Pigmentable binder composition

Abstract: A pigmentable binder composition comprising a mineral lubricating oil derivative and a modified hydrocarbon resin containing carboxylic acid, carboxylic acid anhydride or hydroxyl groups, and as a further component an amorphous homopolymer or copolymer of an alpha-olefin. These compositions have good weatherability and are useful in the manufacture of pigmented surface coating or sealing material such as roofing felt, road dressing and marking composition, sealants, pipe coatings and specialist surfaces such as cycle tracks and courts for sports activities.

Description: This invention relates to a pigmentable binder composition for use in the manufacture of pigmented surface coating or sealing material such as roofing felt, road dressing and marking compositions, sealants, pipe coatings and specialist surfaces such as cycle tracks and courts for sports activities. Binder compositions which are pigmentable are known from UK P 1.226.234 which discloses compositions including an oil, a petroleum resin, a coumarone-indene resin and a thermoplastic rubber. European Patent Application 0179510 discloses similar mixtures in which the petroleum resin and/or the coumarone-indene resin is modified to the extent that they contain carboxylic acid, carboxylic acid anhydride or hydroxyl groups. These compositions are compatible with pigments and with fillers and/or aggregates. FR-A-1469702 describes a process for the preparation of agglomerated materials comprising the mixing of a hydrocarbon binder such as atactic polypropylene with crushed rocks, particularly siliceous rocks, pre-treated by coating with a tension-reducing, hydraulic substance such as "Portland" cement or "Portland" clinker. EP-A-211103 describes a process for the preparation of a road surfacing material in which heated, granular mineral material is coated firstly with an amorphous copolymer of an alpha olefin and then with bitumen. In order to produce a wide range of coloured surface coating or sealing materials, principally for use under all weather conditions, the nature, type and proportions of sand, aggregate, and mineral filler which are incorporated into the binder composition along with an appropriate pigment, vary to a large degree, but of course are dictated by the end-use of the surface coating or sealing material. For example, in the manufacture of roofing felt, sand and an appropriate aggregate and/or filler can be blended with a binder composition and a pigment at an elevated temperature and coated on a membrane in a manner similar to the manufacture of bituminous roofing felt. Hitherto brightly-coloured bituminous surface coating or sealing materials which can withstand a wide range of climatic conditions over extended periods of time have not been available in large or economically- viable quantities. There is an increasing demand by designers and architects for materials, especially roofing materials, which can be pigmented and which are as reliable as conventional bituminous or asphaltic-based materials. We have now found a very useful pigmentable binder composition in that it can be mixed effectively with aggregate, mineral and other fillers and pigments to produce pigmented material for surface dressing, road-marking, roofing, waterproofing, sealing and other purposes, and in that the pigmented material has good weatherability and therefore can be used over a wide range of climatic conditions. According to the present invention, a pigmentable binder composition comprises a mineral lubricating oil derivative and a modified hydrocarbon resin containing carboxylic acid, carboxylic acid anhydride or hydroxyl groups, characterised in that the composition also includes as a further component an amorphous homopolymer or copolymer of an alpha olefin. This binder composition possesses high-temperature stability and resistance to low-temperature brittleness and can be readily blended with a wide range of aggregate, mineral and other fillers and pigments to produce brightly- pigmented coating or sealing materials. The amorphous alpha olefin polymer is suitably atactic polypropylene, an amorphous copolymer of propylene, butene-1 and optionally a minor proportion of ethylene, or mixtures thereof. When atactic polypropylene (APP) is used in the binder composition according to the invention, this may be pure material or may be by-product material obtained from the manufacture of isotactic polypropylene. When a propylene/butene-1 copolymer is used, this may contain from 0 to 15% of units derived from ethylene with the remainder derived from propylene and butene-1, preferably in the proportions of 60 to 70% by weight from one and the remainder from the other. Suitable materials are described in US Patent 4707413 (Col. 3, reference copolymer (a)), and are commercially available as "Vestoplast". The amount of amorphous alpha olefin polymer in the binder composition can be in the range 5 to 40% by weight, preferably in the range 10 to 30% by weight. Suitable mineral lubricating oil derivatives are obtained by solvent-extraction of a mineral lubricating oil or of a Bright-Stock. Suitable solvents are e.g. phenol, liquid sulphur dioxide and in particular furfural. Other suitable materials include heavy distillate and deasphalted oil. These derivatives may be used in proportions of 30-99%w, preferably 60-95%w, based on the binder composition. Suitable