EP4496846A1 - Kautschukzusammensetzung enthaltend additiv und dessen verwendung - Google Patents
Kautschukzusammensetzung enthaltend additiv und dessen verwendungInfo
- Publication number
- EP4496846A1 EP4496846A1 EP23713348.3A EP23713348A EP4496846A1 EP 4496846 A1 EP4496846 A1 EP 4496846A1 EP 23713348 A EP23713348 A EP 23713348A EP 4496846 A1 EP4496846 A1 EP 4496846A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fatty acid
- rubber
- rubber composition
- weight
- additive
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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- 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
- C08K3/02—Elements
- C08K3/04—Carbon
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- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- 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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/32—Properties characterising the ingredient of the composition containing low molecular weight liquid component
- C08L2207/322—Liquid component is processing oil
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/02—Crosslinking with dienes
Definitions
- the present invention relates to a rubber composition which contains rubber and at least one rubber additive based on a fatty acid ester.
- the present invention further relates to the use of the rubber additive in a rubber composition, and to a tire in which at least one component is at least partially made from the rubber composition according to the invention, as well as methods for producing the same.
- Background of the invention The trend in the development of tread compounds for all-season and winter tires in recent years has been determined by improvements in the properties of tire grip (grip) at low temperatures and tire abrasion (stiffness). To achieve this, the respective rubber compositions contain, for example, rubbers with a long chain length. This results in poor processing (high viscosity, lack of green strength) of the rubber mixture.
- the composition includes rubber compound and glycerol fatty acid monoester as well as silica.
- US 2019/0233622 A1 discloses ethoxylated glycerin esterified with fatty acids for use in rubber compositions for tires with improved processability and abrasion resistance (see claim 1, paragraphs [0001] to [0003]).
- Tire wear is largely determined by the glass transition temperature of the rubber (Tan delta max peak, DMA).
- An improvement in the rolling resistance of the tires produced is not described in US 2019/0233622 Al.
- Rolling resistance is influenced by materials that change the tan delta at 60°C. Abrasion and rolling resistance are independent variables and the person skilled in the art would not necessarily conclude that an improvement in one means an improvement in the other.
- An object of the present invention is to develop a new additive for winter and all-season tires that improves the processing properties of the rubber composition used to manufacture these tires. At the same time, the remaining performance properties of the tires, in particular the rolling resistance and the properties regarding snow grip and adhesion under dry conditions, as well as the tire wear, should not be impaired or should even be at least partially improved.
- a further object of the invention is to improve the extrusion properties as well as the condition of the surfaces and edges of extrudates (Garvey Die) made from the rubber composition.
- a rubber composition which contains rubber and at least one rubber additive, characterized in that the at least one rubber additive comprises fatty acid esters, which fatty acid esters consist of at least one C 8 - to C 22 -Fatty acid and at least one compound selected from C 2 - to C 4 -alkoxylate of a polyol, polyethylene glycol, polypropylene glycol and / or copolymer of ethylene oxide and propylene oxide.
- the at least one rubber additive comprises fatty acid esters, which fatty acid esters consist of at least one C 8 - to C 22 -Fatty acid and at least one compound selected from C 2 - to C 4 -alkoxylate of a polyol, polyethylene glycol, polypropylene glycol and / or copolymer of ethylene oxide and propylene oxide.
- a further aspect of the present invention relates to the use of fatty acid esters of at least one C 8 to C 22 fatty acid and at least one compound selected from C 2 to C 4 alkoxylate of a polyol, polyethylene glycol, polypropylene glycol and/or copolymer of ethylene oxide and propylene oxide as a rubber additive in a rubber composition to improve the Mooney viscosity and/or extrusion properties of the rubber composition and/or to improve at least one of abrasion, wet grip and/or rolling resistance of a tire made from the rubber composition.
- a further aspect of the present invention relates to a method of producing a tire, characterized in that one or more components of the tire are made from a rubber composition as defined herein and the rubber composition is cured.
- a further aspect of the present invention relates to a tire in which at least one component has been made at least partially from a rubber composition as defined herein, and the tire is preferably an all-season or winter tire, wherein the component is in particular a tread.
- Preferred embodiments are the subject of the subclaims. Embodiments of the inventions include the following: the components listed and can in particular consist of these.
- Figures 1a-d show various extrudates (after 24 hours and after a week, at 60 rpm and 151 rpm) which were produced from the rubber compositions A and B as described in Example 3 ( Figure 1a: after 24h at 151/min; Figure 1b: after 24h at 60 1/min; Figure 1c: after a week at 15 1/min; Figure 1d: after a week at 601/min).
- Figures 2a-b show various extrudates after 24h (at 60 1/min and 151/min), which were produced from the rubber compositions C and D as described in Example 4 ( Figure 2a: after 24h at 151/min; Figure 2b: after 24 hours at 601 rpm).
- Figures 3a-d show various extrudates (after 24 hours and after a week, at 60 rpm and 151 rpm) which were produced from the rubber compositions E and F as described in Example 5 ( Figure 3a: after 24 hours at 151 /min; Figure 3b: after 24 hours at 60 1/min; Figure 3c: after a week at 15 1/min; Figure 3d: after a week at 601/min).
- Figures 4a-b show various extrudates (at 15 1/min and 60 1/min) which were produced from the rubber compositions G to J as described in Example 6 ( Figure 4a: after 24h at 151/min; Figure 4b: after 24h at 601 rpm).
- Figure 5 shows the course of the material pressure of the rubber compositions G to J from Example 6 at different shear rates.
- fatty acid esters consisting of at least one C 8 to C 22 fatty acid (fatty acid component, as defined in more detail below) and at least one compound selected from C 2 to C 4 alkoxylate a polyol, polyethylene glycol, polypropylene glycol and / or copolymer made from ethylene oxide and propylene oxide (polyol component, as defined in more detail below) have positive properties in a rubber composition.
- the components of the rubber composition according to the invention are described in more detail below.
- the fatty acid ester according to the invention is made from at least one compound selected from C 2 to C 4 alkoxylate of a polyol, polyethylene glycol, polypropylene glycol and/or copolymer of ethylene oxide and propylene oxide (polyol component), which esterifies with a C 8 to C 22 fatty acid became.
- the polyol component has 2 to 8 hydroxyl groups, such as 2 to 6 hydroxyl groups.
- the polyol component preferably has between 2 and 4 hydroxyl groups.
- the polyol component used to produce the fatty acid ester has 2 or 3 hydroxyl groups.
- the polyol component has no aromatic groups.
- the polyol component according to the invention consists only of carbon, hydrogen and oxygen.
- the fatty acid ester is made from C 8 to C 22 fatty acid and at least one polyether such as polyethylene glycol (PEG), polypropylene glycol (PPG) and/or copolymer of ethylene oxide and propylene oxide.
- the copolymers of ethylene oxide and propylene oxide can be random copolymers or block copolymers. It is known to those skilled in the art that polyethers with higher molecular weights are polymolecular, that is, they consist of distributions of macromolecules with different molecular weights.
