Method for applying, to an inorganic surface, a PVC composition having improved adhesion to surfaces

Abstract

The present invention relates to a method for applying, to an inorganic surface, a self-adhesive PVC composition which comprises a composition (C) comprising: an optionally protected aminosilane; and at least one compound selected from a titanium complex, a zirconium complex and an optionally protected isocyanate compound;
said method comprising a step of activating said surface, selected from heat treatment, a shot-peening step, a plasma treatment step, cleaning With solvent and a step of silica application.

Claims

1. Method for applying, to an inorganic surface, a self-adhesive PVC composition comprising a composition (C) comprising: an optionally protected aminosilane; and at least one compound selected from among a titanium complex, zirconium complex and/or an optionally protected isocyanate compound; said method comprising an activation step of said surface, selected from among heat treatment, a shot peening step, plasma treatment step, solvent cleaning and a silicification step.

2. The method according to claim 1 wherein the PVC composition, after the surface treatment step, is applied by injection moulding, by extrusion, by rotational moulding or by compression moulding.

3. The method according to claim 1, wherein the inorganic surface is a surface in glass or metal.

4. The method according to claim 1, wherein the inorganic surface is in glass.

5. The method according to claim 1, wherein the inorganic surface is in metal.

6. The method according to claim 4, wherein the composition (C) comprises: an optionally protected aminosilane; and a protected isocyanate or a titanium complex.

7. The method according to claim 4, wherein surface activation is performed by heat treatment.

8. The method according to claim 4, wherein the application of the PVC composition is performed by extrusion.

9. The method according to claim 5, wherein the composition (C) comprises: an optionally protected aminosilane; and a protected isocyanate or a titanium complex.

10. The method according to claim 5, wherein surface activation is performed by heat treatment, preferably via radiating heat.

11. The method according to claim 5, wherein application of the PVC composition is performed by extrusion.

Description

COMPARTIVE EXAMPLE 1

(1) A PVC composition was prepared using a PVC base (Kwert 65) containing 30 weight % of T8 trimellitate plasticizer marketed by ADK Palmarole, 1.5 weight % of stabilizer (Ca/Zn), 0.5 weight % of co-stabilizer (phosphite-type antioxidant ADK STAB 1500, marketed by Adeka Palmarole), 2% Tetrabutyl titanate.

(2) A glass surface was treated at ambient temperature with methyl-ethyl-ketone before being heated in an oven to 200 C.

(3) The PVC composition was applied by extrusion (Escuyer 40) under the following conditions: die head temperature of 170 C., with a temperature profile of 160 to 180 C.; and extrusion rate of 35 rpm.

(4) This composition did not exhibit any adhesion to the glass surface.

COMPARTIVE EXAMPLE 2

(5) A PVC composition was prepared using a PVC base (Kwert 65) containing 30 weight % of T8 trimellitate plasticizer marketed by ADK Palmarole 1.5 weight % of stabilizer (Ca/Zn), 0.5 weight % of co-stabilizer (phosphite-type antioxidant, ADK STAB 1500, marketed by Adeka Palmarole), 2% of 3-(aminopropyl)triethoxysilane additive.

(6) A glass surface was treated at ambient temperature with methyl-ethyl-ketone before being heated in an oven to 200 C.

(7) The PVC composition was applied by extrusion (Escuyer 40) under the following conditions: die head temperature of 170 C., with a temperature profile of 160 to 180 C.; and extrusion rate of 35 rpm.

(8) The peel force showed that adhesion strength was less than 20 N (adhesive failure) on the glass surface.

EXAMPLE 1PVC COMPOSITION OF THE INVENTION

(9) A PVC composition was prepared using a PVC base (Kwert 65) containing 29 weight % of T8-10 plasticizer, 1.5 weight % of stabilizer (Ca/Zn), 0.5 weight % of co-stabilizer, 2.9 weight % of 3-(aminopropyl)triethoxysilane and 1.5 weight % of Bis[2-[(2-aminoethyl)amino]ethanolato][2-[(2-aminoethyl)amino]ethanolato-O](propan-2-olato)titanate.

