阅读说明：本技术 热塑性烯烃组合物 (Thermoplastic olefin composition ) 是由 P·S·瓦利亚 M·P·艾伦 于 2020-04-07 设计创作，主要内容包括：本发明公开了以下各项：一种热塑性烯烃组合物,其包括(a)具有小于1.0dg/min的熔体流动速率和高熔体强度的弹性体,以及(b)具有大于35dg/min的熔体流动速率的聚丙烯；一种用于制成上述组合物的方法；以及一种由上述组合物制成的制品。(The invention discloses the following: a thermoplastic olefin composition comprising (a) an elastomer having a melt flow rate of less than 1.0dg/min and a high melt strength, and (b) a polypropylene having a melt flow rate of greater than 35 dg/min; a process for making the above composition; and an article made from the above composition.)

1. A thermoplastic olefin composition comprising:

(a) an elastomer having a melt flow rate of less than 1.0dg/min and a high melt strength having a tan delta of less than 2.5; an elastomer to polypropylene ratio wherein the concentration of the elastomer is from 0.6 to 0.8; and

(b) polypropylene having a melt flow rate greater than 35dg/min and present in a concentration having a polypropylene to elastomer ratio greater than or equal to 0.2;

wherein the thermoplastic olefin composition provides a compound having a Shore A hardness of less than 95 and an elongation viscosity ratio at a 1.0:0.25 Hencky strain of greater than 1.5.

2. The composition of claim 1, wherein the elastomer, component (a), is an ethylene-a polymer component.

3. The composition of claim 1, wherein the elastomer, component (a), has a density of between 0.85 and 0.89 grams per cubic centimeter.

4. The composition of claim 1, wherein the elastomer is an ethylene-alpha olefin elastomer having a melt index of less than 1.0 and a tan delta of less than 2.5, and a strain of less than or equal to 10%, when tested according to dynamic mechanical spectroscopy at a rate of 0.1 rad/sec and at 180 ℃.

5. The composition of claim 1, wherein the ratio of the melt tan δ of the elastomer to the melt tan δ of the polypropylene is less than 0.25 as measured by a parallel plate rheometer at 0.1 radians/sec and at 180 ℃.

6. The composition of claim 1, wherein the concentration of the polypropylene, component (b), is from 0.2 to 0.4 polypropylene to elastomer ratio.

7. A process for making a thermoplastic olefin composition comprising compounding (a) an elastomer having a melt flow rate of less than 1.0dg/min and (b) a polypropylene having a melt flow rate of greater than 35 dg/min.

8. A thermoplastic olefin skin article made from the composition of claim 1, wherein the article simultaneously exhibits: (1) an elongational viscosity ratio greater than 1.5 at a 1.0:0.25 Hencky strain; (2) a shore a hardness of less than 95; and (3) a tensile elongation of less than 400% at 23 ℃ and 95 ℃ when tested according to ASTM D638-14 type V at 500 mm/min.

Technical Field

The present invention relates to a thermoplastic olefin composition; and more particularly, to a thermoplastic olefin composition prepared by combining a high melt flow polypropylene with a high melt strength polyolefin elastomer.

Background

Automotive interiors are a key area for automotive OEM differentiation. Thermoplastic olefin (TPO) soft skin layers are commonly used to cover hard surfaces of automotive interiors, such as instrument panels and door panels; and TPO skins are often used to replace leather surfaces while achieving a leather-like feel and aesthetic. Aesthetically, the surface of a TPO skin typically requires low gloss properties to provide a luxurious appearance. Mechanically, the TPO skin may also be used as a cover layer for an airbag placed under the TPO skin, and therefore it is desirable that the TPO skin should be easily torn without expansion during airbag deployment. From a process perspective, when extruding known TPO skins using high melt strength polyolefin elastomers (POE) in combination with low melt index polypropylene, the TPO skins exhibit high pressure and torque during extrusion, which may limit the output values to below the rated conditions of the extrusion equipment. Therefore, compounded TPOs should have good melt strength so that parts made from the compounded TPOs do not thin or tear during molding.