hydrocarbon resins include petroleum resins and coumarone-indene resins. Petroleum resins may be prepared by polymerization of unsaturated hydrocarbons present in unsaturated petroleum fractions, such as thermally cracked fractions and unsaturated hydrocarbons obtained in the pyrolysis of hydrocarbons. Coumarone-indene resins may be prepared by polymerization of unsaturated hydrocarbons present in coal tar distillates. The resins can then be modified by, for example treating them with unsaturated carboxylic acids or anhydrides, in particular maleic anhydride, or by mild oxidation. They may also be obtained by modifying the preparation of the resins, e.g. by polymerization of unsaturated hydrocarbons in the presence of unsaturated carboxylic acids or anhydrides, in particular maleic anhydride, or in the presence of hydroxyl group containing unsaturated carboxylic acids or esters thereof, such as hydroxyethylmethacrylate. The resin component of the binder composition conveniently has an acid value in the range 1-100, preferably in the range 5-50 mg KOH/g, and is suitably present in the range of 1 to 70% by weight, preferably 5-40% by weight. The mineral lubricating oil derivative and the resin component may be blown partially or completely before being blended with the amorphous alpha olefin polymer. It has also been found that, surprisingly, the binder composition according to the present invention can have incorporated therein an inert filler material, for example ground lime-stone, up to above 40%, e.g. 10-30%, by weight without having any deleterious effects on the properties of the binder composition. The pigmentable binder composition may also contain minor proportions, e.g. 0-30% by weight preferably 0.5-10% by weight, of other components such as blown or unblown bitumen; flux oil; natural or synthetic rubber e.g. optionally-hydrogenated, linear or branched, e.g. star-shaped, block copolymers of styrene and a conjugated diene (e.g. butadiene or isoprene); waxes, such as paraffin waxes; tackyfiers, such as Li salts of C₁₀₋₄₀ (hydroxy) fatty acids, e.g. Li (hydroxy) stearate to render the binder composition self-adhesive. The pigmentable binder composition can be prepared by established techniques for the intimate mixing of components of the type employed in the composition according to the invention, e.g. by means of a blender mixer at elevated temperatures. The surface coating or sealing material in which the pigmentable binders may be used usually contain mineral aggregates and fillers, in proportions of e.g. 5-98 %w, preferably 20-95%w, based on the coating or sealing material. Suitable mineral aggregates are stone chips, gravel, slag and sand. Suitable fillers are mineral dusts, ground chalk, ground limestone and talc. The pigmentable binders according to the present invention may be present in proportions of e.g. 1-15%w, preferably 4-8%w, based on the coating or sealing material. Pigments may be used in proportions of 0-10%w, preferably 0.05-2%w, based on the coating or sealing material. Suitable pigments are e.g. red and yellow iron oxides, titanium oxide (white), chromex green, cobalt blue, etc. According to a further feature of the present invention, there is provided a pigmented surface coating or sealing material characterised in that it is a blend of the pigmentable binder composition according to the invention, a pigment and a mineral aggregate and/or filler. The present invention is further illustrated by the following Examples: Examples 1 to 4 A Bright-Stock furfural extract (BFE) was mixed with a modified coumarone-indene resin and with one of the following polymers in a mixer at 180°C for 30 minutes:- (a) Poly alpha-olefin (propylene/butene-1 copolymer available as "Vestoplast")(trade name) (b) By-product atactic polypropylene blend (APP) obtained ex DERBIT (c) Thermoplastic Rubber - Styrene/butadiene star copolymer containing 30% styrene ("CARIFLEX" TR1184)(trade name) The resulting binder compositions were tested and the results presented in Table A Composition Comparative Ex. Ex 1 Ex 2 Ex 3 BFE 62 49 56 49 Coumarone-Indene Resin-modified 26 21 24 21 "Vestoplast" (trade name) - 30 20 - APP Blend - - - 30 Thermoplastic Rubber 12 - - - Properties Softening Point (ASTM D 36°C) 81.6 146.5 136.9 150.3 Cold Bending (DIN 52123°C) -30 -30 -25 -30 Flow Resistance (DIN 52123°C) 65 >145 135 >145 Penetration at 25°C (ASTM D5 0.1mm) 76 49 56 41 From the results presented in Table A it can be seen that the pigmentable composition according to the invention has markedly superior properties over the composition employing a thermoplastic rubber. Examples 4 to 6 A Bright-Stock furfural extract was blended with a modified coumarone-indene resin and "Vestoplast" (trade name) and also pulverised limestone in a mixer at 180°C for 30 minutes. The binder compositions of varying concentrations of limestone were tested and their properties are given in Table B below: Composition Ex 2 Ex 4 Ex 5 Ex 6 BFE 56 50 48 39 Coumarone-Indene resin-modified 24 22 20 17 "Vestoplast" (trade name) 20 18 16 14 Limestone 0 10 20 30 Properties Softening Point [°C] 136.9 136.1 136.0 140.1 Cold Bending [°C] -25 -25 -25 -25 Flow Resistance [°C] 135 140 145 150 Penetration [0.1mm] 56 54 49 39 From the results presented in Table B it can be seen that the presence of limestone surprisingly has no significant effect on the softening point, cold bending and flow resistance properties.

