GB2031911A - A method of preparing a plastisol - Google Patents
A method of preparing a plastisol Download PDFInfo
- Publication number
- GB2031911A GB2031911A GB7932626A GB7932626A GB2031911A GB 2031911 A GB2031911 A GB 2031911A GB 7932626 A GB7932626 A GB 7932626A GB 7932626 A GB7932626 A GB 7932626A GB 2031911 A GB2031911 A GB 2031911A
- Authority
- GB
- United Kingdom
- Prior art keywords
- plastisol
- adhesion
- polymer
- plastisols
- weight
- 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.)
- Granted
Links
- 229920001944 Plastisol Polymers 0.000 title claims abstract description 43
- 239000004999 plastisol Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 12
- 239000004014 plasticizer Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 5
- -1 acrylic compound Chemical class 0.000 claims abstract description 5
- 238000013329 compounding Methods 0.000 claims abstract description 5
- 229920001519 homopolymer Polymers 0.000 claims abstract description 5
- 125000003277 amino group Chemical group 0.000 claims abstract description 4
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000003368 amide group Chemical group 0.000 claims abstract description 3
- 229920000768 polyamine Polymers 0.000 claims description 7
- 239000002318 adhesion promoter Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 abstract description 7
- 229920000915 polyvinyl chloride Polymers 0.000 description 14
- 239000004800 polyvinyl chloride Substances 0.000 description 13
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229960001124 trientine Drugs 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 235000010216 calcium carbonate Nutrition 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- KYXHKHDZJSDWEF-LHLOQNFPSA-N CCCCCCC1=C(CCCCCC)C(\C=C\CCCCCCCC(O)=O)C(CCCCCCCC(O)=O)CC1 Chemical compound CCCCCCC1=C(CCCCCC)C(\C=C\CCCCCCCC(O)=O)C(CCCCCCCC(O)=O)CC1 KYXHKHDZJSDWEF-LHLOQNFPSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229960004488 linolenic acid Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 125000002636 imidazolinyl group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229960004011 methenamine Drugs 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid 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
- 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
- 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
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
- C08L77/08—Polyamides derived from polyamines and polycarboxylic acids from polyamines and polymerised unsaturated fatty acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
A plastisol is prepared from a paste-grade powder of a homopolymer and/or copolymer of vinyl chloride, vinylidene chloride or an acrylic compound and adhesion promotors containing amido and/or amino groups by dry heating the polymer together with 0.5 to 10% by weight of the adhesion promotor, based on the polymer, at a temperature of 100 to 180 DEG C, e.g. during spray drying, and then compounding the powder so obtained with a plasticizer. The plastisol obtained exhibits improved adhesion properties at lower baking temperatures.
Description
SPECIFICATION
A method of preparing a plastisol
This invention relates to the production of plastisols.
Plastisols based on paste-grade powders of specific polymers have long been known, cf. K. Weinmann,
Deutsche Farben-Zeitschrift, Vol. 19. pp 93 to 106 (1965). Polymers which are particularly suitable are polyvinyl chlorides, vinyl chloride/vinyl acetate copolymers and other vinyl chloride copolymers, polyvinyl lidene chloride and vinylidene chloride copolymers. Recently plastisols based on acrylate homopolymers and copolymers have been disclosed in German Auslegeschriften Nos. 2454235 and 25 29 732.
When producing coatings on substrates such as steel plate (which can be primed or unprimed) adhesion promoters must be added to the plastisols in order to obtain an adequate adhesion. Known primers for PVC plastisols are polyamines and polyaminoamides, which may optionally be combined with further additives, e.g., basically reacting alkali metal or alkaline earth metal compounds (cf. German Auslegeschrift No. 02 037). The action of such primers is completely satisfactory if sufficiently high baking temperatures are used when the plastisol is gelled. However, considerable adhesion problems occur if gelling is performed at lower temperatures, e.g. below 140 and particularly at 100 to 1200C. Even the hitherto known additional activators do not permit the production of really good adhering coatings at such low temperatures.