Conventional solutions to increase the melt strength of TPO soft skin applications include the use of: (1) thermoplastic vulcanizate, (2) rheology modification, or (3) compounded TPO comprising a combination of high melt strength POE and a small portion of low melt flow polypropylene. Thermoplastic vulcanizates and rheology modification involve reactive extrusion processes that can add significantly to the cost of the resulting TPO skin product. In addition, reactive extrusion often involves additional compounds such as phenolics and/or peroxides to achieve the desired modification/crosslinking. Residual peroxide, phenolics, low molecular weight species formed by decomposition of the peroxide or phenolics, and other crosslinking agents can increase the undesirable odor and undesirable VOC emissions in the finished TPO skin product. For example, U.S. patent No. 6,114,486a teaches a rheology modification process involving reactive extrusion with peroxides and/or crosslinkers; and the process of the above-mentioned patent is undesirable due to the odor and cost associated with reactive compounding and extrusion.

Compounded TPOs composed of high melt strength POE in combination with low melt flow polypropylene, on the other hand, are often difficult to extrude due to the high melt viscosity of the compounded mixture. Additionally, known TPO soft skin layers may not work properly when used for airbag deployment because the elongation and tear strength properties of such TPO soft skin layers are often too high due to the amount of elastomer or rubber added to the known TPO soft skin layers. Thus, the excessively high elongation and tear strength properties of such TPO soft skin layers make it difficult for the airbag to deploy without expanding the TPO soft skin layer. It is desirable to produce a soft TPO skin that can enhance processing and reduce tensile elongation and tear strength.

Generally, it is desirable that a TPO soft skin layer made from an ethylene/alpha-olefin copolymer have a preferred Melt Flow Rate (MFR), sometimes referred to as Melt Index (MI), of about 0.05 grams per 10 minutes (g/10min) to 5.0g/10min as determined according to ASTM D1238-13 (conditions: 190 degrees Celsius (deg.C.) for ethylene-based olefins under a 2.16 kilogram load) and 230 deg.C for propylene-based olefins, i.e., [190 deg.C/2.16 kg ] or [230 deg.C/2.16 kg ]).

Heretofore, High Melt Strength polymers such as ENGAGE (available from Dow Chemical Company) combined with High Melt Strength or low Melt flow (e.g., less than (<)3MI) polypropylene (PP) have been used as formulations for producing TPO soft skin layers as disclosed in "High Melt Strength Polyolefin elastomers for Extrusion Profiles, Thermoforming, and Extrusion Blow Molding" (High Melt Strength Polyolefin Elastomer for Extrusion Profiles, Thermoforming, and Extrusion Blow Molding) "of SPE automotive TPO Global conference white book, 10.2007 and in U.S. Pat. No. 9,938,385, which discloses examples including the use of PP with an MFR <2.6 dg/min (dg/min). The processes disclosed in the above references are undesirable because the resulting TPO skin formulations made by the above processes have excessively high melt viscosities; and products made from the formulation have high gloss, excessive tensile elongation and/or tear strength at room temperature (RT; 23 ℃) and/or above RT temperatures.

Other references, such as U.S. patent nos. 8,431,651 and 6,828,384, disclose undesirable processes that result in products with undesirable properties, such as: (1) too high a gloss level, (2) too high a melt viscosity, (3) unacceptable tensile properties at RT and/or higher, and/or (4) unacceptable tear properties at RT and/or higher. For example, U.S. patent No. 8,431,651 discloses that the ratio of the melt tan δ of the very low density ethylene polymer component to the melt tan δ of the polypropylene (PP) component is in the range of 0.5 to 4 as measured by a parallel plate rheometer at 0.1 rad/sec and at 180 ℃. For example, 6,828,384 teaches that Linear Low Density Polyethylene (LLDPE) is required and that the melt flow rate of the PP used must be less than 1.0. The use of LLDPE is undesirable because LLDPE increases hardness and the low melt flow rate of PP results in high melt viscosity.

JP05830902B2 discloses a thermoplastic elastomer composition containing: 30 to 70 weight percent (wt%) of a polypropylene resin, component (A; and 30 to 70 wt% of an ethylene-alpha-olefin copolymer, component (B), having a Mooney stress relaxation zone at 125 ℃ of 180 to 300. in the process described in JP05830902B2, a 30 to 70 wt% PP range too wide to achieve a desired Shore A hardness of <95 increased Shore A hardness of 95 or higher is undesirable because TPO skin is not felt to be soft and flexible at a Shore A hardness level of 95 or higher. in some cases, a PP concentration of <40 wt% is required, and in many cases, a PP concentration of <35 wt% is required to achieve the desired hardness of the TPO skin. "Profile extrusion" describes the extrusion of shaped products having various configurations, but profile extrusion does not include sheet or film products. Extruded sheets for instrument panel and door panel coverings are subjected to a secondary process in which the sheet is heated and shaped in a thermoforming tool to achieve the desired form and dimensions.