(10) A glass surface was treated at ambient temperature with methyl-ethyl-ketone before being heated in an oven to 200 C.

(11) The PVC composition was applied by extrusion (Escuyer 40) under the following conditions: die head temperature of 170 C., with a temperature profile of 160 to 180 C.; and extrusion rate of 35 rpm.

(12) The adhesion strength measured by implementing the peel test was higher than 40 N on the glass surface. The heat stability of the material (measured at 200 C.) was 30 minutes.

EXAMPLE 2PVC COMPOSITION OF THE INVENTION

(13) A PVC composition was prepared using a PVC base (Kwert 65) containing 29 weight of T8-10 plasticizer, 1.5 weight % of stabilizer (Ca/Zn), 0.5 weight % of co-stabilizer, 2.9 weight % of 3-(aminopropyl)triethoxysilane protected by a tert-butoxycarbonyl function and 1.5 weight % of Bis[2-[(2-aminoethyl)amino]ethanolato][2-[(2-aminoethyl)amino]ethanolato-O](propan-2-olato)titanate.

(14) A glass surface was treated at ambient temperature with methyl-ethyl-ketone before being heated in an oven to 200 C.

(15) The PVC composition was applied by extrusion (Escuyer 40) under the following conditions: die head temperature of 170 C., with a temperature profile of 160 to 180 C.; and extrusion rate of 35 rpm.

(16) The adhesion strength measured by implementing the peel test was higher than 40 N on the glass surface. The measured heat stability (at 200 C.) was 106 minutes.

EXAMPLE 3PVC COMPOSITION OF THE INVENTION

(17) A PVC composition was prepared using a PVC base (Kwert 65) containing 26 weight % of T8-10 plasticizer, 1.5 weight % of stabilizer (Ca/Zn), 0.5 weight % of co-stabilizer, 10 weight % of 3-(aminopropyl)triethoxysilane and 1.3 weight % of Tetrabutyl titanate.

(18) A glass surface was treated at ambient temperature with methyl-ethyl-ketone before being heated in an oven to 200 C.

(19) The PVC composition was applied by extrusion (Escuyer 40) under the following conditions: die head temperature of 170 C., with a temperature profile of 160 to 180 C.; and extrusion rate of 35 rpm.

(20) The adhesion strength measured by implementing the peel test was higher than 40 N on the glass surface.

EXAMPLE 4PVC COMPOSITION OF THE INVENTION

(21) A PVC composition was prepared using a PVC base (Kwert 70) containing 27 weight % of T8-10 plasticizer, 1.5 weight % of stabilizer (Ca/Zn), 0.5 weight % of co-stabilizer, 5.3 weight % of 3-(aminopropyl)triethoxysilane protected by a tert-butoxycarbonyl function and 1.4 weight % of Bis[2-[(2-aminoethyl)amino]ethanolato][2-[(2-aminoethyl)amino]ethanolato-O](propan-2-olato)titanate.

(22) A glass surface was treated at ambient temperature with methyl-ethyl-ketone before being heated in an oven to 200 C.

(23) The PVC composition was applied by extrusion (Escuyer 40) under the following conditions: die head temperature of 170 C., with a temperature profile of 160 to 180 C.; and extrusion rate of 35 rpm.

(24) The adhesion strength measured by implementing the peel test was higher than 40 N on the glass surface.

EXAMPLE 5PVC COMPOSITION OF THE INVENTION

(25) A PVC composition was prepared using a PVC base (Kwert 65) containing 29 weight % of T8-10, 1.5 weight % of stabilizer (Ca/Zn), 0.5 weight % of co-stabilizer, 2.9% of 3-(trimethoxysilylpropyl)diethylenetriamine protected by a tert-butoxycarbonyl function and 1 weight % of Tetrabutyl titanate.

(26) A glass surface was treated at ambient temperature with methyl-ethyl-ketone before being heated in an oven to 200 C.