The present invention provides plastisols made with readily available, conventional adhesion promoters or primers capable of giving coatings having satisfactory adhesion, particulary on metal substrates, when gel led at relatively low temperatures of approximately 100 to 1 400C without the other characteristics of the plastisols suffering.
These new plastisols are made by compounding with plasticizers a modified polymer powder which has itself been made by a simple straightforward method.
It has surprisingly been found that this problem can be solved if the polymers are dry heated jointly with the adhesion promoters and are only subsequently processed to a plastisol by the addition of plasticizers.
According to one aspect of the invention therefore, a plastisol is prepared by dry heating at 100 to 180"C, a paste-grade powder of a homopolymer and/or copolymer of vinyl chloride, vinylidene chloride or an acrylic compound with 0.5 to 10% by weight based on the weight of the polymer, of an adhesion promoter containing amido and/or amino groups, and then compounding the modified polymer powder with a plasticizer to give a plastisol.
According to a preferred embodiment the polymer and the adhesion promotor are dry heated together by spray drying a dispersion comprising the polymer and the adhesion promotor. The preferred temperature for the dry heating of the two components is between 120 and 140"C.
Suitable polymers for the production of plastisols are in particular PVC resins and PVC copolymers, as described in greater detail by K. Weinmann,loc. cit. It is also possible to use polyvinylidene chloride and vinylidene chloride copolymers. Afurther group of suitable polymers are the acrylate and methacrylate homopolymers and copolymers described in my German Auslegeschriften 2454235 and 2529732. Among the particularly suitable and consequently preferred acrylate and methacrylate polymers are those containing carboxyl or epoxy groups as functional groups.
The particularly preferred primers are polyaminoamides, more particularly known as hardeners for epoxy resins. In the production thereof monomeric and oligomeric fatty acids are used with approximately 12 to 18
C-atoms in the basic fatty acids, which are obtained by heating unsaturated fatty acids, optionally using catalysts. The preferred dimerized fatty acids are obtained by isomerisation of 2,1 2-linolenic acid to 9,11-linolenic acid followed by Diels-Alder dimerization and are then converted into polyaminoamides by reaction with polyamines, e.g., triethylene tetramine. They are commercially available, for example under the tradenames VERSAMID (Schering AG), MERGINAMID (Harburger Fettchemie) or CASAMID (Akzo
Chemie).In General the products contain acid amine groups, primary amino groups, secondary amino groups and imidazoline groups.
Amidoamines have proved particularly suitable as primers for plastisols based on PVC or vinyl chloride copolymers. Polyamines such as ethylene diamine, diethylene triamine, hexamethylene tetramine or polyethylene imine also lead to a certain improvement. Polyamines and amidoamines are very suitable as primers for acrylates and methacrylates, particularly polymers with functional groups, e.g., carboxyl or epoxy grouups. The combination of polyaminoamides with carboxyl group-containing acrylate and methacrylate polymers provides particularly well adhering coatings on primed as well as bright metal sheets.
According to the invention the method is performed particularly simply and effectively if the adhesion promoter is added as such or in the form of a concentrated aqueous solution or dispersion (optionally using an emulsifier) to an aqueous dispersion of the polymer, as obtained in conventional manner by suspension or emulsion polymer-isation. From the thus formed dispersion containing the primer it is possible to subsequently separate the polymer by spray drying in a manner known per se, whilst simultaneously performing the joint heating of the components required by the invention.Suitable processes for the spray drying of polymer dispersion, which may also contain further additives, are described in British Patent 1 461 478 and German Auslegeschrift 21 46753. it is important that the spray drying conditions are selected in such a way that the basic polymer and the primer are jointly heated for a sufficient time period and to such a temperature that the desired activation takes place, without deterioration and the simultaneous undesired discolouration of the product. Therefore the conditions (temperature and dwell time) are chosen in such a way that the temperature of the material to be dried is as high as possible, whilst avoiding deterioration or disintegration. Thus, at the highest temperatures the dwell time must be correspondingly reduced.For example atomizing drying using the countercurrent principle is suitable and in this hot air at approximately 130 to 170"C is blown from below into the drying tower. The air exit temperature is between appriximately 60 and 1 205C. The temperatures are obviously dependent on the tower geometry and the construction of the spraying nozzle.