- polyethylene glycols, polypropylene glycols and/or copolymers of ethylene oxide and propylene oxide with an average molecular weight in the range of approximately 200 to 1500 g/mol, for example 200 to 800 g/mol, such as approximately 400 g/mol, can be used for the production.
- Position of the fatty acid ester can be used.
- the fatty acid ester according to the invention is made from polyethylene glycol (PEG), polypropylene glycol (PPG) and/or copolymer of ethylene oxide and propylene oxide, which has been esterified with a C 8 to C 22 fatty acid.
- the fatty acid ester according to the invention is made from polyethylene glycol or polypropylene glycol.
- the fatty acid ester is made from at least one polyethylene glycol or polypropylene glycol with a molecular weight of 200 to 800 g/mol, in particular 400 g/mol to 600 g/mol.
- the fatty acid ester is made from at least one polyethylene glycol with a molecular weight of 200 (PEG 200) to 800 g/mol (PEG 800), such as 400 to 600 g/mol, in particular 400 g/mol (PEG 400).
- the fatty acid ester is made from at least one polypropylene glycol with a molecular weight of 200 to 800 g/mol, such as 400 to 600 g/mol, in particular 600 g/mol.
- the fatty acid ester is made from at least one random copolymer of ethylene oxide and propylene oxide with a molecular weight of 200 to 800 g/mol, such as 400 to 600 g/mol, in particular 400 g/mol.
- the random copolymer of ethylene oxide and propylene oxide has an ethylene oxide group content of 10 to 30% by weight.
- the fatty acid ester is made from at least one block copolymer of ethylene oxide and propylene oxide with a molecular weight of 50 to 4500 g/mol, such as 200 to 3000 and in particular 500 to 2500 g/mol.
- the ethylene oxide/propylene oxide block copolymer has an ethylene oxide group content of 10 to 80% by weight, such as 10 to 55% by weight.
- the block copolymers can be constructed in which there are polypropylene glycol molecules in the middle and polyoxyethylene groups at both ends.
- the ethylene oxide/propylene oxide block copolymers to be used according to the invention are commercially available compounds. They can be produced by reacting polypropylene glycol with ethylene oxide.
- ethylene oxide/propylene oxide block copolymers are the Pluronic PE polymers from BASF SE, such as Pluronic PE 3100, Pluronic PE 3500, Pluronic PE 4300, Pluronic PE 6100, Pluronic PE 6120, Pluronic PE 6200, Pluronic PE 6400, Pluronic PE 6800, Pluronic PE 8100, Pluronic PE 9200, Pluronic PE 9400, Pluronic PE 10100, Pluronic PE 10300, Pluronic PE 10400 and Pluronic PE 10500.
- the fatty acid ester is prepared from at least one C 2 to C 4 alkoxylate of a polyol .
- Polyols are substances that have at least two free hydroxyl groups.
- the hydrocarbon portion of the polyol is a group containing carbon and Contains hydrogen, with at least two carbon atoms bonded to a hydroxyl group. It can be straight-chain or branched, in particular straight-chain, and optionally interrupted by a heteroatom.
- a C 2 - to C 4 -alkoxylate of a polyol is a polyol that has been reacted with a C 2 - to C 4 -alkylene oxide, whereby several reactions can take place in succession on a hydroxyl group of the polyol.
- Examples of C 2 to C 4 alkylene oxides are ethylene oxide, propylene oxide and 1-butene oxide. The polyols are reacted with the C 2 to C 4 alkylene oxide using standard processes.
- Mixed C 2 to C 4 alkoxylates can also be used, in which a polyol is reacted using a mixture of C 2 to C 4 alkylene oxides (mixture of ethylene oxide and propylene oxide and/or 1-butylene oxide).
- the fatty acid ester consists of at least one polyol alkoxylate with up to 10, such as 5 to 10, e.g. B. 7 alkylene oxide units produced.
- the C 2 to C 4 alkoxylate of a polyol may have an average molecular weight in the range of about 200 to 1500 g/mol, such as about 200 to 800 g/mol, especially 300 to 500 g/mol.
- the C 2 to C 4 alkoxylate of a polyol has 2 to 8 hydroxyl groups, such as 2 to 6 hydroxyl groups.
- the C 2 to C 4 alkoxylate of a polyol used to produce the fatty acid ester has between 2 and 4 hydroxyl groups, such as 2 or 3 hydroxyl groups.
- the fatty acid ester is made from at least one polyol ethoxylate with up to 10, such as 5 to 10, e.g. B. 7 ethylene oxide units (EO units) produced.
- the fatty acid ester consists of at least one polyol propoxylate with up to 10 like 5 to 10, e.g. B.
- the polyol ethoxylate or polyol propoxylate preferably has between 2 and 4 hydroxyl groups.
- the polyol of the C 2 to C 4 alkoxylate may be a C 2 to C 15 polyol. This means that the polyol has 2 to 15 carbon atoms.
- the C 2 to C 15 polyol component of the alkoxylate is preferably C 2 to C 10 polyol and in particular C 2 to C 6 polyol.
- the polyols preferably have 2 to 8 hydroxyl groups, such as 2 to 8 and in particular 2 to 4 hydroxyl groups, such as 2 or 3 hydroxyl groups.
- the polyol of the C 2 - to C 4 - alkoxylate is selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, glycerin and mixtures thereof and is in particular glycerin.
- Sugar alcohols such as sorbitol, maltitol, mannitol, xylitol and mixtures thereof can also be used as polyols that can be reacted with a C 2 -C 4 alkylene oxide. This has the further advantage that the fatty acid esters produced in this way can be produced more sustainably.
- the polyol component of the fatty acid ester is a substance from the group consisting of polyethylene glycol, polypropylene glycol, ethoxylated glycerin, ethoxylated trimethylolpropane, ethoxylated pentaeryrthritol, ethoxylated sorbitol and/or mixtures thereof.
- the fatty acid ester is prepared from C 8 to C 22 fatty acid and ethoxylated glycerol, in particular up to 10, such as 5 to 10, e.g. B. has 7 ethylene oxide units.
- Such a glycerol according to the invention is commercially available, for example, as Aduxol-Gly-07 from Shurer & Schläpfer.
- only one polyol component is used to produce the fatty acid ester (however, this includes higher molecular weight alcohols that have a certain molecular weight distribution, such as PEG 400).
- at least two different polyol components are used to produce the fatty acid ester.
- a mixture of PEG, PPG and/or PEG-PPG copolymer can be used to produce the fatty acid ester.
- Fatty acid component The fatty acid component according to the invention is based on C 8 to C 22 fatty acids.
- fatty acids have 8 to 22 carbon atoms.
- fatty acids usually mean aliphatic saturated and unsaturated carboxylic acids with almost exclusively unbranched carbon chains (see, for example, Römpp Chemie Lexikon 9th edition 1990, volume 2, p.1343).
- “fatty acids” also include acids that have unsaturations.
- branches or heteroatoms can be present as long as this does not significantly affect the aliphatic character of the acids.