Disclosure of Invention

The present invention relates to TPOs having several beneficial properties, including for example TPOs having the following properties: (1) reduced tensile properties and (2) reduced tear properties, while achieving: (3) high melt strength, (4) enhanced processing, and (5) low gloss. According to the present invention, a formulation is prepared, wherein the formulation has enhanced extrusion; and the realization is as follows: good melt strength, low gloss, <95 Shore A hardness, reduced tensile elongation and reduced tear strength.

In one embodiment, the present invention provides a method comprising combining a high melt strength POE with a high melt flow PP. For example, in a preferred embodiment, the TPO composition of this invention comprises (a) an elastomer having an MFR of <1.0, and (b) a polypropylene having an MFR greater than (>)35 dg/min; wherein the polypropylene content may be 20 wt% to 40 wt%. In the preferred embodiment described above, the TPO composition of this invention has a melt tan delta ratio (180 ℃, 10 percent (10%) strain, 0.1 radians/second (rad/s)) >0.25 between the ethylene and PP phases.

In another embodiment, the elastomeric skin composition includes, for example, (a) an ethylene-alpha olefin is present at 60 to 80 weight percent and consists of a high melt strength grade having a fractional melt index <1.0MFR and a density of 0.85 grams per cubic centimeter (g/cc) to 0.89 g/cc; and wherein (ii) the polypropylene is present at 40 to 20 wt% and consists of a high melt flow grade with a melt index >35 MFR.

In yet another embodiment, a hot formed TPO soft skin can be produced from the above-described elastomeric skin composition, wherein the resulting TPO skin simultaneously exhibits: (1) an elongational viscosity ratio >1.5 at 1.0:0.25 Hencky strain (Hencky strain); (2) a shore a hardness of < 95; and (3) a tensile elongation at RT and 95 ℃ of < 400% when tested according to ASTM D638-14 type V at 500 millimeters per minute (mm/min).

In yet another embodiment, the TPO skins of the present invention can be used to cover hard surfaces of automotive interiors such as instrument panels, door panels, arm rests, and consoles.

Drawings

FIG. 1 is a graphical illustration showing capillary viscosities measured for compounds containing ENGAGE 7387 and various polypropylenes having a polypropylene melt flow rate in the range of 0.5dg/min to 120 dg/min.

FIG. 2 is a graphical illustration showing elongational viscosity versus Hencky strain for various formulations.

Fig. 3 is a bar graph showing the ratio of elongational viscosities for various formulations.

Fig. 4 is a bar graph showing 60 degree gloss for various formulations.

Detailed Description

In a broad embodiment, the thermoplastic olefin (TPO) composition of the invention comprises (a) an elastomer having a melt flow rate <1.0 and high melt strength, and (b) a polypropylene having a melt flow rate > 35.

The elastomeric compounds useful in preparing the TPO compositions of the present invention may include one or more elastomeric compounds known in the art. For example, the elastomeric compound may include one or more high melt strength POE compounds. By "high melt strength" grade of POE is meant herein an ethylene-alpha olefin elastomer having a melt index of <1.0 and a tan delta (G "/G') of <2.5 when tested according to dynamic mechanical spectroscopy at a rate of 0.1rad/s and at 180 ℃; and a strain less than or equal to (≦) 10%.

For example, the elastomeric compound may include an ethylene/α -olefin interpolymer, optionally containing a diene, such as an ethylene-butene copolymer and an ethylene propylene diene monomer, and mixtures thereof. Examples of alpha-olefins suitable for use in the present invention may include the alpha-olefins defined and described in paragraphs [0072] to [0078] of U.S. patent application publication No. 2007/0167575, with the proviso that the elastomer is a high melt strength grade.

In a preferred embodiment, the elastomeric compounds may include commercially available elastomers such as ENGAGE 7487, 7387, and 7280 (available from the Dow chemical company); and elastomeric compounds may include NORDEL4785, 3745P, and 3722P (available from the dow chemical company). In another embodiment, VISTALON^TMAnd EXACT^TM(available from ExxonMobil) and TARMER^TMAvailable from Mitsui Chemical, may also be used in the present invention, provided that these products are provided in high melt strength grades.

The amount of elastomeric compound used to prepare the TPO compositions of the invention can be, for example, from 60 wt% to 85 wt% in one embodiment, from 65 wt% to 80 wt% in another embodiment, and from 70 wt% to 75 wt% in yet another embodiment. If the elastomer content is greater than 85 wt%, the resulting product may not have sufficient temperature resistance and parts formed from this material may soften or deform when exposed to temperatures of 120 ℃; this is considered to be a high end exposure condition for many instrument panel skins. If the elastomer content is below 60 wt%, the Shore A hardness of the resulting product may be too high, resulting in an undesirable hard feel.

Examples of some advantageous properties exhibited by elastomeric compounds may include softness/feel, flexibility, melt strength, and ultra-long term durability in combination with UV stabilizers.

The polypropylene compounds useful in preparing the TPO compositions of this invention may include one or more polypropylene compounds known in the art having an MFR greater than (>)35 dg/min. For example, the polypropylene compound may include a polypropylene component, such as homopolymer polypropylene, impact copolymer polypropylene, and random copolymer polypropylene, as well as mixtures thereof.

In a preferred embodiment, the polypropylene compounds may include commercially available polypropylene compounds such as TI4900, TI7100, F1000HC, and CP1200B (available from Braskem Company); and Adstif HA801U and Adstif EA5076 (available from LyondellBasell), and mixtures thereof.

The amount of polypropylene compound used to prepare the TPO composition of this invention can be, for example, from 15 wt% to 40 wt% in one embodiment, from 20 wt% to 35 wt% in another embodiment, and from 25 wt% to 30 wt% in yet another embodiment. If the polypropylene content is below the above range, the product may not have sufficient temperature resistance and parts formed from this material may soften or deform when exposed to temperatures of 120 ℃; this is considered to be a high end exposure condition for many instrument panel skins. If the polypropylene content is above the above range, the Shore A hardness of the product may be too high, resulting in an undesirable hard feel.

Examples of some advantageous properties exhibited by polypropylene compounds may include improved high temperature stability (pattern retention and dimensional stability) and reduced gloss.

In addition to elastomers and polypropylene, the TPO compositions of this invention may also include other additional optional compounds or additives; and such optional compounds may be added to the composition with the elastomer or polypropylene. Optional additives or reagents useful in preparing the TPO compositions of the invention may include one or more optional compounds known in the art for their use or function. For example, the optional additives may include fillers (up to, e.g., 50 wt%), colorants, oils, antioxidants, Ultraviolet (UV) stabilizers, anti-scratch/mar additives, processing aids, and mixtures thereof. Other minor components known in the art for improving, for example, stiffness, appearance, softness, and processability, can be added to the TPO composition.

The amount of optional compounds used to prepare the TPO compositions of the invention can be, for example, from 0 wt% to 50 wt% in one embodiment, from 0.01 wt% to 40 wt% in another embodiment, and from 2 wt% to 30 wt% in yet another embodiment.

For example, when antioxidants are used, if too little antioxidant is added to the composition, the polymer can degrade due to long term heat exposure and excessively high processing temperatures. Typical amounts of antioxidants may range from 0 wt% to 0.2 wt%.

For example, when a UV stabilizer is used, if too little UV stabilizer is added to the composition, the color of the TPO skin layer may fade or the physical properties of the skin layer may decrease due to UV exposure. Typical levels of uv stabilizers may be <1 wt%.

In some embodiments, oil may be used to soften/reduce the shore a hardness of the skin. Typical levels of oil may be <10 wt% to prevent oil blooming or reduce melt strength.

For example, when a colorant is used, the colorant content (typically in the form of a masterbatch) can typically be 0.5 wt% (without carrier) to 4 wt%. If the colorant content is too low, poor color quality may result; if the colorant content is too high, a decrease in physical properties may result.

For example, when a filler is used, the filler may be in the range of 0 wt% to 30 wt%. Too high filler content can result in high stiffness, high hardness or reduced thermoformability. When the content of the filler used is too low, the performance of secondary processing such as laser welding and scribing may be deteriorated.

In a general embodiment, the process of the present invention for making a thermoplastic olefin (TPO) composition comprises the step of intermixing (a) an elastomer having a melt flow rate <1.0 and (b) a polypropylene having a melt flow rate > 35.

In a preferred general embodiment, a TPO composition can be prepared by the following steps: (i) dry blending all components except the colorant, and then (ii) feeding the dry blended material into a 42:1, 25 millimeter (mm) co-rotating twin screw extruder produced by geneva (Century).

Using the general procedure described above, sheets can be extruded on a 1.5 inch Killion single screw extrusion line with a length to diameter ratio of 24: 1. A 12 inch coat hanger die may be used to produce a sheet (or film) having a thickness of 1.8 mm. A three-roll stack with a top roll containing a hair cell pattern can be used to emboss a film having a deep pattern of about 170 micrometers (μm) and cool the sheet. A common black colorant at a concentration of 2 wt% can be dry blended into the formulations of the present invention to provide color. Melt temperatures and processing conditions are described herein in the tables below.

The techniques and steps of compounding the ingredients of the composition and the extrusion process can be performed using compounding equipment and extrusion processes known in the art.

Some advantageous properties exhibited by TPO compositions may include, for example, that the capillary viscosity of high flow PP may be lower (which in turn may result in lower extruder pressures and higher extrusion rates); and the resulting sheet made from the TPO composition can exhibit lower gloss.

As noted above, once the TPO composition of this invention is made, the TPO composition can be used to make a product or article, such as a TPO skin for automotive applications. In a general embodiment, a method for making a TPO article, such as a TPO skin layer, includes processing a TPO composition by a molding or extrusion process; or a milling and slush molding process (e.g., extruded and thermoformed skins can be prepared as described herein).

For example, in one embodiment, a TPO composition can be converted into a TPO skin layer by the following steps and conditions:

step (1): the pellets are dry blended and compounded in an extruder, such as a twin screw extruder. Typical melt temperatures may be, for example, 200 ℃ to 240 ℃.

Step (2): the compounded pellets from step (1) above, along with the colorant, are fed into a single screw extruder where the fed material is conveyed, melted, mixed/dispersed, and pumped through a slot die. The slot die controls the thickness and width of the formed sheet passing through the slot die. In one embodiment, a melt pump may be used in addition to the extruder to pump the material through the die to ensure a more uniform thickness. In another embodiment, if a melt pump and die are used in step (1), the extruder in this step (2) may optionally be skipped. In yet another embodiment, if the fed materials are dry blended and directly extruded using a single screw extruder, the extruder in step (1) may optionally be skipped; that is, in this example, the components of the composition can be compounded and extruded using a single screw extruder, provided that the single screw extruder produces sufficient dispersion and distribution, thereby eliminating the need to compound using a twin screw extruder as described in step (1) above. Typical melt temperatures may be, for example, 200 ℃ to 240 ℃. In yet another embodiment, the sheet formed in this step (2) may be melt laminated to a scrim or TPO foam.

And (3): stacking the sheet extruded from the above step (2) through a roller to cool the material; and in optional embodiments, the material may be embossed with a desired finish/pattern.

And (4): the sheet from step (3) above is then wound into a roll.

And (5): in an optional embodiment, the sheet may be surface treated and coated with a Polyurethane (PU) lacquer/topcoat to further reduce the gloss of the sheet; and improve the scratch, abrasion and chemical resistance properties of the sheet. The topcoat formed in this step (5) is typically cured at, for example, about (. about. -) 100 ℃ to 120 ℃.

And (6): the compacted sheet (skin only) or double laminate (skin laminated to the foam) is then heated to a temperature of 170 ℃ to 190 ℃ and thermoformed into the desired shape. For example, thermoforming may be via negative vacuum forming (where the pattern comes from the mold surface). A lesser amount of thermoforming may be positive vacuum formed wherein the pattern is provided by the embossed sheet and maintained during the thermoforming process.

And (7): the thermoformed part from step (6) above is then wrapped on a substrate such as a rigid instrument or door panel surface. For example, thermoformed parts are either glued in place or back-foamed with urethane that secures the skin to the substrate by a skin-foam-substrate construction.

The skin construction of the present invention may comprise a structure consisting of one or more layers, i.e. a single-layer, double-layer or multi-layer structure. Additionally, the skin construction may also include a double laminate (TPO skin-TPO/PP foam), a skin scrim, a skin foam, and the like.

The surface layer may be coated with a topcoat having a thickness of up to 40 μm in one embodiment, 5 μm to 40 μm in another embodiment, and 10 μm to 40 μm in yet another embodiment. Topcoats can be advantageously used, for example, (1) to enhance scratch, abrasion, scratch and chemical resistance of the skin layer; (2) enhance the feel of the skin, and/or (3) reduce the gloss of the skin.

Exemplary substrates that may be used for the top finish may include polyurethane dispersion (solvent or water based) based finish products from Stahl.

TPO compositions provide TPO articles, such as TPO skins, that exhibit several beneficial properties, including, for example: (1) reduced tensile properties; (2) reduced tear properties; (3) high melt strength properties, (4) enhanced processing properties; and (5) low gloss properties. For example, the TPO skin layer may have a tensile elongation at 23 ℃ of 50% to >1,000% in one embodiment; from 100% to > 750% in another embodiment, and from 150% to 600% in yet another embodiment; and in yet another embodiment from 200% to 400%. The tensile properties of a TPO skin can be measured by, for example, ASTM D638. The test specimens were die cut to the specified geometry. The test can be performed at a temperature of 23 ℃ in the transverse extrusion direction. The samples were tested at 500mm/min according to ASTM D638 with V-type geometry.

For example, the TPO skin layer may have a tensile elongation at 95 ℃ of, for example, 50% to 800% in one embodiment; 75% to 500% in another embodiment, and 90% to 400% in yet another embodiment. The test specimens were die cut to the specified geometry. The test can be performed at a temperature of 95 ℃ in the transverse extrusion direction. The samples can be tested at 500mm/min according to ASTM D638 with V-type geometry.

For example, the tear strength properties of the TPO skin layer may be from 10 kilonewtons per meter (kN/m) to 25kN/m in one embodiment; from 12.5kN/m to 25kN/m in another embodiment, and from 12.5kN/m to 25kN/m in yet another embodiment; and in yet another embodiment from 15kN/m to 22.5 kN/m. The tear properties of a TPO skin layer can be measured by ASTM D624-00. The test specimens were die cut to obtain a standard pant-like geometry. Testing can be performed in the machine extrusion direction. Method ASTM D624 was utilized at a test temperature of 23 ℃ and at a rate of 500 mm/min.

For example, the melt strength ratio property of a TPO skin layer may in one embodiment be>1; 1 to 4 in another embodiment, 1.25 to 4 in yet another embodiment, and 1.25 to 4 in yet another embodiment>1.4 to 4; and in yet another embodiment is>1.5 to 4. Can be controlled at 0.1s by using extensional viscosity clamp (EVF) geometry and rotating drum design^-1And the melt strength properties of the TPO skin layers were tested at 190 ℃. Measurements were obtained using a TA Instruments ARES Classic RSAIII equipped with EVF geometry accessories. The elongational viscosity ratio was determined by dividing the elongational viscosity at 1.0 Hencky strain by the elongational viscosity at 0.25 Hencky strainAnd (4) rate.

For example, it can be observed that the enhanced processing properties of the TPO skin layer have a decrease in capillary viscosity at 215 ℃ from 1,700 pascal seconds (Pa-s) to 550Pa-s in one embodiment; in another embodiment from 1,600 to 550Pa-s, and in yet another embodiment from 900 to 550 Pa-s. Can be processed by ASTM D3835-16 at 215 deg.C and X400-20 mold (1.016mm diameter X20.320 mm long mold, 120 degree taper angle) at 100s^-1The enhanced processing properties of the TPO skin layer were measured at shear rates of (a).

For example, the gloss properties of the TPO skin layer may be 4.3 Gloss Units (GU) to 1.3GU in one embodiment; 3.7GU to 1.3GU in another embodiment, and 2.9GU to 1.3GU in yet another embodiment; and in yet another embodiment from 2.4GU to 1.3 GU. The gloss properties of a TPO skin layer can be measured at 60 ° gloss; and the skin can be measured in the cross extrusion direction (per ASTM D523) on the textured side of the TPO soft skin using a BYK Gardner 4561 micro gloss meter.

The TPO compositions can be used to make a variety of articles and the articles can be used in a variety of applications including, for example, soft skin layers of TPO for automotive interior applications; artificial leather seat application; and soft covers for commercial, off-road and marine applications; and soft covers for furniture surfacing applications.

Examples of the invention

The following examples are provided to illustrate the invention in further detail, but should not be construed to limit the scope of the claims. All parts and percentages are by weight unless otherwise indicated.

The various ingredients, components or raw materials used in the following inventive example (inv. ex.) and comparative example (comp. ex.) are explained below and in table I:

TABLE I raw materials

⁽¹⁾"PP" is polypropylene.

Examples 1-5 and comparative examples A-C

General procedure for extrusion

The formulations described in Table II below were prepared by mixing the components, not including the colorant, and then compounding the components on a 42: 125 mm co-rotating twin screw extruder (available from Century) at a rate of-14.5 kg/hr.

The composition of comp.ex.a-C is a conventional formulation for producing TPO soft skin layers, wherein high melt strength ethylene copolymers are utilized in combination with low melt flow rate polypropylene. Ex.1-5 were prepared and tested to show that the desired properties of the compositions of the present invention were achieved when utilizing polypropylene having a melt flow rate of >35 dg/min.

TABLE II-formulations (in weight percent)

Formulation ═ form

For zones 1, 2 and 4-9, the zone temperatures of the extruder were 140 deg.C, 190 deg.C and 215 deg.C, respectively. A double 3mm hole die was used at a temperature of 215 ℃. The extruder was operated at 200 Revolutions Per Minute (RPM).

Pellets of the compound were extruded into sheets on a Killion single screw extrusion line with a length to diameter ratio of 24:1 of 1.5 inches. A 304.8mm coat hanger die was used to produce a sheet of 1.8mm thickness. A three-roll stack with a top roll containing a capillary pattern was used to emboss a film with a-170 μm deep pattern and cool the film. 2% of a generally black colorant was dry blended into the formulation to provide color. The basic operating conditions are described below in table III, and the specific melt pressures and RPM for each formulation are reported in table IV.

TABLE III general operating conditions for sheet extrusion on a 1.5 inch Killion line

TABLE IV melt pressure observed during sheet extrusion

As the melt flow rate of the polypropylene increases, the melt pressure on the extruder decreases. This is expected because the fractional melt index and low melt index polypropylenes generally exhibit higher melt viscosities at processing shear rates. With high melt flow polypropylene, if the pressure or torque of the extruder is limited by the formulation ("form."), e.g., form.1 to form.3, the throughput can be increased by using the formulations form.4 to form.8.

Experiment 1-capillary viscosity

Capillary viscosity was measured via ASTM D-3835. An X400-200 mold (1.016mm diameter × 20.320mm long mold, 120 ° taper angle) was used at a test temperature of 215 ℃. The polymer shear rate ranged from 10s^-1To 1,000s^-1。

The capillary viscosity decreases as the melt index of the polypropylene increases from 0.5MFR to 35MFR to 120 MFR. Formulations containing polypropylene with similar melt index exhibit similar melt index for the compounded system. Form.1 contains 68.6% 0.5MFR polypropylene. For 10s, in contrast to form.1^-1、100s^-1And 500s^-1With a polypropylene having an MFR of 2, form.3 showed a reduction in melt viscosity of 26%, 7% and 2%, respectively. For 10s, in contrast to form.1^-1、100s^-1And 500s^-1With a polypropylene having an MFR of 35, form.4 showed a reduction in melt viscosity of 61%, 47% and 33%, respectively. For 10s, in contrast to form.1^-1、100s^-1And 500s^-1Shear rate of (2), containing a polypropylene having an MFR of 120Form.7 of the olefin showed a reduction in melt viscosity of 80%, 67% and 57%, respectively.

Experiment 2-190 ℃ tensile viscosity

Extensional viscosity measurements were made using a TA Instruments ARES Classic RSAIII equipped with EVF geometry fittings. The EVF geometry consists of a dual barrel design. The cartridge connected to the instrument sensor (upper) remains stationary and records the force, which is converted into torque. The drum connected to the instrument motor rotates clockwise while rotating around the central drum, which also rotates in a clockwise direction.

Rectangular strips 10mm wide were punched out of the provided 0.6mm thick sheets (compression molded to this thickness) using a Charpy die in combination with a hydraulic press. The strips were cut into (4) 20mm long samples using scissors.

The test environment was controlled by using a Forced Convection Oven (FCO) on ARES. FCO utilizes a plant nitrogen environment and measures temperature in the oven chamber space using a platinum resistance thermometer. After the EVF geometry was installed, the instrument was provided with a preheat time of approximately 45 minutes (min) at 190 ℃ to ensure that the entire geometry reached equilibrium at the test temperature. Once the sample has been loaded and the test started, a 120 second(s) delay is set in the extensional viscosity method to allow time for the sample to equilibrate. Even with the delay, the instrument will wait until the oven air temperature is within +/-0.10 ℃ to begin the test. Starting from the time the sample is loaded into the gripper, it takes approximately 220s to start the pre-stretching step of the test.

