WO2018177483A1 - Oxyde de zirconium stabilisé par un oxyde d'un métal de transition, en tant que promoteur d'adhérence pour des corps moulés en plastique - Google Patents

Oxyde de zirconium stabilisé par un oxyde d'un métal de transition, en tant que promoteur d'adhérence pour des corps moulés en plastique Download PDF

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Publication number
WO2018177483A1
WO2018177483A1 PCT/DE2018/200028 DE2018200028W WO2018177483A1 WO 2018177483 A1 WO2018177483 A1 WO 2018177483A1 DE 2018200028 W DE2018200028 W DE 2018200028W WO 2018177483 A1 WO2018177483 A1 WO 2018177483A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxide
zirconium
adhesive
polymer
molding
Prior art date
Application number
PCT/DE2018/200028
Other languages
German (de)
English (en)
Inventor
Wolfgang Fischer
Original Assignee
Lisa Dräxlmaier 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 Lisa Dräxlmaier GmbH filed Critical Lisa Dräxlmaier GmbH
Publication of WO2018177483A1 publication Critical patent/WO2018177483A1/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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C08G2170/00—Compositions for adhesives
    • C08G2170/20—Compositions for hot melt adhesives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium

Definitions

  • the present invention relates to the use of a zirconium (di) oxide-based ceramic powder containing at least partially rare earth metal-stabilized tetragonal and / or cubic zirconium (di) oxide in a thermoplastic or thermoset polymer molding to improve adhesion in the bonding of adhesives with the polymer molding, the underlying polymer molding, and a method for producing the molding and its use.
  • plastics account for between 15 and 20 percent by weight and are increasing in automotive engineering. These are both exterior and interior parts, for example, blends, d. H. Mixtures of high impact polypropylene with other polyolefins for many years, the most important class of materials in the manufacture of such components, such as automobile bumpers and dashboards represent.
  • Polymeric materials in particular thermoplastics, but also thermoset materials, tend in tensile and bending stresses adversely cracking in the material structure with resulting total failure, as well as lack or declining adhesive force in bonding.
  • stressed parts in the vehicle interior for example in door panels, instrument panels in the airbag area with firing channel or outdoors in bumper systems or in the cable / electrical area of the engine compartment high loads can occur. It is desirable in the event of damage first to prevent cracking and its spread, as well as a component breakage, but also a replacement of adhesives.
  • the object of the present invention is therefore to provide a polymer molding which is suitable for the production of bonded parts with high mechanical strength and ensures in addition to a high elongation at break improved adhesion for adhesives. Furthermore, the task also extends to a simple and economical process for producing such moldings.
  • the shaped body or the joining part comprises a thermoplastic or thermosetting polymer and a ceramic powder based on zirconium (di) oxide, where the zirconium (di) oxide is an at least partially transition metal oxide-stabilized tetragonal ( and / or cubic)
  • Zirconium (di) oxide includes.
  • the transition metal oxide-stabilized serves
  • Zirconium (di) oxide preferably as an adhesion promoter and improvers of the breaking and / or breaking elongation of the resulting shaped body or a corresponding coating or intermediate layer, for example as an adhesive or paint.
  • a particular advantage of the invention is that zirconium dioxide (ZrO 2 ), which hitherto has been known only as a proven ceramic implant material and is considered a fracture-resistant and damage-tolerant material, positively influences the mechanical properties of plastics, in particular with regard to the adhesion of adhesives.
  • ZrO 2 zirconium dioxide
  • Y 2 O 3 3 mol% yttrium oxide
  • Zirconia particles (Zr0 2 ) from the tetragonal to the monoclinic phase. Due to the resulting increase in volume of about 4%, the crack edges
  • the adhesion of adhesives preferably polyurethane hot-melt adhesives, can be markedly increased on the molding.
  • the polymer molding may for example be made of a polymer compound.
  • Polymer molding can be advantageously extended to coatings in the form of paints or intermediate layers in the form of adhesives.
  • the polymer is selected from the group consisting of acrylonitrile-butadiene-styrene (ABS), styrene-acrylonitrile (SAN), polystyrene (PS), polycarbonate (PC), polymethyl methacrylate (PMMA), polyolefins, preferably polyethylene (PE) or, particularly preferred, polypropylene (PP), reinforced or unreinforced, polyamides (PA),
  • Polyurethanes PUR
  • polyacrylates PUR
  • fiber-reinforced This allows numerous plastic vehicle components,
  • the ceramic powder based on transition metal oxide-stabilized tetragonal (and / or cubic) zirconium (di) oxide is from 0.001 to 15% by weight and the plastic is from 85 to 99.999% by weight in the molded article or article
  • the zirconia has a content of 3 to 1 2 mol%
  • Transition metal oxide preferably yttria
  • the zirconium dioxide (Zr0 2 ) can be advantageously stabilized with cerium oxide (Ce0 2 ).
  • the most important stabilizing oxide is yttrium oxide (Y 2 O 3 ).
  • An addition of 3 to 1 2 mol% of yttrium oxide has proven to be particularly suitable since, at this concentration, the zirconium dioxide powder is completely in the form of the tetragonal modification. This has due to the characteristic mechanism of conversion gain tetragonal monoclinic on a very high mechanical load capacity.
  • the adhesive-coated molding preferably has an adhesive force> 1 25 N / 5 cm, depending on the zirconium (di) oxide content. This value refers by way of example to a PP molded body. This means an advantageous increase in the adhesive force or
  • Adhesion for adhesives compared to pure PP preferably has an adhesive force> 152 N / 5 cm with a zirconium (di) oxide content of> 10%. This value refers by way of example to a PP molded body. This means a further advantageous increase in adhesion or adhesion for adhesives compared to the pure PP.