- the fatty acid component according to the invention consists of a mixture of different fatty acids.
- the fatty acid component can be at least two, such as include at least three, four or five different C 8 to C 22 fatty acids.
- Typical examples of fatty acids that can be used as fatty acid components in the present invention are caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, elaidic acid, vaccenoic acid, petroselinic acid , linoleic acid, linolenic acid, ricinoleic acid, 12-hydroxystearic acid, arachidic acid, gadoleic acid, gondoic acid, behenic acid, cetoleic acid and erucic acid.
- the fatty acid component according to the invention consists only of carbon, hydrogen and oxygen.
- the fatty acid component according to the invention comprises at least one mono- or di-unsaturated C 16 to C 20 fatty acid.
- a diunsaturated fatty acid is a fatty acid whose carbon chain has two double bonds.
- the fatty acid component according to the invention comprises at least one monounsaturated C 16 to C 20 fatty acid and at least one diunsaturated C 16 to C 20 fatty acid. In a further particularly preferred embodiment, the fatty acid component according to the invention comprises at least one monounsaturated C 16 to C 20 fatty acid, at least one diunsaturated C 16 to C 20 fatty acid and at least one triunsaturated C 16 to C 20 fatty acid. In a preferred embodiment, the fatty acid component according to the invention comprises at least one C 18 fatty acid, in particular a C 18:1 fatty acid, such as oleic acid and/or a C 18:2 fatty acid.
- a C 18:1 fatty acid is a fatty acid with 18 carbon atoms whose carbon chain has a double bond.
- a C 18:2 fatty acid is a fatty acid with 18 carbon atoms whose carbon chain has two double bonds.
- the fatty acid component according to the invention comprises at least one C 18:1 fatty acid and at least one C 18:2 fatty acid.
- the fatty acid component according to the invention comprises at least one C 18:1 fatty acid, at least one C 18:2 fatty acid and at least one C 18:3 fatty acid. It is known to those skilled in the art that commercial products used to produce fatty acid esters generally contain mixtures of fatty acids.
- the fatty acids can also be present as technical cuts, such as those produced during the pressure splitting or saponification of natural fats and oils, for example palm oil, palm kernel oil, coconut oil, olive oil, soybean oil, sunflower oil, rapeseed oil or beef tallow.
- the fatty acid ester according to the invention is prepared from a mixture of fatty acids which comprises at least 50% by weight, such as at least 75% by weight, in particular at least 90% by weight, of C 8 to C 22 fatty acids.
- the fatty acid ester according to the invention is prepared from a mixture of fatty acids which comprises at least 50% by weight, such as at least 75% by weight, in particular at least 90% by weight, of C 12 to C 20 fatty acids.
- the fatty acid ester according to the invention is prepared from a mixture of fatty acids which comprises at least 50% by weight, such as at least 75% by weight, in particular at least 90% by weight, of C 16 to C 20 fatty acids.
- the mixture of fatty acids preferably comprises 50 to 100% by weight, such as 75 to 100% by weight, in particular 90 to 100% by weight, of C 16 to C 20 fatty acids.
- the fatty acid ester according to the invention is prepared from a mixture of fatty acids which contains at least 50% by weight, such as at least 65% by weight, in particular at least 75% by weight, of saturated or mono- or polyunsaturated C18 -Fatty acids include.
- the fatty acid ester according to the invention is prepared from a mixture of fatty acids which comprises 50 to 95% by weight, such as 65 to 90% by weight, in particular 70 to 85% by weight, of saturated or mono- or polyunsaturated C 18 fatty acids .
- the mixture of fatty acids used for production preferably contains at least 1% by weight of saturated C 18 fatty acid, 10% by weight of C 18:1 fatty acid and/or at least 5% by weight of C 18:2 fatty acid.
- the mixture of fatty acids comprises at least 50% by weight, such as at least 65% by weight, in particular at least 70% by weight, of C 18:1 fatty acid, in particular oleic acid.
- the mixture of fatty acids comprises 50 to 90% by weight, such as 65 to 85% by weight, in particular 70 to 80% by weight, of C 18:1 fatty acid, in particular oleic acid. In one embodiment, the mixture of fatty acids comprises 0.1 to 30% by weight, such as 1 to 15% by weight, in particular 5 to 12% by weight, of C 18:2 fatty acid, in particular linoleic acid. In a preferred embodiment, the mixture of fatty acids comprises 65 to 85% by weight of C 18:1 fatty acid and 1 to 15% by weight of C 18:2 fatty acid.
- the mixture of fatty acids comprises at least 5% by weight, such as at least 10% by weight, in particular at least 15% by weight, of C 18:1 fatty acid, in particular oleic acid.
- the mixture of fatty acids can comprise 5 to 50% by weight, such as 10 to 40% by weight, in particular 15 to 35% by weight, of C 18:1 fatty acid, in particular oleic acid.
- the mixture of fatty acids can comprise 10 to 90% by weight, such as 25 to 75% by weight, in particular 40 to 65% by weight, of C 18:2 fatty acid, in particular linoleic acid.
- the mixture of fatty acids comprises 10 to 40% by weight of C 18:1 fatty acid and 25 to 75% by weight of C 18:2 fatty acid, such as 15 to 35% by weight of C 18:1 fatty acid and 40 up to 65% by weight C 18:2 fatty acid.
- the mixture of fatty acids can comprise 0.1 to 30% by weight, such as 1 to 20% by weight, in particular 2 to 15% by weight, of C 18:3 fatty acid.
- the mixture of fatty acids comprises 10 to 40% by weight of C 18:1 fatty acid, 25 to 75% by weight of C 18:2 fatty acid and 1 to 20% by weight of C 18:3 fatty acid .
- the mixture of fatty acids comprises 15 to 35% by weight of C 18:1 fatty acid and 40 to 65% by weight of C 18:2 fatty acid and 2 to 15% by weight of C 18:3 fatty acid.
- the acid number of the fatty acid used or the fatty acid mixture used is preferably 100 to 300 mg KOH/g, in particular 150 to 250 mg KOH/g.
- the acid number is measured using DIN EN ISO 2114.
- the saponification number of the fatty acid used or the fatty acid mixture used is preferably 100 to 300 mg KOH/g, in particular 150 to 250 mg KOH/g.
- the saponification number indicates the amount of potassium hydroxide in mg that is required to saponify 1 g of the sample to be examined.
- the saponification number is measured using DIN EN ISO 3681.
- the iodine number of the fatty acid used or the fatty acid mixture used is preferably 10 to 200 g iodine/100 g, in particular 50 to 150 g iodine/100 g.
- the iodine number indicates the degree of unsaturation of the sample.
- the iodine number is measured using DIN EN ISO 39612018-1.
- Fatty acid esters The esterification of the polyols with the fatty acids can be carried out in a known manner.
- the acidic catalysts that can be used here are, for example, hypophosphorous acid, methanesulfonic acid, butanesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, alkylbenzenesulfonic acid, sulfosuccinic acid and/or mixtures thereof. It is also recommended to carry out the esterification at elevated temperatures, for example at 140 to 250 ° C, preferably at 180 to 240 ° C.