Claims: Claims for the following Contracting States : DE, GB, FR, IT, NL, SE, CH, LI, BE, AT, LU, GR A pigmentable binder composition comprising a mineral lubricating oil derivative and a modified hydrocarbon resin containing carboxylic acid, carboxylic acid anhydride or hydroxyl groups, characterised in that the composition also includes as a further component an amorphous homopolymer or copolymer of an alpha-olefin. Binder composition as claimed in claim 1 wherein the further component is atactic polypropylene, an amorphous copolymer of propylene, butene-1 and optionally a minor proportion of ethylene, or mixtures thereof. Binder composition as claimed in claim 1 or 2 characterised in that the amount of amorphous alpha olefin polymer is in the range 5 to 40% by weight of the composition. Binder composition as claimed in claim 1, 2 or 3 characterised in that the hydrocarbon resin is a petroleum resin or a coumarone-indene resin. Binder composition as claimed in claim 4 characterised in that the resin component has an acid value in the range 1 to 100 mg KOH/g. Binder composition as claimed in any one of claims 1 to 5 characterised in that the resin component is present in the range 1 to 70% by weight of the composition. Binder composition as claimed in any one of the preceding claims characterised in that the mineral lubricating oil derivative is Bright-Stock furfural extract. Binder composition as claimed in any one of the preceding claims characterised in that the mineral lubricating oil derivative is employed in the range 30 to 99% by weight of the composition. Binder composition as claimed in any one of the preceding claims characterised in that an inert filler is included in the composition. A pigmented surface coating or sealing material characterised in that it is a blend of the pigmentable binder claimed in any one of the preceding claims, a pigment and a mineral aggregate or filler. Claims for the following Contracting State : ES A process for the preparation of a pigmentable binder composition which comprises mixing a mineral lubricating oil derivative, a modified hydrocarbon resin containing carboxylic acid, carboxylic acid anhydride or hydroxyl groups, and, as a further component, an amorphous homopolymer or copolymer of an alpha-olefin. A process as claimed in claim 1 wherein the further component is atactic polypropylene, an amorphous copolymer of propylene, butene-1 and optionally a minor proportion of ethylene, or mixtures thereof. A process as claimed in claim 1 or 2 characterised in that the amount of amorphous alpha olefin polymer is in the range 5 to 40% by weight of the composition. A process as claimed in claim 1, 2 or 3 characterised in that the hydrocarbon resin is a petroleum resin or a coumarone-indene resin. A process as claimed in claim 4 characterised in that the resin component has an acid value in the range 1 to 100 mg KOH/g. A process as claimed in any one of claims 1 to 5 characterised in that the resin component is present in the range 1 to 70% by weight of the composition. A process as claimed in any one of the preceding claims characterised in that the mineral lubricating oil derivative is Bright-Stock furfural extract. A process as claimed in any one of the preceding claims characterised in that the mineral lubricating oil derivative is employed in the range 30 to 99% by weight of the composition. A process as claimed in any one of the preceding claims characterised in that an inert filler is included in the composition. A process for the preparation of a pigmented surface coating or sealing material characterised by blending the pigmentable binder claimed in any one of the preceding claims with a pigment and a mineral aggregate or filler.

Inventors: KORENSTRA JAN, VAN GOOSWILLIGEN GERRIT, VONK WILLEM CORNELIS, KORENSTRA, JAN, VAN GOOSWILLIGEN, GERRIT, VONK, WILLEM CORNELIS
Applicants: SHELL INT RESEARCH, SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1989
Main classification: C08L57
IPC codes: E01C7, C08L57, C08L23, E01F9