The particle size of the polymer powder must be such that it is optimal for plastisol production. For PVC the most preferred particule size is 0.1 to 10 microns and for polymethylmethacrylate approximately between 1 and 50 microns. Any coarse particles produced by sintering can be separated by subsequent screening or sifting and grinding.
The following Examples illustrate the invention. All values in the tables are average figures from three determinations.
Example 1:
a) 30 g of a PVC powder produced by emulsion polymerization were dispersed in 30 ml of water. 0.75 of
polyaminoamide (from a dimeric fatty acid and triethylene tetramine) were dissolved in water and
stirred into the dispersion. This was followed by filtering and drying for about 5 minutes at 1300C in a
vacuum drying chamber. A plastisol was produced from this powder by using butylbenzyl phthalate
as the plasticizer and calcium carbonate and calcium oxide as activators.
For comparison purposes a second plastisol was produced using materials, but the primer was added
as such to the plastisols in the conventional manner.
The two plastisols were tested as a coating on steel plate primed by electro coating (EC-primed). Good
adhesion was obtained in the case of the plastisol produced according to the invention after gelling for
20 minutes at 120 to 1300C. whereas this only occurred at 140 C with the comparative product
b) As described above a copolymer of 13 parts by weight of butyl methacrylate, 85 parts by weight of
methylene methacrylate and 2 parts by weight of methacrylic acid, containing free carboxyl groups,
was dispersed in water and mixed with 2.5% by weight of a polyaminoamide and subsequently dried
together with the latter. For comparison purposes once again a second plastisol was produced using
identical substances, but the primer was only added when compounding the plastisol.
The plastisol produced according to the invention gave good adhesion after gelling for 20 minutes at 1 20 C, whereas the comparative product only showed adequate adhesion after baking at higher
temperatures.
Example 2:
A PVC dispersion was produced by emulsion polymerization. This dispersion was subsequently divided
into three parts, one part being directly spray-dried (A), whereas a concentrated solution of a commercial
polyaminoamide of triethylene tetramine and dimeric acid (B) or triethylene tetramine/tetraethylene
pentamine 1:1 and dimeric acid (C), respectively, was stirred into the other two parts. If necessary the
dispersion was stabilized by lowering the pH value by adding phosphoric acid. After screening off coarse
particles the latex samples were spray-dried in conventional manner. The air inlet temperature was
approximately 1 50 C and the air outlet temperature approximately 70"C.
Plastisols of the following composition were produced from the thus obtained PVC powders, whereby in the case of samples A1 and A2 the polyaminoamides used for samples B and C were incorporated into the
plastisol with the other ingredients, whereas in the case of samples B and C according to the invention the
primer was added before spray drying in the manner described hereinbelow:
Parts by weight
Polyvinyl chloride 20
Butylbenzyl phthalate 36
CaCO3 40
CaCO3 (coated) 10
CaO 2
Polyaminoamide 0.4
E.C.-primed metal sheets were coated with the plastisols and subsequently the adhesion was tested after
gelling for 20 minutes at different temperatures. Table 1 gives the results obtained and in this and the
following Tables the following meanings are used: + good adhesion - no adhesion (coating can be peeled off by hand).
TABLE I
Gelling temperature A1 A2 G C 100 - - + + 110 - - + + 120 - - + + 1400C + + + +
Adhesive bonds were produced from plastisols A, B and C and although it was found that the plastisols according to the invention did not in all cases improve the shear strength, there is a definite improvement in the adhesion.In the automobile industry a cohesion break (K) is certainly preferable to an adhesion break (A), because in the first case both areas of fracture are coated with plastisol material in the case of a break, so that at least better corrosion protection is obtained The following Table 2 shows the values obtained using two different commercial polyaminoamides, one based on dimerzed fatty acids (A1 and B) and one based on monomer fatty acids (A2 and C).