- the fatty acid ester is prepared by heating in hypophosphorous acid. As described above, the fatty acid ester can be prepared from a mixture of different fatty acids and/or polyols.
- the fatty acid ester according to the invention consists only of carbon, hydrogen and oxygen.
- the fatty acid ester according to the invention is prepared from at least one C 2 to C 4 alkoxylate of a C 2 to C 6 polyol and at least one C 12 to C 22 fatty acid, preferably at least one unsaturated C 16 to C 20 - fatty acid.
- the fatty acid ester is preferably a partial ester (ie, not all -OH groups of the polyol from which the ester is formed are esterified) and in particular is at least 40% by weight, such as at least 70% by weight.
- the fatty acid ester according to the invention consists essentially of monofatty acid esters.
- the fatty acid ester according to the invention is a monofatty acid ester of C 2 to C 4 alkoxylate of a C 2 to C 6 polyol and at least one C 16 to C 20 fatty acid, preferably an unsaturated C 16 to C 20 fatty acid.
- the fatty acid ester according to the invention is a monofatty acid ester of polyethylene glycol and at least one C 12 to C 22 fatty acid, preferably at least one unsaturated C 16 to C 20 fatty acid.
- the fatty acid ester according to the invention is a monofatty acid ester of polypropylene glycol and at least one C 12 to C 22 fatty acid, preferably at least one unsaturated C 16 to C 20 fatty acid.
- the fatty acid ester according to the invention is a monofatty acid ester of copolymer of ethylene oxide and propylene oxide and at least one C 12 to C 22 fatty acid, preferably at least one unsaturated C 16 to C 20 fatty acid.
- the copolymer of ethylene oxide and propylene oxide may be a random copolymer or block copolymer.
- the fatty acid ester according to the invention is a mixture of monofatty acid esters of polyethylene glycol or polypropylene glycol, the mixture of fatty acids used for production containing at least 50% by weight of C 16 to C 20 fatty acids, preferably at least 50% by weight of saturated or (multiple ) C 18 unsaturated fatty acid.
- the mixture of fatty acids used for this purpose can comprise 50 to 95% by weight, such as 65 to 90% by weight, in particular 70 to 85% by weight, of saturated or (poly)unsaturated C 18 fatty acids.
- the mixture comprises at least 10% C 18:1 fatty acid and/or at least 5% by weight C 18:2 fatty acid.
- the fatty acid ester according to the invention is a mixture of monofatty acid esters of polyethylene glycol or polypropylene glycol, the mixture of fatty acids used for production being 65 to 85% by weight of C 18:1 fatty acid and/or 1 to 15% by weight of C 18 :2 - fatty acid includes.
- the fatty acid ester according to the invention is a mixture of monofatty acid esters of polyethylene glycol or polypropylene glycol, the mixture of fatty acids used for production being 10 to 40% by weight of C 18:1 fatty acid and/or 25 to 75% by weight of C 18:2 - fatty acid and / or 1 to 20% by weight of C 18:3 - fatty acid.
- the mixture of fatty acids comprises 15 to 35% by weight of C 18:1 fatty acid and 40 to 65% by weight of C 18:2 fatty acid and 2 to 15% by weight of C 18:3 fatty acid.
- the fatty acid ester according to the invention is an ester of polyol ethoxylate or polyol propoxylate and a C 8 to C 22 fatty acid ester mixture, preferably a C 12 to C 22 fatty acid ester mixture.
- the fatty acid ester according to the invention is an ester of ethoxylated glycerol or trimethylolpropane, which has up to 10, such as 5 to 10, ethylene oxide units, and a fatty acid ester mixture, the mixture of fatty acids used for production containing at least 50% by weight of C 16 - to C 20 fatty acids, preferably 50 to 95% by weight of saturated or unsaturated C 18 fatty acid.
- the fatty acid ester according to the invention is an ester of ethoxylated glycerol or ethoxylated trimethylolpropane, which has up to 10, such as 5 to 10, ethylene oxide units, and a fatty acid ester mixture, the mixture of fatty acids used for production being 65 to 85% by weight of C 18:1 fatty acid and/or 1 to 15% by weight.
- C 18:2 - fatty acid includes.
- the fatty acid ester according to the invention is an ester of ethoxylated glycerol or ethoxylated trimethylolpropane, which has up to 10, such as 5 to 10, ethylene oxide units, and a fatty acid ester mixture, the mixture of fatty acids used for production being 10 to 40% by weight of C 18:1 fatty acid and/or 25 to 75% by weight of C 18:2 fatty acid and/or 1 to 20% by weight of C 18:3 fatty acid.
- the fatty acid ester according to the invention is a monoester of ethoxylated glycerol or ethoxylated trimethylolpropane, which has 5 to 10 ethylene oxide units, and a fatty acid ester mixture, the mixture of fatty acids used for production preferably containing at least 50% by weight of saturated or unsaturated C 18 - fatty acid, in particular 65 to 85% by weight, C 18:1 - fatty acid and / or 1 to 15% by weight of C 18:2 - fatty acid.
- the fatty acid ester according to the invention is a monoester of ethoxylated glycerol or ethoxylated trimethylolpropane, which has up to 10, such as 5 to 10, ethylene oxide units, and a fatty acid ester mixture, the mixture of fatty acids used for production being 10 to 40 wt -% C 18:1 - fatty acid and / or 25 to 75% by weight of C 18:2 - fatty acid and / or 1 to 20% by weight of C 18:3 - fatty acid.
- the fatty acid ester has an acid number (SZ) of 0 to 10 mg KOH/g, such as 2 to 8 mg KOH/g.
- the acid number can be measured using DIN EN ISO 2114.
- the fatty acid ester has a hydroxyl number (OHZ) of 5 to 200 mg KOH/g, such as 100 to 190 mg KOH/g and 120 to 180 mg KOH/g.
- the hydroxyl number is the amount of potassium hydroxide (KOH) in milligrams (mg) that corresponds to the hydroxyl groups that are acetylated in 1 gram of the tested product under specified test conditions.
- KOH potassium hydroxide
- the measurement of the hydroxyl number can be determined using DIN-EN-ISO 4629-1:2016-12.
- the fatty acid ester has a pour point of 5 to -50°C, such as 0 to -40°C and -10 to -30°C.
- the pour point is the lowest temperature at which the oil will flow when it is cooled under specified conditions.
- the pour point can be measured using DIN-ISO 3016.
- the fatty acid ester has a dynamic viscosity of 50 to 1000 mPas, such as 70 to 700 mPas and 100 to 400 mPas.
- the dynamic viscosity is defined as the quotient of the shear stress and the velocity gradient.
- the dynamic viscosity can be measured using DIN-ISO 3219.
- a viscometer e.g. a Roto Visko 1 viscometer from Haake
- a rheometer e.g. Modular Compact 302 from Anton Paar
- the rubber composition according to the invention contains at least one rubber additive which comprises fatty acid esters.
- the rubber additive may consist of the fatty acid ester.
