Patent Application
20220298325
Embodiments of the present disclosure relate to a filled composition comprising a substrate, functional filler, and an inorganic additive for reducing the odour of the filled composition, wherein the inorganic additive is present in an amount sufficient to reduce the odour of the filled composition absent the inorganic additive, and to related uses, methods and articles of manufacture.
Polymers, such as polypropylene, polyethylene, polystyrene, polyvinyl chloride, polyisoprene, polybutadiene, polyisobutylene, polyurethane, polyacetal, polyamides, and polyesters, silane terminated polymers, silicones, polysulfides, epoxy, and acrylics, are widely used in consumer and industrial applications, and in many instances there is a desire or requirement to control odour levels. For example, filled polymers such as talc-filled polypropylene, are widely used in automotive or other industrial applications. For interior and under the hood automotive applications, odour levels of the final parts are required to meet specifications given by the car manufacturers. In interior/under the hood automotive parts, mineral fillers such as talc or fibers such as glass or natural fibers, are often used in polymers such as polypropylene for reinforcement, thermal resistance and dimensional stability. However, these fillers can also lead to an increase in odour. Further, UV exposure through sunlight may affect materials used in automotive parts, for example, through polymer degradation which can adversely affect the colour, shape and/or mechanical properties (e.g., tensile strength) of the materials used, and can increase odour levels. Thus, there is ongoing need to develop new and improved filled compositions for use in automotive applications and the like.
In accordance with a first aspect, there is provided a filled composition including a substrate and an inorganic additive for reducing the odour of the filled composition, wherein the inorganic additive comprises a precipitated calcium carbonate having a specific surface area greater than about 18 m2/g, an inter-particle pore volume of at least about 0.05 cm3/g, an intra-particle pore volume of less than about 0.1 cm3/g, and a Dp (elementary particle size) of less than or equal to about 100 nm.
In accordance with a second aspect, the filled composition can further include a functional filler selected from natural fibers, a glass fiber, a mineral filler other than the inorganic additive, and combinations thereof; optionally, wherein the mineral filler is selected from diatomaceous earth, ground calcium carbonate, kaolin, talc, HAR talc, micronized talc, wollastonite, and combinations thereof.
In accordance with a third aspect, the functional filler is surface treated, optionally wherein the surface treatment includes or is an organic moiety, for example a polyalkylene glycol, for example, polyethylene glycol, or alkyl sulfonate, for example, a C10-C20 alkyl sulfonate, or a C14-C17 alkyl sulfonate.
In accordance with a fourth aspect, there is provided a use of such inorganic additive for reducing the odour of a composition comprising a substrate.
In accordance with a fifth aspect, there is provided an article formed from the filled composition.
In accordance with a sixth aspect, there is provided a method of reducing the odour of a filled composition comprising a substrate and mineral filler, comprising adding to the filled composition such inorganic additive for reducing the odour of the filled composition.
In accordance with a seventh aspect, there is provided a method of making a filled composition, the method comprising combining a substrate, a functional filler and a sufficient amount of an inorganic additive for reducing the odour of the filled composition such that the odour of the filled composition comprising the inorganic additive is reduced compared to the filled composition absent the inorganic additive.
The details, examples and preferences provided in relation to any particular one or more of the stated aspects of the present invention apply equally to all aspects of the present invention. Any combination of the embodiments, examples and preferences described herein in all possible variations thereof is encompassed by the present invention unless otherwise indicated herein, or otherwise clearly contradicted by context.
It has surprisingly been found that improvements in the odour of a composition, for example, a mineral-filled polymer, is achievable by incorporation of a relatively low amount of an inorganic additive (that is, an inorganic additive other than the mineral filler) comprising precipitated calcium carbonate. The precipitated calcium carbonate can have a specific surface area greater than about 18 or greater than about 24 or greater than about 30 m2/g, an inter-particle pore volume of at least about 0.05 or at least about 0.08 or at least about 0.1 cm3/g, an intra-particle pore volume of less than about 0.1 or less than about 0.08 or less than about 0.05 cm3/g, and a Dp (elementary particle size) of less than or equal to about 100 nm or less than or equal to about 80 nm or less than or equal to about 60 nm or from about 10 nm to about 60 nm or from about 30 nm to about 60 nm. This, in turn, may enable greater use of relatively inexpensive mineral fillers in filled compositions, for example, filled polymer compositions, without adversely affecting other properties, for example, the mechanical performance, of the filled composition.