(27) The PVC composition was applied by extrusion (Escuyer 40) under the following conditions: die head temperature of 170 C., with a temperature profile of 160 to 180 C.; and extrusion rate of 35 rpm.

(28) The adhesion strength measured by implementing the peel test was higher than 40 N on the glass surface.

EXAMPLE 6: PVC COMPOSITION OF THE INVENTION

(29) A PVC composition was prepared using a PVC base (Kwert 65) containing 29 weight % of T8-10, 1.5 weight % of stabilizer (Ca/Zn), 0.5 weight % of co-stabilizer, 5.8 weight % of 3-trimethoxysilylpropyl)diethylenetriamine and 1.4 weight % of Tetrabutyl titanate.

(30) A glass surface was treated at ambient temperature with methyl-ethyl-ketone before being heated in an oven to 200 C.

(31) The PVC composition was applied by extrusion (Escuyer 40) under the following conditions: die head temperature of 170 C., with a temperature profile of 160 to 180 C.; and extrusion rate of 35 rpm.

(32) The adhesion strength measured by implementing the peel test was higher than 20 N on the glass surface and was lower than the strength of the material in Example 4.

COMPARTIVE EXAMPLE 3

(33) A PVC composition was prepared using a PVC base (Kw 80) containing 42 weight % of DINP plasticizer, 1.7 weight % of stabilizer (Ca/Zn), 0.5 weight % of co-stabilizer (epoxidized soybean oil), 9 weight % of filler (CaCO3).

(34) A glass surface was treated at ambient temperature with methyl-ethyl-ketone before being heated in an oven to 200 C.

(35) The PVC composition was applied by extrusion (Escuyer 40) under the following conditions: die head temperature of 170 C., with a temperature profile of 160 to 180 C.; and extrusion rate of 35 rpm.

(36) The peel strength measured by implementing the peel test on this material was about 2 N on the steel surface.

EXAMPLE 8 OF THE INVENTION

(37) A PVC material was prepared under the same conditions as the material in Example 6 with the addition of 3-(trimethoxysilylpropyl)diethylenetriamine in a content of 1.2 weight with 0.7 weight % of tetrabutyl titanate.

(38) A stainless steel surface was treated at ambient temperature with methyl-ethyl-ketone before being heated in an oven to 200 C.

(39) The PVC composition was applied by extrusion (Escuyer 40) under the following conditions: die head temperature of 170 C., with a temperature profile of 160 to 180 C.; and extrusion rate of 35 rpm.

(40) The peel strength measured by implementing the peel test was 55.6 N on the steel surface.

EXAMPLE 9 OF THE INVENTION

(41) A PVC composition was prepared using a PVC base (Kwert 65) containing 26 weight % of T8-10 plasticizer, 1.5 weight % of stabilizer (Ca/Zn), 0.5 weight % of co-stabilizer, 10 weight % of 3-(aminopropyl)triethoxysilane protected by tert-Butyl carbamates and 1.3 weight % of commercial polyisocyanate: Desmodur BL 3272 MPA.

(42) A glass surface was treated at ambient temperature with methyl-ethyl-ketone before being heated via infrared radiation to a temperature of 300 C. for 30 seconds. The PVC composition was applied by extrusion (Escuyer 40) under the following conditions: die head temperature of 170 C., with a temperature profile of 160 to 180 C.; and extrusion rate of 35 rpm.

(43) The adhesion strength of the system obtained by extrusion and measured by the peel test after cooling was higher than 40 N.

EXAMPLE 10 OF THE INVENTION

(44) A PVC composition was prepared using a PVC base (Kwert 65) containing 26 weight % of T8-10 plasticizer, 1.5 weight % of stabilizer (Ca/Zn), 0.5 weight % of co-stabilizer, 20 weight % of 3-(aminopropyl)triethoxysilane protected by tert-Butyl carbamates and 2.6 weight % of commercial polyisocyanate: Desmodur BL 3272 MPA.