- the rubber additive contains at least 50% by weight, preferably at least 70% by weight, in particular at least 90% by weight, of fatty acid esters.
- the rubber additive can also have other components.
- the rubber additive contains fatty acid esters and/or fatty acid soaps, in particular zinc and/or potassium fatty acid soaps.
- the rubber additives of the present invention can preferably be present in a mixture which contains one or more solid carrier materials and one or more fatty acid esters and, if appropriate, other components.
- Inorganic fillers such as silicas
- waxy materials such as polyethylene waxes
- silica is used as the carrier material.
- examples of commercially available silicas that can be used in the blend of the present invention are Sipernat 22 and Sipernat 50 from Evonik.
- Other components that can be included in the mixture include: B. amides, amino alcohols and soaps can be used.
- Several fatty acid esters according to the invention can also be present in a mixture.
- the weight ratio of carrier material to fatty acid ester in the mixture is, for example, 10/90 to 90/10, more preferably 20/80 to 80/20 and particularly preferably about 30/70 or 33/67.
- the rubber composition according to the invention contains at least one rubber.
- the rubber is a rubber that can be crosslinked by sulfur crosslinking.
- rubbers are used that are particularly suitable for producing tread compounds that can be used in the production of tires.
- Preferred diene rubbers are butadiene rubber, polyisoprene and styrene-butadiene rubber.
- the rubber composition comprises at least one styrene-butadiene rubber, natural rubber, polyisoprene and/or butadiene rubber and optionally their functionalized forms.
- the rubber composition contains at least one styrene-butadiene rubber (styrene-butadiene copolymer). This can be either solution-polymerized styrene-butadiene rubber (SSBR) or emulsion-polymerized styrene-butadiene rubber (ESBR), although a mixture of at least one SSBR and at least one ESBR can also be used.
- SSBR solution-polymerized styrene-butadiene rubber
- ESBR emulsion-polymerized styrene-butadiene rubber
- styrene-butadiene rubber and “styrene-butadiene copolymer” are used synonymously in the context of the present invention.
- the styrene-butadiene copolymer(s) used can be end group modified with modifications and functionalizations and/or functionalized along the polymer chains.
- the modification can be those with hydroxy groups and/or ethoxy groups and/or epoxy groups and/or siloxane groups and/or amino groups and/or aminosiloxane and/or carboxy groups and/or Phthalocyanine groups and/or silane sulfide groups act.
- other modifications known to those skilled in the art, also referred to as functionalizations are also possible.
- a low-cis polybutadiene is e.g. B. Li-BR (lithium-catalyzed butadiene rubber) with a cis content of 20 to 50% by weight.
- the polybutadiene used can be end-group modified and/or functionalized along the polymer chains. Reference should be made to the possibilities disclosed above in connection with the modification and functionalization of styrene-butadiene rubber, if necessary adapted to the requirements of BR as a rubber material.
- the rubber composition contains at least one styrene-butadiene rubber, preferably in amounts of 40 to 100 phr, particularly preferably 70 to 90 phr.
- oil-extended rubber can also be added to the rubber compositions according to the invention.
- the amounts of oil-extended rubber used it is customary to “weigh” the oil content, so that recipes with “rubber” amounts of over 100 phr, such as e.g. B. up to 200 phr, e.g. B. in the range 40 or 70 to 140 or 150 phr.
- oil-extended rubber can be added so that the sum of the solid rubber components (see the definition above) is such that a total of 100 parts by weight of rubber is present.
- the rubber additive is used to reduce the amount of oil in oil-extended rubber. In this case, less oil is used in the rubber composition according to the invention than would be the case in a rubber composition with oil-extended rubber without the rubber additive.
- the rubber composition contains at least one styrene-butadiene rubber which is at the polymer chain ends and/or along the Polymer chains (“back bone functionalized”) are functionalized with at least one of the above-mentioned groups.
- the functional groups are particularly preferably groups that can bind to silica, such as in particular hydroxy groups and/or ethoxy groups and/or epoxy groups and/or siloxane groups and/or aminosiloxane and/or Carboxy groups and/or silane sulfide groups.
- the rubber composition contains 5 to 95 phr, preferably 10 to 30 phr, of at least one butadiene rubber.
- the rubber composition according to the invention can also contain natural and/or synthetic polyisoprene. Both cis-1,4-polyisoprene and 3,4-polyisoprene can be used here.
- the rubber composition preferably contains cis-1,4-polyisoprene with a cis-1,4 content of more than 90% by weight. Natural rubber is a rubber with a high cis-1,4 content.
- the polyisoprene used can also be end group modified and/or functionalized along the polymer chains. Reference should be made to the possibilities disclosed above in connection with the modification and functionalization of styrene-butadiene rubber, if necessary adapted to the requirements of polyisoprene as a rubber material.
- the rubber composition comprises at least one styrene-butadiene rubber and at least one butadiene rubber, in particular 5 to 95 phr of butadiene rubber and 5 to 80 phr of styrene-butadiene rubber.
- the rubber composition comprises at least one styrene-butadiene rubber, at least one butadiene rubber and at least one natural rubber, in particular 5 to 80 phr butadiene rubber. rubber, 5 to 80 phr styrene-butadiene rubber and 5 to 60 phr natural rubber.
- the rubber composition comprises at least one liquid polymer (viscous liquids at normal temperature) such as LIR (liquid polyisoprene), LBR (liquid polybutadiene) and L-SBR (liquid styrene-butadiene).
- LIR liquid polyisoprene
- LBR liquid polybutadiene
- L-SBR liquid styrene-butadiene
- Kurapren LIR30 and Kurapren LIR50 from Kuraray Co., Ltd. can be used as liquid polyisoprene. be used.
- As the liquid polybutadiene for example LBR-302, LBR-307, LBR-305 LBR-352 or LBR-361 from Kuraray Co., Ltd. be used.
- the liquid styrene-butadiene that can be used is L-SBR-820 or L-SBR-841 from Kuraray Co., Ltd.
- the rubber composition according to the invention can contain other rubbers in comparatively small amounts, such as 0.1 to 50 phr.
- Further additives The rubber composition of the present invention may contain further additives and components, in particular one or more fillers, one or more catalysts or activators for sulfur crosslinking and optionally further additives.
- the rubber composition of the present invention contains other additives and ingredients suitable for the production of tread compounds for tires.
- the rubber composition preferably contains at least one filler.
- the rubber composition can contain 5 to 300 phr, preferably 30 to 300 phr, in particular 50 to 200 phr of at least one filler, meaning the total amount of all fillers contained.
- the total filler content is 30 to 150 phr, particularly preferably 60 to 140 phr, again preferably 80 to 130 phr, again particularly preferably 100 to 130 phr and again very particularly preferably 110 to 130 phr.
- fillers known to those skilled in the art, such as soot, carbon nanotubes, silica, aluminosilicates, layered silicates such as kaolin, calcium carbonate (chalk), starch, calcium carbonate, barium sulfate, magnesium oxides, aluminum oxides, titanium dioxide, or rubber gels.
- the rubber composition preferably contains at least one silica as a filler.
- the silicas can be the silicas known to those skilled in the art which are suitable as fillers for rubber compositions.
- a finely divided, precipitated silica which has a nitrogen surface (BET surface) (according to DIN ISO 9277) of 35 to 350 m2/g, preferably of 35 to 260 m2/g , particularly preferably from 100 to 260 m2 / g and very particularly preferably from 115 to 235 m2 / g, and a CTAB surface (according to ASTM D 3765) from 30 to 400 m2 / g, preferably from 30 to 250 m2 / g, particularly preferably from 80 to 250 m2/g and very particularly preferably from 80 to 230 m2/g.
- Silicas can therefore be used, for example: B.
- silane coupling agents can be used in a rubber composition.
- One or more different silane coupling agents can be used in combination with one another.
- the rubber composition can therefore contain a mixture of different silanes.
- silane Coupling agents react with the surface silanol groups of the silica or other polar groups during the mixing of the rubber or the rubber composition (in situ) or before the filler is added to the rubber in the sense of a pretreatment (premodification).
- All silane coupling agents known to those skilled in the art for use in rubber compositions can be used as silane coupling agents.
- Such coupling agents known from the prior art are bifunctional organosilanes which have at least one alkoxy, cycloalkoxy or phenoxy group on the silicon atom as a leaving group and which, as other functionality, have a group which optionally, after cleavage, undergoes a chemical reaction with the double bonds of the polymer.
- the rubber composition according to the invention contains at least one plasticizer, the total amount of plasticizer preferably being 5 to 150 phr.
- the plasticizers used in the present invention include all plasticizers known to those skilled in the art, such as aromatic, naphthenic or paraffinic mineral oil plasticizers, such as. B. MES (mild extraction solvate) or RAE (Residual Aromatic Extract) or TDAE (treated distillate aromatic extract), or rubber-to-liquid oils (RTL) or biomass-to-liquid oils (BTL) preferably with a content of polycyclic aromatics of less than 3% by weight according to method IP 346 or facts, or plasticizer resins or natural oils (sunflower oil, rapeseed oil).
- the rubber composition may contain 5 to 40 phr, preferably 10 to 30 phr, of plasticizer.
- the rubber additive is used to reduce the amount of plasticizer in the rubber composition or to replace a plasticizer. In this case, less plasticizer is used in the rubber composition according to the invention than would be the case in a rubber composition without the rubber additive. This can be advantageous in certain cases, for example for environmental protection or economic reasons.
- the rubber composition preferably also contains substances required for crosslinking, such as zinc oxide, accelerators and/or sulfur. It is particularly advantageous if the rubber composition according to the invention contains zinc oxide or zinc-containing compounds for activating sulfur vulcanization.
- the vulcanization of the rubber composition is optionally carried out in the presence of sulfur and/or sulfur donors and with the aid of vulcanization accelerators, whereby some vulcanization accelerators can also act as sulfur donors and sulfur and/or sulfur donors as well as vulcanization accelerators in the prior art known amounts can be used. Sulfur and/or sulfur donors as well as one or more accelerators are added to the rubber composition in the stated amounts in the last mixing step.
- the accelerator is selected from the group consisting of thiazole accelerators and/or mercapto accelerators and/or sulfenamide accelerators and/or thiocarbamate accelerators and/or thiuram accelerators and/or thiophosphate accelerators and/or thiourea accelerators and/or xanthate accelerators and/or guanidine accelerators.
- sulfenamide accelerator which is selected from the group consisting of N-cyclohexyl-2-benzothiazolesufenamide (CBS) and/or N,N-dicyclohexylbenzothiazole-2-sulfenamide (DCBS) and/or benzothiazyl-2-sulfenmorpholide ( MBS) and/or 2,2 ⁇ -dibenzothiazyl disulfide (MBTS) and/or N-tert-butyl-2-benzothiazylsulfenamide (TBBS).
- CBS N-cyclohexyl-2-benzothiazolesufenamide
- DCBS N,N-dicyclohexylbenzothiazole-2-sulfenamide
- MBS benzothiazyl-2-sulfenmorpholide
- MBTS 2,2 ⁇ -dibenzothiazyl disulfide
- TBBS N-tert-butyl-2-benzothiazyls
- a sulfenamide accelerator, particularly preferably CBS, is preferably used in combination with the guanidine accelerator DPG (1,3-diphenylguanidine).
- the amount of DPG is 0 to 5 phr, preferably 0.1 to 3 phr, particularly preferably 0.5 to 2.5 phr, very particularly preferably 1 to 2.5 phr.
- the rubber composition can contain customary additives in customary parts by weight.
- the additives can be selected from the list consisting of anti-aging agents, activators, waxes, resins, mastication aids and processing aids and mixtures thereof.
- anti-aging agents examples include N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (6PPD), N,N'-diphenyl-p-phenylenediamine (DPPD), N,N'-ditolyl-p-phenylenediamine (DTPD), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD) and 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ) can be used.
- the rubber composition according to the invention preferably comprises 0.1 to 3 phr of anti-aging agents.
- activators examples include zinc oxide and fatty acids (e.g.
- the rubber composition according to the invention preferably comprises 0.5 to 10 phr, preferably 2 to 5 phr, of activators.
- the rubber composition according to the invention preferably comprises 0.1 to 3 phr of waxes.
- Plasticizer resins such as, for example, can be used as resins.
- the rubber composition according to the invention preferably comprises 5 to 150 phr, preferably 15 to 50 phr of resins.
- the rubber composition according to the invention preferably comprises 0.1 to 3 phr of mastication aids.
- fatty acid salts such as: B. zinc soaps are used.
- the inventive The rubber composition according to the invention preferably comprises 0.5 to 10 phr, preferably 2 to 5 phr, processing aids.
- the rubber composition contains a) 0.1 to 3 phr of anti-aging agents, b) 0.5 to 10 phr, preferably 2 to 5 phr of activators, c) 0.1 to 3 phr of waxes, d) 5 to 100 phr, preferably 15 to 50 phr resins, e) 0.1 to 3 phr mastication aids, and f) 0.5 to 10 phr, preferably 2 to 5 phr processing aids.
- the proportion of the total amount of further additives is 3 to 150 phr, preferably 3 to 100 phr and particularly preferably 5 to 80 phr.
- the rubber composition preferably contains between 0.1 to 40 phr of fatty acid esters, as well as 1 to 40, 2 to 40, 3 to 40, 4 to 40 or 5 to 40.
- the rubber composition contains 1 to 30 phr, as well 2 to 30, 3 to 30, 4 to 30 and especially 5 to 30 phr fatty acid esters.
- the fatty acid esters according to the invention can either be added to an existing rubber composition in a so-called “on top” use (in addition to other plasticizers). In such a case, use concentrations between 0.5 to 5 phr are preferred.
- the fatty acid esters according to the invention can also be used to completely or at least partially replace other plasticizers.
- the composition has a rolling resistance, tan delta, that is at least 5%, preferably 10%, in particular 15% lower, after vulcanization 60 ° C, and / or a 5%, preferably 10%, in particular 15% higher wet adhesion, tan delta at 0 ° C.
- the composition preferably has improved processability, in particular a Mooney viscosity that is at least 5%, preferably 10%, in particular 15% lower and/or a correspondingly lower material pressure during extrusion.
- the composition preferably has an improved stiffness, in particular a tensile strength and/or elongation at break and/or tensile strength module 100% and/or tensile strength module 300% higher by at least 5%, preferably 10%, in particular 15%.
- the above-mentioned improvements can be determined in comparison to an otherwise identical composition which, instead of the additive according to the invention, comprises a rubber additive known from the prior art in an identical amount. To check, two otherwise identical rubber compositions are produced and their properties are then compared.
- the improvements mentioned above can be determined in comparison to an otherwise identical composition which, instead of the additive according to the invention, comprises a plasticizer known from the prior art in an identical amount.
- Commercially available materials such as Tudalen 4192, can be used as known plasticizers.
- two otherwise identical rubber compositions are produced and their properties are then compared.
- the above improvements can also be determined in comparison to an otherwise identical composition, which does not contain the rubber additive according to the invention.
- two identical rubber compositions are produced and the rubber additive according to the invention is additionally added to one of them.
- the properties of the two rubber compositions are then compared with each other.
- the rubber composition is suitable for producing tread compounds for tires.
- the rubber composition according to the invention is also suitable for treads which consist of various tread mixtures arranged next to one another and/or one below the other (multi-component treads).
- the rubber additive defined above is usually produced by simply mixing the components. This continues until a desired homogeneous mixture is achieved. Suitable mixing devices are known to those skilled in the art.
- the rubber composition according to the invention is produced in a conventional manner, with a basic mixture, which contains all components with the exception of the vulcanization system (sulfur and substances influencing vulcanization), generally being first produced in one or more mixing stages and then The finished mixture is produced by adding the vulcanization system.
- the composition can then be further processed, e.g. B. by an extrusion process, and into the appropriate shape, e.g. B.
- tires are understood to mean pneumatic vehicle tires and solid rubber tires, including tires for industrial and construction site vehicles, truck, car and two-wheeler tires.
- the tire has the rubber composition according to the invention at least in the tread.
- the present invention further relates to a method for producing a tire, wherein one or more components of the tire are produced from the rubber composition according to the invention and the rubber composition is cured.
- the use of the rubber composition according to the invention can significantly improve the process for producing tires and treads.
- the present invention further relates to the use of fatty acid esters of at least one C 8 to C 22 fatty acid and a compound selected from C 2 to C 4 alkoxylate of a polyol, polyethylene glycol, polypropylene glycol and/or copolymer of ethylene oxide and propylene oxide as rubber additives - tive in a rubber composition to improve the Mooney viscosity and/or extrusion properties of the rubber composition and/or to improve at least one of abrasion, wet grip and/or rolling resistance of a tire made from the rubber composition.
- At least one of the properties mentioned is improved compared to a rubber composition which, instead of the rubber additive according to the invention, comprises a known rubber additive in an identical amount.
- Materials known in the prior art that are used as rubber additives can be used as known rubber additives.
- two otherwise identical rubber compositions are produced and their properties are then compared.
- at least one of the properties mentioned is improved by at least 5%, preferably at least 10%, compared to a rubber composition which, instead of the rubber additive according to the invention, comprises a known rubber additive in an identical amount.
- At least one of the properties mentioned is improved by at least 5%, preferably at least 10%, compared to an otherwise identical rubber composition, ie the rubber additive according to the invention is additionally added to the rubber composition.
- the rubber additive according to the invention is additionally added to the rubber composition.
- two identical rubber compositions are produced and the rubber additive according to the invention is additionally added to one of them.
- the properties of the two rubber compositions are then compared.
- at least one of the properties mentioned is improved by at least 5%, preferably at least 10%, compared to a rubber composition which, instead of the rubber additive according to the invention, comprises a known plasticizer in an identical amount, and is otherwise identical.
- Known plasticizers can be commercially available materials such as Tudalen 4192 can be used.
- the extrusion properties of the rubber composition are improved compared to a rubber composition which, instead of the rubber additive according to the invention, comprises a known plasticizer in an identical amount or which does not contain any plasticizer and is otherwise identical.
- the extrusion properties are understood to mean properties such as the extrusion speed, injection swelling, extrusion rate, material pressure, material temperature and/or the surface/edge properties of the extrudate.
- the surface quality and/or edge quality of the extrudate is improved.
- the surface is assessed using a grading system of AE, where A represents the top grade.
- the edges are assessed using a grading system of 1-10, with 10 being the best grade (according to ASTM D 2230).
- the rubber additive according to the invention can be used in particular in a rubber composition for treads.
- the use according to the invention uses a mixture which contains a) one or more solid carrier materials, and b) one or more fatty acid esters, and c) optionally further components such as amides, amino alcohols and/or soaps.
- Inorganic fillers such as silicas
- waxy materials such as polyethylene waxes
- a silica is used as the carrier material.
- the weight ratio of carrier material to fatty acid ester in the mixture is, for example, 10/90 to 90/10, more preferably 20/80 to 80/20 and particularly preferably about 30/70 or 33/67.
- Example 1 Preparation of the rubber additives according to the invention a) Rubber additive A 1217.8 g of ethoxylated glycerol (Aduxol GLY-07 from Shurer + Schläpfer), 835.7 g of fatty acid and 2.0 g of hypophosphorous acid were presented.
- the oleic acid mixture had an acid number of 201.0 mg KOH/g, a saponification number of 202.0 mg KOH/g and an iodine number of 100.0 g iodine/100 g.
- the iodine number was determined according to DIN EN ISO 3961 2018-11 and the saponification number according to DIN EN ISO 3681.
- the mixture was slowly heated to 230 °C and a vacuum was applied. The course of the reaction was monitored by measuring the acid number.
- the fatty acid ester produced had an acid number of 4.6 mg KOH/g. From the measurement of the hydroxyl number it could be deduced that predominantly a monoester was obtained.
- Rubber additive B 592.2 g of polyethylene glycol 400, 408.7 g of fatty acid and 1.0 g of hypophosphorous acid were presented. The fatty acid used was desti.
- Soybean oil fatty acid is used, which contains 2 - 6% C 18 , 20 – 29% C 18:1 , 47 - 58% C 18:2 , 4 - 10% C 18:3 , 9 - 12% C 16 , 0 - 1% C 16:1 , and 0 - 1% C 12+14 contains.
- the soybean oil fatty acid used had an acid number of 194 to 204 mg KOH/g, a saponification number of 195 - 206 mg KOH/g and an iodine number of 125 - 139 g iodine/100 g.
- the mixture was slowly heated to 230 °C and a vacuum was applied. The course of the reaction was monitored by measuring the acid number.
- the fatty acid ester produced had an acid number of 1.9 mg KOH/g.