TABLE 2
Shear strength (N/mm2 A1 A2 B C on EC-base after 20 minutes at 120 C 07A 0.4A 0.7K 0.70K Peel strength (N/cm) after 3 minutes at 120"C 103 A 126 A 103 K 83 K
Example 3
Example 2 was repeated, but diisobutyl phthalate was used as the plasticizer instead of butylbenzyl phthalate. The results are given in the following Table 3 and show a considerable improvement in the case of the plastisols produced according to the invention, particularly in connection with the cohesion break.
TABLE 3
Shear strength (N/mm2 A1 A2 B C after 20 minutes at 120 0.54A 0.42A 057k 0.61k Peei strength (N/cm) after 20 minutes at 1200C 70 A 85 A 59 A 96 K
Example 4
If in the case of the plastisols of Example 2 the drying agent CaO is omitted values are once again obtained which stress the advantages of working according to the invention, as shown by the following Table 4.
TABLE 4
Peel strength (N/cm) A1 A2 B C on EC-base after 20 minutes at 120 C 48 A 60 A 83 K 66 K after20minutesat140 C 116A 91 A 100K 85K
Example 5
From the PVc powders produced according to Example 2 plastisols with the following composition were produced:
Parts by weight
Polyvinyl chloride 29
Butylbenzyl phthalate 36
CaCO3 52
The samples differ only with regard to the way in which the polyaminoamide is added before (B and C) and after spray-drying (A); The superiority of the plastisols produced according to the invention with regard to adhesion on metal substrates is once again demonstrated.
TABLE 5
A1 A2 B C
Adhesion on EC-base after 20 minutes at 100 C - - + + 110'C - - + + 1200C - - + + 140"C - - + +
Example 6
Example 2 was repeated, but the polyvinyl chloride was replaced by a copolymer of vinyl chloride and 5% by weight vinyl acetate. The results are given in Table 6.
TABLE 6
Gelling Temperature A2 C 110 - + 1200C - + 140"C - +
The results of the above examples show that-as a result of the method according to the invention surprising improvements are obtained regarding the adhesion characteristics. A further advantage of the products produced according to the invention is that they give the plastisols an excellent stability (low flow tendency, measured in Pascal seconds Pa.s). It is therefore possible in certain cases to obviate the use of thixotropic agents or highly dispersed fillers, such as precipitated or coated chalk.
Simple polyamines such as diethylene triamine or triethylene tetramine are virtually inactive as primers when added to PVC plastisols. However, they lead to an improvement of the adhesion if, in accordance with the invention, they are heated together with the PVC and are incorporated in this way into plastisols. In this case of acrylate and methacrylate polymers with free carboxyl groups very good adhesion characteristics are obtained if such simple polyamines are added according to the invention.
Claims (8)
1. A method of preparing a plastisol which comprises dry heating to a temperature of about 100 to 1800C a paste-grade powder of a homopolymer and/or copolymer of vinyl chloride, vinylidene chloride or an acrylic compound with 0.5 to 10% by weight, based on the polymer, of an adhesion promoter containing amido and/or amino groups, and then compounding the modified polymer powder so obtained with a plasticizer to give a plastisol.
2. A method according to claim 1, in which the polymer is spray-dried together with the adhesion promotor.
3. A method according to claim 1 or 2, in which the polymer and the adhesion promotor are heated to 120 to 1400C.
4. A method according to any one of claims 1 to 3, in which 2 to 4% by weight of adhesion promotors, based on the polymers, are used.
5. A method according to any of claims 1 to 4, in which the adhesion promotor is a polyaminoamide.
6. A method according to claim 5, in which the polyaminoamide is the product of the reaction of a dimerized unsaturated fatty acid of 12to 18 carbon atoms with a polyamine.