Test Methods
The odour of the (optionally filled) compositions described herein, for example, polymer compositions, or articles formed therefrom may be determined by any suitable method. In certain embodiments, odour is determined in accordance with VDA 270, for example, VDA 270 (variant C3). In accordance with Standard VDA 270 Samples are placed in hermetic bags (0.3 g/I, equating to 0.3 g of sample in 9 litres of 10 air), then submitted to thermal cycle at about 80° C. (variant C3). Odour evaluation is performed by 5 trained persons. Each person rates the odour according to the following scale:
1—not perceptible
2—perceptible, not disturbing
3—clearly perceptible, but not disturbing
4—disturbing
5—strongly disturbing
6—not acceptable
The 5 ratings for each sample are then averaged to provide the VDA 270 test result. Suitable kits for testing odour according to VDA 270 are available, for example, from companies such as Odournet GmbH.
Further, in certain embodiments, improvements in a mechanical property (e.g., stiffness) of the filled composition may be simultaneously achievable by incorporation of the inorganic additive. In certain embodiments, the mechanical property is the dimensional stability or structural integrity of the filled composition, as may be determined by any suitable measurement method. In certain embodiments, the mechanical property is stiffness. In other embodiments, for example, embodiments in which the filled composition is a filled polymer composition, by “stiffness” is meant the relative flexibility of the filled composition. Stiffness in this sense is a desirable property for automotive interior parts and components. In such embodiments, stiffness is directly linked to flexural modulus. The higher the flexural modulus, the stiffer the material. The lower the flexural modulus, the more flexible it is. The stiffness of the filled polymer composition or article formed therefrom may be determined by any suitable method. In certain embodiments, the stiffness of the filled polymer composition or article formed therefrom is determined by measuring its flexural modulus in accordance with ISO 178.
Particle size dp is determined by permeability measured according to a method derived from BS 4359-2. The basis of this method is the measurement of the air permeability of a pellet, which is analogous to the “Blaine” or the “Lea & Nurse method”. The calculation of the dp derives from the Carman & Malherbe formula:
dp=ds×e
−3.2(ε−0.45)
As used herein, “specific surface area” means the area of the surface of the inorganic additive with respect to unit mass, determined according to the BET method by the quantity of argon adsorbed on the surface of said particles so to as to form a monomolecular layer completely covering said surface (measurement according to the BET method, AFNOR standard X11-621 and 622 or ISO 9277).
Intra-particle pore volume represents the pore volume contained within the individual particles, and cannot be measured for individual precipitated calcium carbonate particles due to their non-porous nature. Inter-particle pore volume represents the pore volume in the interstitial spaces between the particles, and is determined by nitrogen adsorption, in accordance with the following method. Pore size properties (e.g. total pore volume; which for precipitated calcium carbonate particles is also the inter-particle pore volume; and average pore size) are measured using the cylindrical shape assumption (4V/A), which is part of the BJH (Barrett-Joyner-Halenda) model. The BJH model is derived from the same N2 absorption isotherm that is used for BET specific surface area calculation (measurement according to the BET method, AFNOR standard X11-621 and 622 or ISO 9277). The BJH model is described in Barrett et al., Am. Chem. Soc., 73 (1951), pages 373 to 380, the contents of which are incorporated herein by reference. A Micromeritics TRISTAR 3000 and Micromeritics VACPREP 061 may, for example, be used. The samples may, for example, be degassed in an oven overnight at 105° C., followed by 180° C. for 30 minutes under nitrogen flow and cooling for 30 minutes under nitrogen flow. The isotherm may, for example, be measured for relative pressures P/Po ranging from 0.05 to 0.98. Average pore size refers to pore diameter. Porous volume is cumulative and obtained by BJH on the desorption branch for pore sizes between 1.7 and 50 nm.
In accordance with any of the embodiments of the present disclosure described herein, the inorganic additive can be present in an amount sufficient to reduce the odour of the filled composition by:
Also, the inorganic additive can be present in an amount of from about 0.5 to about 10 wt %, or from about 1 to about 6 wt %, or from about 1 to about 2 wt %, based on the total weight of the filled composition.
