WO2020234243A1 - Pâte pour protéger le plancher de véhicules - Google Patents

Pâte pour protéger le plancher de véhicules Download PDF

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Publication number
WO2020234243A1
WO2020234243A1 PCT/EP2020/063830 EP2020063830W WO2020234243A1 WO 2020234243 A1 WO2020234243 A1 WO 2020234243A1 EP 2020063830 W EP2020063830 W EP 2020063830W WO 2020234243 A1 WO2020234243 A1 WO 2020234243A1
Authority
WO
WIPO (PCT)
Prior art keywords
paste
weight
polyvinyl chloride
paste according
copolymer
Prior art date
Application number
PCT/EP2020/063830
Other languages
German (de)
English (en)
Inventor
Wolfgang JOHANN
Nadine KIMLING
Original Assignee
Henkel Ag & Co. Kgaa
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 Henkel Ag & Co. Kgaa filed Critical Henkel Ag & Co. Kgaa
Publication of WO2020234243A1 publication Critical patent/WO2020234243A1/fr

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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
    • 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

Definitions

  • the present invention relates to a paste which is particularly suitable as underbody protection for vehicles which, in addition to polyvinyl chloride, has a copolymer of vinyl chloride and vinyl acetate, the total content of polyvinyl chloride in the paste being at least 30% by weight.
  • Objects made of metal such as those used in vehicle, machine and device construction, often have to be provided with an abrasion-resistant coating as protection against damage.
  • vehicle construction in particular in the automotive sector, these are primarily the underbody area of the vehicle and the wheel houses, which are exposed to an increased risk of damage, for example from falling rocks.
  • seams for example weld seams as they result from the assembly, must be sealed against the ingress of dust and water.
  • so-called plastisols are usually used, i.e. dispersions of organic plastics in plasticizers, which gel when heated to higher temperatures and harden when cooled.
  • No. 5,563,188 relates to a coating composition against impact stress based on PVC with high film strength and long shelf life.
  • the strong increase in film strength with simultaneous achievement of high storage stability is attributed to the fact that polyvinyl copolymers are used, in particular those with a high K value which at the same time have a high acetate content.
  • the coating compositions described in the publication are composed of PVC, polyvinyl acetate copolymer, calcium carbonate, hollow plastic spheres, plasticizers, dyes and additives.
  • No. 3,772,237 describes a sealing compound which has a vinyl dispersion resin, a vinyl mixed resin, a ketone aldehyde condensation resin, fillers, plasticizers and NH2-organofunctional silanes as adhesion promoters. Good adhesion properties are ascribed to the claimed sealing compound.
  • CN 105 017 879 discloses a plastisol for automobile chassis and a corresponding manufacturing process.
  • the main components of the plastisol are PVC paste resin and dioctyl phthalate (DOP).
  • No. 5,205,963 describes yellowing-resistant, overpaintable plastisol compositions made from homopolymers or copolymers of vinyl chloride or mixtures thereof, which, in addition to the usual additives, contain optical brighteners and optionally strongly acidic ion exchangers and are suitable for overpaintable seals, especially seam and fold seals, in body construction.
  • optical brighteners and optionally strongly acidic ion exchangers and are suitable for overpaintable seals, especially seam and fold seals, in body construction.
  • a first object of the present invention is a paste which a) 15 to 45 wt .-% of a copolymer of vinyl chloride and vinyl acetate; b) 35 to 45% by weight of a plasticizer; and c) comprises homopolymeric polyvinyl chloride, the total content of polyvinyl chloride in the paste being at least 30% by weight, the total content of polyvinyl chloride being composed of the proportions of polyvinyl chloride from the copolymer and the homopolymeric polyvinyl chloride and the details of the weight percentages % each based on the total weight of the paste, characterized in that the proportion of vinyl acetate in the copolymer is 4 to 7 mol%.
  • the total content of polyvinyl chloride in the paste according to the invention is composed of the proportions of polyvinyl chloride from the copolymer and the homopolymeric polyvinyl chloride.
  • a copolymer of vinyl chloride and vinyl acetate is to be understood as a copolymer which is formed from vinyl chloride monomer units and vinyl acetate monomer units.
  • the paste according to the invention fulfills both the requirements of DBL 6909 for underbody protection and DBL 6070 for seam sealing, and that is necessary with a layer thickness that is up to 40% less than with conventional materials.
  • the copolymer in the paste according to the invention has a certain proportion of vinyl acetate monomer units. Therefore, the proportion of vinyl acetate monomer units is 4 to 7 mol%.
  • the proportion of copolymer in the paste according to the invention is preferably 20 to 25% by weight, based on the total weight of the paste.
  • the copolymer used in the paste according to the invention is preferably an emulsion polymer. It has surprisingly been found that a copolymer produced by means of emulsion polymerization contributes to a further reduction in the amount of material required, with the standards required in the automotive industry for underbody protection and seam sealing being achieved despite the reduced amount of material. Without being tied to a specific theory, the particle size distribution achieved by means of emulsion polymerization is considered to be particularly advantageous. An embodiment is therefore preferred in which the copolymer has an average particle size (D50) of 0.5 to 2 ⁇ m, preferably 0.7 to 1.5 ⁇ m, determined in accordance with the static laser light scattering method.
  • D50 average particle size
  • copolymers has proven to be advantageous which have a chain length value K of 65 or more.
  • An embodiment is therefore preferred in which the copolymer has a K value of 65 or more, preferably 65 to 100, particularly preferably 65 to 90.
  • the K value can be determined in accordance with DIN EN ISO 1628-2.
  • the mechanical strength of the paste in particular its abrasion resistance, could be increased if the total content of polyvinyl chloride in the paste was at least 30% by weight, based on the total weight of the paste.
  • a further improvement in the abrasion resistance could be achieved by increasing the proportion of polyvinyl chloride, the processability of the paste being adversely affected above a certain proportion.
  • An embodiment of the paste according to the invention is therefore preferred in which the total content of polyvinyl chloride in the paste is 30 to 50% by weight, preferably 35 to 45% by weight, based in each case on the total weight of the paste.
  • the paste according to the invention has 5 to 25% by weight, preferably 7 to 20% by weight, of homopolymeric polyvinyl chloride.
  • the paste according to the invention is also characterized by a high proportion of plasticizers, which makes up 35 to 45% by weight of the total weight of the paste.
  • the plasticizer is preferably selected from the group of phthalates, in particular the esters of phthalic acids.
  • the plasticizer is particularly preferably selected from the esters of isophthalic acid in which the ester groups each have 5 to 12, preferably 6 to 11 carbon atoms, which are either linear chains, but preferably branched.
  • the plasticizer is diisononyl phthalate and / or diisodecyl phthalate.
  • the paste according to the invention is characterized by a high level of stability, which makes it particularly suitable for sealing seams, for example weld seams. It has proven advantageous here if the paste has a high solids content.
  • An embodiment is therefore preferred in which the paste according to the invention has a solids content of at least 96% by weight, preferably 96 to 99% by weight, based on the total weight of the paste.
  • the paste must be specific
  • the paste must be processed so that it can be integrated into the usual work processes.
  • the materials used for the coating are usually sprayed on.
  • An embodiment of the paste according to the invention is therefore preferred in which it can be sprayed.
  • the paste according to the invention preferably has a viscosity of 2 to 4 Pas, particularly preferably 2.5 to 3.5 Pas, determined at 20 ° C. (Z4, 400 s -1 , Bingham).
  • the paste according to the invention has hollow microspheres, preferably in an amount of 0 to 15% by volume, particularly preferably 0 to 10% by volume, based on the total volume of the paste.
  • the paste according to the invention is free from hollow microspheres.
  • the paste according to the invention has a density of 1.0 to 1.5 g / cm 3 , preferably 1.15 to 1.25 g / cm 3 , determined in accordance with DIN 51757.
  • the low density of the paste according to the invention could a significant weight reduction can be achieved without impairment of the protective effect or the sealing effect being observed.
  • the paste according to the invention also has fillers, preferably in an amount of 10 to 20% by weight, particularly preferably 12 to 15% by weight, in each case based on the total weight of the paste.
  • the filler can be calcium carbonate, for example.
  • the paste according to the invention therefore has 0 to 0.25% by weight, preferably 0.1 to 0.25% by weight, of zinc oxide, based on the total weight of the paste.
  • An embodiment in which the proportion of calcium oxide is less than 1.5 % By weight is, preferably 0 to 1% by weight, in particular 0.5 to 1% by weight, based in each case on the total weight of the paste.
  • the paste according to the invention is characterized by high abrasion resistance and stability, which makes it particularly suitable for use in vehicle construction.
  • the present invention therefore also provides the use of the paste according to the invention as underbody protection of vehicles, in particular automobiles, and / or for sealing seams, in particular weld seams.
  • the paste is preferably applied at a temperature of 20 to 45 ° C., particularly preferably 25 to 40 ° C., for example by means of spraying.
  • the paste according to the invention it was surprisingly possible to reduce the required layer thickness without any impairment of the protective effect being found.
  • An embodiment is therefore preferred in which the paste is used in a layer thickness of 250 ⁇ m to 1200 ⁇ m, preferably 280 to 1000 ⁇ m.
  • a paste according to the invention with the composition shown in Table 1 was subjected to various tests, the information in the table each relating to the total weight of the paste.
  • the proportion of vinyl acetate units in the copolymer used was 5 mol%.
  • the paste according to the invention had a tensile strength of 6.0 MPa, determined in accordance with DIN 53504, and a tensile elongation of 400%, determined in accordance with DIN 53504.
  • the paste according to the invention also had excellent overpaintability and good stability.
  • FIG. 1 shows the abrasion resistance of the paste according to the invention in comparison with the target values specified by the automotive industry.
  • the lower curve shows the target values as specified by the automotive industry, while the upper curve shows the values achieved with the paste according to the invention.
  • the abrasion resistance was determined in accordance with ASTM D968-51, with chilled cast blasting media being used instead of sand as the specified blasting media (Diamant GH-K 4-5 mm, Würth).
  • the target values for the paste according to the invention have already been achieved with significantly smaller layer thicknesses than required.
  • the abrasion resistance of the paste according to the invention with a dry layer thickness of 500 ⁇ m was 0.3 l / pm, while the abrasion resistance required by industry for such layer thicknesses is 0.15 l / pm.
  • FIG. 2 shows the stability of the paste according to the invention, which is used as a measure of the suitability for seam sealing.
  • the seam sealing compound is drawn onto an electrolytically galvanized, KTL-coated steel sheet in the form of a strip parallel to the edge of the test sheet using a doctor blade with a gap width of 80 mm and a defined gap height (wet layer thickness).
  • the test sheet provided with the seam sealing compound is stored freely hanging for 20 minutes at room temperature.
  • the sheet metal provided with the seam sealing compound is exposed to a temperature load of 60 ° C. in the dryer for 5 minutes. This is followed by a temperature load of 140 ° C. for 20 minutes.
  • the test sheet is then used to measure whether and how far the applied seam sealing compound has slipped off the lower edge of the test sheet. The slip distance is given in mm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Sealing Material Composition (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une pâte qui peut être employée notamment pour protéger le plancher de véhicules, laquelle comprend, en plus de polychlorure de vinyle, un copolymère issu du chlorure de vinyle et de l'acétate de vinyle, la teneur totale de la pâte en polychlorure de vinyle valant au moins 30 % en poids.
PCT/EP2020/063830 2019-05-21 2020-05-18 Pâte pour protéger le plancher de véhicules WO2020234243A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19175589.1 2019-05-21
EP19175589 2019-05-21

Publications (1)

Publication Number Publication Date
WO2020234243A1 true WO2020234243A1 (fr) 2020-11-26

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2020/063830 WO2020234243A1 (fr) 2019-05-21 2020-05-18 Pâte pour protéger le plancher de véhicules

Country Status (1)

Country Link
WO (1) WO2020234243A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3772237A (en) 1971-03-24 1973-11-13 Union Carbide Corp Vinyl paste sealant composition
JPH0481477A (ja) * 1990-07-24 1992-03-16 Honda Motor Co Ltd 耐チッピング塗料
US5205963A (en) 1991-07-12 1993-04-27 Ems-Togo Ag Vinyl chloride plastisol compositions containing optical brighteners and process for their production
US5563188A (en) 1990-06-05 1996-10-08 Stankiewicz Gmbh Impact resistant coating composition
JP3588906B2 (ja) * 1996-04-11 2004-11-17 東ソー株式会社 ペースト用塩化ビニル共重合体組成物及びそれよりなる発泡体、発泡体の製造方法並びにその用途
CN105017879A (zh) 2015-08-20 2015-11-04 韩功篑 一种汽车底盘塑溶胶及其制备方法
US20190040170A1 (en) * 2016-02-09 2019-02-07 Tosoh Corporation Vinyl chloride-vinyl acetate copolymer particles and automobile underbody coating agent

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3772237A (en) 1971-03-24 1973-11-13 Union Carbide Corp Vinyl paste sealant composition
US5563188A (en) 1990-06-05 1996-10-08 Stankiewicz Gmbh Impact resistant coating composition
JPH0481477A (ja) * 1990-07-24 1992-03-16 Honda Motor Co Ltd 耐チッピング塗料
US5205963A (en) 1991-07-12 1993-04-27 Ems-Togo Ag Vinyl chloride plastisol compositions containing optical brighteners and process for their production
JP3588906B2 (ja) * 1996-04-11 2004-11-17 東ソー株式会社 ペースト用塩化ビニル共重合体組成物及びそれよりなる発泡体、発泡体の製造方法並びにその用途
CN105017879A (zh) 2015-08-20 2015-11-04 韩功篑 一种汽车底盘塑溶胶及其制备方法
US20190040170A1 (en) * 2016-02-09 2019-02-07 Tosoh Corporation Vinyl chloride-vinyl acetate copolymer particles and automobile underbody coating agent

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Automotive Coatings Formulation Chemistry, Physics and Practices. European Coatings Tech Files", 1 March 2008, VINCENTZ NETWORK, ISBN: 9783866309043, pages: 74 - 75, XP002795295 *
VINNOLIT ET AL: "Product Information Vinnolit = registriertes Warenzeichen der Fa. Vinnolit GmbH & Co. KG, Deutschland Raw Material Properties Typical Value* Unit Test Method DIN EN ISO ISO", 1 October 2017 (2017-10-01), XP055702688, Retrieved from the Internet <URL:https://vinnolit.com/vproducts.nsf/allPages/BB260845634CF18FC12582CF00297697/$file/Vinnolit%20E%2070%20SC%20english.pdf?open> [retrieved on 20200609] *

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