7. A method according to claim 1 substantially as described in any one of Examples 1 to 6.
8. A plastisol whenever prepared according to the method of one of claims 1 to 7.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2840996A DE2840996C2 (en) | 1978-09-21 | 1978-09-21 | Process for the production of plastisols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2031911A true GB2031911A (en) | 1980-04-30 |
| GB2031911B GB2031911B (en) | 1983-02-02 |
Family
ID=6049981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7932626A Expired GB2031911B (en) | 1978-09-21 | 1979-09-20 | Method of preparing a plastisol |
Country Status (5)
| Country | Link |
|---|---|
| BE (1) | BE878832A (en) |
| DE (1) | DE2840996C2 (en) |
| FR (1) | FR2436664B3 (en) |
| GB (1) | GB2031911B (en) |
| IT (1) | IT1123278B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2190091A (en) * | 1983-11-12 | 1987-11-11 | Nippon Paint Co Ltd | Coating composition having improved weathering resistance and recoating property |
| AU598935B2 (en) * | 1983-11-12 | 1990-07-05 | Nippon Paint Co., Ltd. | Coating composition having improved weathering resistance and recoating property and resinous composition to be used therein |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3221354A1 (en) * | 1982-06-05 | 1983-12-08 | Schering AG, 1000 Berlin und 4709 Bergkamen | METHOD FOR PRODUCING COATINGS AND ADHESIVE JOINTS WITH POLYVINYL CHLORIDE PLASTISOLS WITH IMPROVED ADHESION AND PLASTISOLS FOR THE METHOD |
| DE3801649C2 (en) * | 1988-01-21 | 1996-09-19 | Solvay Werke Gmbh | Underbody protection composition, process for their preparation and use of an optionally synthetic calcium carbonate for rheology control of underbody protection compounds |
| DE3900054A1 (en) * | 1989-01-03 | 1990-07-12 | Solvay Werke Gmbh | UNDERFLOOR PROTECTION MASS AND METHOD FOR THE PRODUCTION THEREOF |
| DE4112823C2 (en) * | 1991-04-19 | 1996-11-21 | Henkel Teroson Gmbh | Yellowing of topcoats preventing plastisols, process for their preparation and their use |
| DE4421012A1 (en) * | 1994-06-20 | 1995-12-21 | Teroson Gmbh | Acoustically effective plastisols |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2512366C3 (en) * | 1975-03-21 | 1979-10-25 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Process for the production of coatings on metallic materials by coating with polyvinyl chloride |
-
1978
- 1978-09-21 DE DE2840996A patent/DE2840996C2/en not_active Expired
-
1979
- 1979-09-17 FR FR7923131A patent/FR2436664B3/fr not_active Expired
- 1979-09-17 BE BE0/197184A patent/BE878832A/en not_active IP Right Cessation
- 1979-09-20 GB GB7932626A patent/GB2031911B/en not_active Expired
- 1979-09-21 IT IT25919/79A patent/IT1123278B/en active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2190091A (en) * | 1983-11-12 | 1987-11-11 | Nippon Paint Co Ltd | Coating composition having improved weathering resistance and recoating property |
| AU598935B2 (en) * | 1983-11-12 | 1990-07-05 | Nippon Paint Co., Ltd. | Coating composition having improved weathering resistance and recoating property and resinous composition to be used therein |
Also Published As
| Publication number | Publication date |
|---|---|
| IT1123278B (en) | 1986-04-30 |
| FR2436664A1 (en) | 1980-04-18 |
| IT7925919A0 (en) | 1979-09-21 |
| DE2840996C2 (en) | 1984-05-03 |
| GB2031911B (en) | 1983-02-02 |
| DE2840996B1 (en) | 1979-03-29 |
| FR2436664B3 (en) | 1980-11-14 |
| BE878832A (en) | 1980-01-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |