metal parts as they are based on the prescribed thermosctting polymer compositions.
The present invention also encompasses a process for the scaling of seams ofjoint metal parts comprising the steps of applying a plastisol composition according to the invention to joint metal parts in a way that the plastisol composition covers at least partially the scams between the joint metal parts and curing said plastisol composition at a peak metal temperature above 120 °C, but preferably below 150 °C, more preferably below 140 °C.
Moreover, the present invention encompasses a process for the coating of automobile underbodies comprising the steps of applying a plastisol composition according to the invention to an automobile underbody and curing said plastisol composition at a peak metal temperature above 120 °C, but preferably below 150 °C, more preferably below °C.
In order to achieve superior adhesion of the cured plastisol to the metal parts, it is preferred that within one of the proeesscs according to the invention the plastisol is applied to organically coated, more preferably to cathodically electrocoated metal parts, wherein the organic coatings are preferably based on a thermosctting polymer composition comprising an epoxy and/or acrylic base resin and a polyamine and/or polyisocyanate crosslinker.
Examples:
Adhesion Test: A wedge from 0 to 3mm of the plastisol according to Table 1 is applied on a fresh series of cathodically eleetrocoated CRS steel sheets (Cathoguard 500, BASF, approx. 20 jtm layer thickness). Afterwards the samples are heated at the prescribed peak metal temperature for I 2mm using a circulating air drying oven. After cooling for approx. I to 2 hours the sample is tested for fracture pattern. The whole underbody wedge is cut twice down to the substrate into three approximately 10mm wide stripes. The whole width of the wedge starting from the thick end is to be cut. The plastisol wedge is manually torn off in a slow and even manner.
Evaluation of fracture pattern: "1" = 95-100% cohesive break pattern "2" = 95-tOO % cohesive break pattern, maximum 5% adhesive break pattern at the edges "3" = 75-95 % cohesive break pattern "4" = 50-75 % cohesive break pattern "5" = 25-50% cohesive break pattern "6"= 0-25 % cohesive break pattern oi of, ov of (fl 3-63) suoq.rnnoip4j JOUi1 JO OJflJX1J 1 I I P!X0!U WflLUI3J!j £ £ £ £ P0tm1 91 911 91 9 awuoqn) wIliDftlj /HO)I U 0 T 011 OLljiA-OUITUy o oz GPIU!t?OU!WBXlOd L9 0111A1I ogi oi oi JawouoaToJ-aJnJoaeTAu!A ituAjodoj JAJ OL-99 OEljt?A-)j 00 00 OO[ 001 aotucjouowoHJAd Ot' ---1IIUId jXUOUOSI1Q jAxoqjAqio-= j >j -OfE --Xanq-u = (J) rjnuuoj --Ot' - ________________ __________________ UOO4)/cLI = 0) UipJ0DDU J04S3 I)!DV OIU4!J XTJnq-u = )J J ---01' jf4)P = OAflJdIflo') £ oidmxil z T aidwxa spunodLuoj I!3A UI lJ spuiiodrnoo oqjo rniotu OAiT3OdSOJ Oqi PUI SUOT1IS0dUIOO ioriia vqj. ii:
The test rcsults of the plastisols according to Table 1 that arc Ustcd in Table 2. In comparison to a plastisol formulation that is based on phthalatc cstcrs only it is evidcnt that thc fracture pattern of the citric cstcrs comprising plastisols show at moderate curing temperaturcs of not more than 130 °C supcrior results in thc adhcsion test. At highcr curing tcmpcraturcs the adhesion pcrformance of the phthalatc comprising plastisol becomcs comparable to the cifric cstcr comprising plastisols, whilc the use ofacetyl-tri-n-butyl citric acid estcr (Example 1) as a plasticizer still gives rise to the bcst adhesion pcrfonnance regardlcss of the respective curing tcmpcrature.
Tab. 2 Results from Adhcsion and Corrosion Tests of cured Plastisols according to Tab. 1 on electrocoated CRS sheets Comparative after cunng (a) Example 1 Example 2 Example 3 _______ __________ _______________ ______________________________ Example 140°C 1 1-2 1-2 1-2 135°C 1 1-2 1-2 1-2 130°C 1 2 2-3 3 125°C 2-3 3 3-4 4-5

Claims (1)

  1. <claim-text>Claims Plastisol suitable for sealing of metal parts comprising a) 20-60 wt.-% of a pulverulent polymer selected from PVC and/or Poly(meth)acrylate resins; b) 10-50 wt.-% of one or more plasticizers, wherein at least 30 wt-% of the total amount ofplastieizers is comprised of citric acid esters according to the following general formula (T): flC(=O)0R2 R10 C(=O)0R3 wherein R1 is selected from hydrogen, branched or linear alkyl group with not more than 5 carbon atoms or an acetyl group; R2, R and R4 are mutually independent from each other selected from a branched or linear ailcyl group with at least 2, but not more than 9 carbon atoms; c) at least 0.5 wt.-%, but preferably not more than S wt.-% of reactive additives based on amino-and/or amido-functional compounds and/or blocked polyurcthanes; d) optionally up to 40 wt.-% of inorganic particulate matter and pigments; e) optionally up to 10 wt.-% of organic solvents.</claim-text> <claim-text>2. Plastisol according to claim 1 wherein the residual Ri is an acetyl group.</claim-text> <claim-text>3. Plastisol according to one or both of the claims 1 and 2 wherein at least one and preferably each of the residuals R2, R and R4 is selected from a linear alkyl group with not more than 7 carbon atoms, preferably not more than 5 carbon atoms.</claim-text> <claim-text>4. Plastisol according to one or more of the preceding claims wherein the citric acid esters according to formula (1) arc selected from acetyl-tri-n-butyl citrate, fri-n-butyl citrate, acetyl-triethyl citrate, triethyl citrate and/or acctyl-2-ethylhexyl citrate and preferably is acetyl-tri-n-butyl citrate.</claim-text> <claim-text>5. Plastisol according to one or more ofthe preceding claims \vhcrein the reactive additivc is selected from polyaminoamides.</claim-text> <claim-text>6. Plastisol according to claim 5 wherein the polyarninoamides possess an amine value of at least 100mg KOH / g, but not more than 500mg KOl-T / g.</claim-text> <claim-text>7. Plastisol according to one or more of the preceding claims wherein the pulverulent polymer is sclccted from PVC resins, wherein the PVC resins prcfcrably comprise a mixture of PVC homopolymers and PVC copolymers, wherein the PVC copolymers arc preferably selected from copolymcrs comprising vinyl acetate, styrene, (meth)aciylates and/or alkyl(mcth)acrylates.</claim-text> <claim-text>8. Plastisol according to claim 7, wherein the weight ratio of PVC copolyniers to PVC homopolymers lies within the range from 1.2 to I.8, preferably within the range from [.2 to 1.6.</claim-text> <claim-text>9. Process for the sealing of seams of joint metal parts comprising the steps of applying a plastisol composition according to one or more of the claims 1 to 8 to joint metal parts in a way that the pastisol composition covers at least partially the seams between the joint metal parts and curing said plastisol composition at a peak metal temperature above 120 °C, but preferably below ISO °C.</claim-text> <claim-text>10. Process for the coating of automobile underbodies comprising the steps of applying a plastisol composition according to one or more ofthe claims I to 8 to an automobile underbody and curing said plastisol composition at a peak metal temperature above 120 °C, but below ISO °C, preferably below 140 °C.</claim-text> <claim-text>11. Process according to one or both of the preceding claims 9 or 10 wherein the plastisol is applied to organically coated metal parts, preferably to cathodically clcctrocoated metal parts.</claim-text>
GB1118223.5A 2011-10-21 2011-10-21 Plastisol composition for sealing and automotive coating Withdrawn GB2495776A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110564080A (en) * 2019-02-18 2019-12-13 艾夫特斯有限公司 Plastisol compositions suitable for sealing metal parts

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Publication number Priority date Publication date Assignee Title
GB1142754A (en) * 1966-03-10 1969-02-12 Grace W R & Co Plastisol compositions containing vinyl chloride polymers
GB1516510A (en) * 1974-11-15 1978-07-05 Teroson Gmbh Plastisol of an organic polymer and a plasticiser
JPH06322218A (en) * 1993-05-14 1994-11-22 Toyo Seikan Kaisha Ltd Acrylic plastisol composition excellent in creep resistance
JPH06322225A (en) * 1993-05-14 1994-11-22 Toyo Seikan Kaisha Ltd Plastisol composition of excellent pot life
GB2278116A (en) * 1993-05-14 1994-11-23 Toyo Seikan Kaisha Ltd Acrylic resin plastisols
WO2001094464A1 (en) * 2000-06-02 2001-12-13 Henkel Corporation A plastisol composition and method for using same
JP2003276757A (en) * 2002-03-20 2003-10-02 Daiwa Can Co Ltd Cap for bottled food with excellent corrosion resistance
JP2004083665A (en) * 2002-08-23 2004-03-18 Zeon Kasei Co Ltd Plastisol and molding
US20100093885A1 (en) * 2008-07-19 2010-04-15 Lanxess Deutschland Gmbh Plasticizer preparations

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1142754A (en) * 1966-03-10 1969-02-12 Grace W R & Co Plastisol compositions containing vinyl chloride polymers
GB1516510A (en) * 1974-11-15 1978-07-05 Teroson Gmbh Plastisol of an organic polymer and a plasticiser
JPH06322218A (en) * 1993-05-14 1994-11-22 Toyo Seikan Kaisha Ltd Acrylic plastisol composition excellent in creep resistance
JPH06322225A (en) * 1993-05-14 1994-11-22 Toyo Seikan Kaisha Ltd Plastisol composition of excellent pot life
GB2278116A (en) * 1993-05-14 1994-11-23 Toyo Seikan Kaisha Ltd Acrylic resin plastisols
WO2001094464A1 (en) * 2000-06-02 2001-12-13 Henkel Corporation A plastisol composition and method for using same
JP2003276757A (en) * 2002-03-20 2003-10-02 Daiwa Can Co Ltd Cap for bottled food with excellent corrosion resistance
JP2004083665A (en) * 2002-08-23 2004-03-18 Zeon Kasei Co Ltd Plastisol and molding
US20100093885A1 (en) * 2008-07-19 2010-04-15 Lanxess Deutschland Gmbh Plasticizer preparations

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110564080A (en) * 2019-02-18 2019-12-13 艾夫特斯有限公司 Plastisol compositions suitable for sealing metal parts
EP3696225A1 (en) 2019-02-18 2020-08-19 Eftec Nv Plastisol composition suitable for sealing of metal parts
CN110564080B (en) * 2019-02-18 2021-09-24 依多科（常熟）汽车材料有限公司 Plastisol compositions suitable for sealing metal parts

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