The EVF geometry method starts with built-in pre-stretching to correct any sag that occurs in the sample due to thermal expansion during pre-heating. The pretensioning distance and rate are selected by the operator. The purpose of the pre-stretch portion of the test is to place the sample under slight tension, followed by a relaxation period (controlled by the operator) when the sample should return to a tension of approximately 0 grams force. Once the pre-stretching portion of the test is complete, the programmed extensional viscosity experiment is initiated. In the case of samples filled with metal fibers, the pre-stretch and relaxation lengths and times are in most cases set to default values of 0.05mm and 30s, respectively. The relaxation time varies depending on whether a particular sample requires more or less time to return to the zero force start.

At 0.1s^-1EVF geometry experiments were performed. Using the strain rate, 40s were required to complete each experiment. At the end of each test, the sample was removed from the holder, the clamps were cleaned using a brass brush, and the oven was again turned off and allowed to return to 190 ℃.

This extensional viscosity test measures viscosity as a function of hencky strain. For thermoforming applications, it is desirable that the elongational viscosity increases with increasing strain. Many parts may experience up to 100% (1 hencky strain) of stretch during thermoforming. If the viscosity does not increase significantly as the part is stretched, localized thinning or tearing may occur in the high stretch areas. An elongational viscosity ratio at 1.0:0.25 hencky strain >1.5 is desirable to prevent further strain in areas that are locally strained to high levels, which may lead to thinning or tearing.

The elongational viscosity ratio at 1.0:0.25 hencky strain for all tested samples was > 1.5. Increasing the MFR of the polypropylene component does not result in a decrease in value. This study shows that all parts should be well formed given the similar slope of elongational viscosity versus hencky strain increase.

Experiment 3 Shore A hardness

As described in table V, all formulation samples described in table V had a shore a hardness < 95. These samples were tested according to ASTM D2240-15 with a 10 second delay.

Experiment 4-tensile elongation at Room temperature

As described in table V, room temperature (23 ℃ and 50% relative humidity [ RH ]) tensile elongation was > 400% for the formulation samples containing polypropylene with MFR < 35. All formulation samples containing polypropylene with MFR >35 showed tensile elongation < 400%.

The tensile properties of a TPO skin can be measured by, for example, ASTM D638. The test specimens were die cut to the specified geometry. Testing can be performed at RT in the transverse extrusion direction. The samples were tested at 500mm/min according to ASTM D638 with V-type geometry.

Experiment of tensile elongation at 5-95 deg.C

As described in table V, the tensile elongation at 95 ℃ of the formulation samples containing polypropylene with MFR 0.5 and 2.0 is > 400%. All formulation samples containing polypropylene with MFR >35 showed tensile elongation < 400%.

The tensile properties of a TPO skin can be measured by, for example, ASTM D638. The test specimens were die cut to the specified geometry. The test can be performed at a temperature of 95 ℃ in the transverse extrusion direction. The samples were tested at 500mm/min according to ASTM D638 with V-type geometry.

Experiment 6-tear Strength at Room temperature

As described in Table V, the room temperature tear strength (23 ℃ and 50%) of the polypropylene formulations containing MFR <35 > 20 kN/m. All formulation samples containing polypropylene with MFR >35 showed tear strength <20 kN/m. Thus, for applications requiring reduced tear strength, formulation samples containing polypropylene having MFR >35 may be more desirable.

The tear properties of a TPO skin layer can be measured by ASTM D624. The test specimens were die cut to obtain a standard pant-like geometry. Testing can be performed in the machine extrusion direction. Method ASTM D624 was utilized at a test temperature of 23 ℃ and at a rate of 500 mm/min.

TABLE V-summary of test results from experiments 3-6

Experiment of 7-60 degree (60 degree) glossiness

The 60 ° gloss was measured on the textured side of the TPO soft skin using a BYK Gardner 4561 mini gloss meter in the cross extrusion direction. In addition, the surface appearance of 300mm × 100mm × 0.7mm was also noted.

As shown in FIG. 4, the gloss level of TPO flexible sheets containing polypropylene having MFR >35 is reduced. This is desirable because many OEMs desire a TPO soft skin gloss level < 2.0.