In accordance with any of the embodiments of the present disclosure described herein, the filled composition can further comprise a functional filler selected from natural fibers, a glass fiber, a mineral filler other than the inorganic additive, and combinations thereof; optionally, wherein the mineral filler is selected from diatomaceous earth, ground calcium carbonate, kaolin, talc, HAR talc, micronized talc, wollastonite, and combinations thereof.
In accordance with any of the embodiments of the present disclosure described herein, the functional filler can be present in the filled composition in an amount of at least about 5 wt %, or at least about 10 wt %, or from about 5 wt % to about 80 wt %, or from about 10 wt % to about 80 wt %, based on the total weight of the filled composition. Also, the functional filler can be surface treated, optionally wherein the surface treatment comprises or is an organic moiety, for example a polyalkylene glycol, for example, polyethylene glycol, or alkyl sulfonate, for example, a C10-C20 alkyl sulfonate, or a C14-C17 alkyl sulfonate.
In accordance with any of the embodiments of the present disclosure described herein, the substrate is present in the filled composition in an amount of at least about 20 wt % or at least about 25 wt % or at least about 30 wt % or at least about 50 wt %, or from about 20 wt % to about 95 wt %, or from about 70 wt % to about 90 wt %, based on the total weight of the filled composition. The substrate can be a polymer, a blend of polymers, paint or paint base, paper, paper board, or composite; optionally wherein the polymer comprises one or more of polypropylene, polyethylene, polystyrene, polyvinyl chloride, polyisoprene, polybutadiene, polyisobutylene, polyurethane, polyacetal, polyamides, polyesters, silane terminated polymers, silicones, polysulfides, epoxy, and acrylics; and optionally wherein the blend of polymers includes an elastomer. The polymer(s) can be virgin, recycled, or mixtures thereof.
In accordance with any of the embodiments of the present disclosure described herein, the inorganic additive as described herein can be used for reducing the odour of a composition comprising a substrate, also as described herein. Also, the inorganic additive can be used for reducing odour or VOC emissions from a filled composition comprising a substrate and functional filler, wherein the inorganic additive and/or substrate and/or functional filler are as described herein.
In accordance with any of the embodiments of the present disclosure described herein, a method of reducing the odour of a filled composition comprising a substrate as described herein and a mineral filler, comprising adding to the filled composition an inorganic additive as described herein for reducing the odour of the filled composition.
In accordance with any of the embodiments of the present disclosure described herein, a method of making a filled composition can comprise combining a substrate, a functional filler and a sufficient amount of an inorganic additive, each as described herein, for reducing the odour of the filled composition such that the odour of the filled composition comprising the inorganic additive is reduced compared to the filled composition absent the inorganic additive. Optionally, wherein the method can include compounding the substrate, functional filler, and inorganic additive, optionally along with processing aids. An article can be formed from the filled composition as described herein and/or by the above described method further comprising forming, for example, by extrusion or moulding, an article from the filled composition. The article can be an automotive interior article, for example, dashboard, interior trim, or interior body panel.
For the avoidance of doubt, the present application is directed to subject-matter described in the following numbered paragraphs:
Formulation Preparation
A precipitated calcium carbonate sample (PCC-1) having the following physical characteristics was used in the testing:
A Formulation 1 was prepared including:
78 wt % polypropylene homopolymer (“PP”);
20 wt % semi-retted hemp (retting is a process that enables separation of the hemp fibre from the stem. It is achieved by a thermal treatment at high temperature in a controlled atmosphere); and
2 wt % of PCC-1
A Comparative Formulation was prepared including:
80 wt % polypropylene homopolymer (“PP”); and
20 wt % semi-retted hemp.
The Formulation 1 was prepared as follows:
A masterbatch presenting a concentration of additives that is above the required one is prepared.
Odour Control Testing
The Formulation 1 is targeted for use in automotive applications, so all the protocols that were used are mostly for the automotive industry.
The measurements are performed according to the regulation ISO 13725 and involves:
Another odour test was performed according to the Renault method—Champ des Odeurs®
In this method:
The obtained results according to Renault method from the 5 people are averaged, and the average values are presented in Table 1 below.
From the data shown in Table 1, it can be seen that the Comparative Formulation including only PP and hemp does not meet the requirements in terms of odour (global intensity above 2.5). It can also be seen that Formulation 1 including PP, hemp and PCC-1 passed the odour test.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 19290069.4 | Aug 2019 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2020/072109 | 8/6/2020 | WO |