  • the adhesive-coated molding further preferably has an adhesive force> 166 N / 5 cm with a zirconium (di) oxide content of> 12%.
  • This value also refers by way of example to a PP molded body. This means a further advantageous increase in adhesion or adhesion for adhesives compared to the pure PP.
  • the process for producing an adhesion-improved shaped body is carried out by the following steps: a) compounding a thermoplastic or thermosetting polymer with a zirconium (di) oxide-based ceramic powder containing at least partially transition metal oxide-stabilized tetragonal and / or cubic zirconium (di) oxide; b) injection molding, extrusion, hot and cold pressing or rolling;
  • an adhesive improved adhesive coated molding described above is carried out as a vehicle component, in particular as a center console,
  • Instrument panel door trim or as an outer part, in particular as a bumper.
  • the examples tabulate as the polymer an unreinforced polypropylene ("PP") and, for reference, glass fiber reinforced (10%) polypropylene (“PP LGF").
  • PP unreinforced polypropylene
  • PP LGF glass fiber reinforced (10%) polypropylene
  • the polypropylenes and commercially available oxide Zr0 2 -Y 2 0 3 form an example of the adhesion-promoting base for use in an injection molded part.
  • Polypropylene (PP) is applied to an injection molding machine in a proportion of 88-95% by mass of 5-12% by mass of Zr0 2 -Y 2 0 3 93/7 ( "" Amperit ® ”) mixed in the melt, and as a flat shaped body applied.
  • the adhesion tests were carried out on plates (10 ⁇ 10 cm), wherein the decor and the polyurethane hot-melt adhesive used were identical; as well as the amount of glue.
  • the hot melt application temperature was in the range of 30-45 ° C.
  • mechanical strength tests were carried out with the cooled mold part, the results of which are shown in the following Table 1:
  • Table 1 shows first that the admixture of Zr0 2 -Y 2 0 3 causes a significant increase in the adhesive force or adhesion of the adhesive on the molding. Table 1 also shows that the addition of higher proportions of ZrO 2 -Y 2 O 3 further increases the adhesive force of the adhesive. This results in an adjustable adhesion in polymeric materials, especially in polypropylenes.
  • Zr0 2 -Y 2 0 3 acts indirectly, since it is firmly embedded in the polymer matrix matrix, but apparently produces a reduced surface activity, and only becomes effective when applying the hot melt adhesive.
  • Fig. 1 is a schematic representation of an inventive
  • Fig. 2 is a schematic representation of the phase transformation of
  • Fig. 3 is a schematic representation of the conversion gain in
  • Fig. 1 shows a schematic of the structure of a component 1, 2 with an adhesive coating formed as an intermediate layer 3.
  • Adhesives based on e.g. Polyolefin, preferably polyurethane, or acrylate tend under tensile stresses to cracking and cohesion, see. Arrow in Fig. 1, in the material structure with resulting breakage, especially in stressed parts in a vehicle interior or in the cable or electrical area where bending stresses occur.
  • the component 1, 2 and / or the adhesive coating 3 comprise a ceramic powder based on a transition metal oxide-stabilized tetragonal (and / or cubic) zirconium (di) oxide.
  • the transition metal oxide-stabilized zirconium (di) oxide serves as an adhesion promoter both for the moldings 1, 2 and for the adhesive coating 3.
  • the stabilized zirconia in the tetragonal crystal phase may be admixed as a powder in a particular proportion to the adhesive components, for example, one or two component adhesives consisting of polyol and isocyanate hardener prior to mixing or processing, which in the cross-linking reaction in the three-dimensional Matrix is integrated.
  • the adhesive components for example, one or two component adhesives consisting of polyol and isocyanate hardener prior to mixing or processing, which in the cross-linking reaction in the three-dimensional Matrix is integrated.
  • the zirconium dioxide would be conceivable as a filler in powder or fiber form.
  • the zirconia, embedded in the adhesive matrix passes from the tetragonal to the monoclinic crystal phase due to the effect of heat, along with an increase in volume, which then minimizes cracking and increases the adhesive force of the adhesive on a polymer molding.
  • pure zirconia exists in three different phases, which are temperature dependent. From room temperature to ⁇ 1 1 73 ° C, the monoclinic phase is stable. At temperatures above 1137 ° C to ⁇ 2370 ° C the tetragonal phase is present. Above 2370 ° C, the cubic phase is stable.
  • the at least partially transition metal oxide-stabilized tetragonal (and / or cubic) zirconium (di) oxide is evidently able to break down crack energy in the polymer molding and / or the adhesive coating and to increase the adhesive force for adhesives. As shown in Figure 3, a propagating crack strikes a zirconia particle.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne l'utilisation d'une poudre céramique à base de (di)oxyde de zirconium, contenant un (di)oxyde de zirconium tétragonal et/ou cubique, au moins partiellement stabilisé par un oxyde d'un métal des terres rares, dans un corps moulé (1, 2) en un polymère thermoplastique ou thermodurcissable et/ou dans une couche adhésive (3), le (di)oxyde de zirconium stabilisé par un oxyde d'un métal des terres rares étant utilisé en tant que promoteur d'adhérence pour coller des adhésifs à des corps moulés en un polymère.
PCT/DE2018/200028 2017-03-28 2018-03-22 Oxyde de zirconium stabilisé par un oxyde d'un métal de transition, en tant que promoteur d'adhérence pour des corps moulés en plastique WO2018177483A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102017106647.0A DE102017106647B4 (de) 2017-03-28 2017-03-28 Verwendung eines keramischen Pulvers auf der Basis von Seltenerdmetalloxid-stabilisiertem Zirconium(di)oxid als Haftverbesserer für Polymerformkörper, klebstoffbeschichteter Polymerformkörper, Verfahren zur Herstellung eines haftungsverbesserten Polymerformkörpers und dessen Verwendung
DE102017106647.0 2017-03-28