(45) A glass surface was treated at ambient temperature with methyl-ethyl-ketone before being heated via infrared radiation to a temperature of 300 C. for 30 seconds. The PVC composition was applied by extrusion (Escuyer 40) under the following conditions: die head temperature of 170 C., with a temperature profile of 160 to 180 C.; and extrusion rate of 35 rpm.

(46) The adhesion strength of the system obtained by extrusion and measured by the peel test after cooling was higher than 40 N.

EXAMPLE 11

(47) A PVC composition was prepared using a PVC base (Kwert 57) containing 26 weight % of T8-10 plasticizer, 1.5 weight % of stabilizer (Ca/Zn), 0.5 weight % of co-stabilizer, 10 weight % of 3-(aminopropyl)triethoxysilane protected by tert-Butyl carbamates and 2.6 weight % of commercial polyisocyanate: Desmodur BL 3272 MPA.

(48) The glass surface was treated at ambient temperature with methyl-ethyl-ketone before being heated by infrared radiation to a temperature of 300 C. for 30 seconds. The PVC composition was applied by extrusion (Escuyer 40) under the following conditions: die head temperature of 170 C., with a temperature profile of 160 to 180 C.; and extrusion rate of 35 rpm.

(49) The adhesion strength of the system obtained by extrusion and measured by the peel test after cooling was higher than 40 N.

EXAMPLE 12 OF THE INVENTION

(50) A PVC composition was prepared using a PVC base (Kwert 65) containing 26 weight % of T8-10 plasticizer, 1.5 weight % of stabilizer (Ca/Zn), 0.5 weight % of co-stabilizer, 10 weight % of 3-(aminopropyl)triethoxysilane protected by tert-Butyl carbamates and 2.6 weight % of commercial polyisocyanate: Desmodur BL 3272 MPA.

(51) The glass surface was treated at ambient temperature with methyl-ethyl-ketone before being heated in an oven to a temperature of 200 C. The PVC composition was applied by injection under the following conditions: injection head temperature of 180 C., with a temperature profile of 165 to 180 C.; temperature hold or cooling applied for 30 seconds; mould closing pressure of 50 bars; injection time of 1.6 seconds;

(52) mould held at 35 C.

(53) The PVC/glass system, immediately after release from the mould, was subjected to a temperature of 300 C.

(54) The adhesion strength of the system obtained by injection was measured after cooling and was higher than 40 N.

EXAMPLE 13 OF THE INVENTION

(55) A PVC composition was prepared using a PVC base (Kwert 65) containing 39 weight % of TOTM plasticizer, 1.5 weight % of stabilizer (Ca/Zn), 0.5 weight % of co-stabilizer, 1.4 weight % of 3-(aminopropyl)triethoxysilane and 0.85 weight % of commercial titanate complex: TNBT.

(56) A metal surface in stainless steel was treated at ambient temperature with methyl-ethyl-ketone before being heated by infrared radiation to a temperature of 350 C. The PVC composition was applied by extrusion (Escuyer 40) under the following conditions: die head temperature of 170 C., with a temperature profile of 160 to 180 C.; and extrusion rate of 35 rpm.

(57) The adhesion strength of the system obtained by extrusion and measured by the peel test after cooling was higher than 40 N.

EXAMPLE 14 OF THE INVENTION

(58) A PVC composition was prepared using a PVC base (Kwert 57) containing 39 weight % of TOTM plasticizer, 1.5 weight % of stabilizer (Ca/Zn), 0.5 weight % of co-stabilizer, 2.8 weight % of 3-(aminopropyl)triethoxysilane and 0.85 weight % of commercial titanate complex: Kr44.

(59) A stainless steel surface was treated at ambient temperature with methyl-ethyl-ketone before being heated by infrared radiation to a temperature of 350 C. The PVC composition was applied by extrusion (Escuyer 40) under the following conditions: die head temperature of 170 C., with a temperature profile of 160 to 180 C.; and extrusion rate of 35 rpm.

(60) The adhesion strength of the system obtained by extrusion and measured by the peel test after cooling was higher than 40 N.