Publications (1)

Publication Number Publication Date
WO2018177483A1 true WO2018177483A1 (fr) 2018-10-04

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DE (1) DE102017106647B4 (fr)
WO (1) WO2018177483A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3319619A1 (de) 1982-06-04 1983-12-08 Mitsui Toatsu Chemicals, Inc., Tokyo Harzzusammensetzung auf polypropylenbasis
WO2002102912A1 (fr) * 2001-06-19 2002-12-27 3M Innovative Properties Company Film protecteur, feuille adhesive, et structure protectrice pour surfaces de sol
WO2011068697A2 (fr) * 2009-12-02 2011-06-09 3M Innovative Properties Company Nanoparticules de zircone fonctionnalisées et films d'indice élevé fabriqués à partir de celles-ci

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3319619A1 (de) 1982-06-04 1983-12-08 Mitsui Toatsu Chemicals, Inc., Tokyo Harzzusammensetzung auf polypropylenbasis
WO2002102912A1 (fr) * 2001-06-19 2002-12-27 3M Innovative Properties Company Film protecteur, feuille adhesive, et structure protectrice pour surfaces de sol
WO2011068697A2 (fr) * 2009-12-02 2011-06-09 3M Innovative Properties Company Nanoparticules de zircone fonctionnalisées et films d'indice élevé fabriqués à partir de celles-ci

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DE102017106647A1 (de) 2018-10-04

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