- the kinematic viscosity at 20 ° C of the fatty acid ester produced was 95.1 mm2 / sec and the dynamic viscosity at 20 ° C was 94.8 mPa s.
- Rubber additive C 352.8 g polypropylene glycol 600, 161.8 g soy fatty acid (see rubber additive B) and 0.5 g of hypophosphorous acid were presented. The mixture was slowly heated to 230 °C and a vacuum was applied. The course of the reaction was monitored by measuring the acid number.
- the fatty acid ester produced had an acid number of 1.7 mg KOH/g.
- Example 2 Preparation of a rubber additive according to the invention Preparation of the rubber composition
- the mixture was prepared under usual conditions in one or more mixing stages. This was then further processed, e.g. B. by an extrusion process and brought into the appropriate shape.
- the various components of each mixture are listed in the tables below. Table 1 For all mixture examples contained in the table, the quantities given (parts by weight) are based on 100 parts by weight of total rubber (phr).
- Test specimens were produced from all mixtures and the material properties typical for the rubber industry were determined using these test specimens using the test methods specified below: ⁇ Mooney viscosity (MS 1+4, 100 °C), after each mixing stage and after aging, respectively according to DIN EN ISO 289-1, ⁇ Extrusion properties (extrusion speed, injection swelling, extrusion rate, material pressure, material temperature) Surface assessment (Garvey Die: surface AE with A as top grade, edges 1-10 with 10 as top grade), each according to ASTM D 2230, ⁇ Material pressure at Different shear rates were measured with an HDK - Göttfert Rheograph 25 (measuring temperature 100 ° C, nozzle geometry: round, length 10 mm, diameter 1 mm).
- ⁇ Rebound elasticity at RT measured according to ASTM D-8059 ⁇ Shore A hardness at room temperature (RT), measured according to DIN EN ISO 868, ⁇ Tear strength, elongation at break and tensile strength measured according to DIN 53 504, parameters for stiffness, also for tire abrasion, ⁇ Stress values at 100 and 300% elongation at room temperature (module 100%, module 300%), according to DIN 53504, ⁇ Loss factor tan delta at -20 °C, 0 °C and 60 °C according to DIN 53545, o Dynamic mechanical Analysis in which the vulcanized material is clamped and dynamically loaded, o Adhesion to snow can be correlated with the tan delta at -20°C (the larger the tan delta at -20°C, the better the snow adhesion), as described in the Encyclopedia of Polymer Blends, Volume 2: Processing, edited by Avraam I.
- Example 3 Comparison against Process Oil
- the properties of a rubber composition containing additive A prepared in Example 1 (Composition B) were compared to the properties of an otherwise identical rubber composition containing only TDAE oil (Composition A). .
- the comparison shows improved processing properties as well as improved tire handling and comparable tire adhesion properties of the rubber composition B according to the invention.
- the rubber composition according to the invention in particular has a lower rolling resistance, tan delta at 60 ° C.
- Table 2 The relevant information and data are shown in Table 2 below.
- Figures 1a-d Images of different extrudates of compositions A and B (after 24 hours and after a week, at 60 1/min and 15 1/min) are shown in Figures 1a-d.
- Figure 1a shows extrudates of compositions A and B after 24 hours at 15 rpm
- Figure 1b shows extrudates of compositions A and B after 24 hours at 60 rpm
- Figure 1c shows extrudates of compositions A and B after one week at 151 rpm
- the extrudates of the rubber composition B according to the invention in all cases have significantly fewer edges and an improved surface structure.
- the rubber composition B according to the invention has better processability (lower Mooney viscosity) and improved rolling resistance (lower tan delta at 60 ° C).
- Example 4 Comparison against composition without rubber additive according to the invention This example compares the properties of a rubber composition with additive A from Example 1 (composition D) with an otherwise identical rubber composition without the additive (composition C).
- Table 3 Images of various extrudates of compositions C and D after 24 hours at 60 1/min and 15 1/min are shown in Figure 2a and b.
- Figure 2a shows extrudates at 15 rpm
- Figure 2b shows extrudates at 60 rpm.
- the extrudates of the rubber composition D according to the invention have an improved surface structure in both cases.
- the rubber composition D according to the invention has better processability (lower Mooney viscosity), improved tire handling (higher rigidity), better abrasion properties (improved ultimate tear properties and lower DIN abrasion values) and improved wet grip (higher tan delta at 0°C) at a comparable rolling resistance (tan delta at 60°C).
- Example 5 Comparison against Glycerol Monooleate
- the properties of a rubber composition containing additive A prepared in Example 1 (Composition E) were compared to the properties of an otherwise identical rubber composition containing glycerin monooleate instead (Composition F). The comparison shows improved processing properties as well as improved tire handling and comparable to improved tire adhesion properties of the rubber composition E according to the invention.
- the rubber composition according to the invention has in particular a lower rolling resistance, tan delta at 60 ° C.
- Table 4 The relevant information and data are shown in Table 4 below.
- Figure 3a-d Images of different extrudates of the compositions E and F (after 24 hours and after a week, at 60 1/min and 15 1/min) are shown in Figure 3a-d.
- Figure 3a shows extrudates of the compositions E and F after 24 hours at 15 l/min
- Figure 3b shows extrudates of the compositions E and F after 24 hours at 60 l/min
- Figure 3c shows extrudates of the compositions E and F after one week at 151/min
- Figure 3d Extrudates of compositions E and F after one week at 60 1/min.
- the extrudates of the rubber composition B according to the invention in all cases have significantly fewer edges and an improved surface structure.
- the rubber composition E according to the invention has improved tire handling (higher rigidity), improved snow grip (higher tan delta at -20 ° C), improved wet grip (higher tan delta at 0 ° C) and improved rolling resistance (lower tan delta at 60 °C).
- Example 6 Comparison of properties of rubber additives AC
- the properties of rubber compositions containing the additives A to C prepared in Example 1 were compared with the properties of an otherwise identical rubber composition which instead contained more TDAE process oil contains (composition G). The comparison (see the data in Table 5) shows improved processing properties.
- compositions H - J according to the invention have improved extrusion properties (low material pressure, improved extrudates) and lower mixed viscosities.
- Additive C (composition J) has, in addition to improved processing (lower Mooney MS values and material pressures), better ultimate tear properties (tear strength, elongation at break and tear strength) as an indicator of better C&C properties (cut & chip) and higher tan delta values 0°C and 20°C as an indicator of better tire grip in wet and dry conditions.
- Additive B shows an even clearer improvement in processability, evident from lower material pressures, especially at high shear rates, with simultaneously improved tear resistance, without the trade-off between wet braking (comparable tan delta at 0°C) and rolling resistance (comparable tan delta at 60°C).
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP22163392 | 2022-03-21 | ||
| PCT/EP2023/057104 WO2023180263A1 (de) | 2022-03-21 | 2023-03-20 | Kautschukzusammensetzung enthaltend additiv und dessen verwendung |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4496846A1 true EP4496846A1 (de) | 2025-01-29 |
Family
ID=80930208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP23713348.3A Pending EP4496846A1 (de) | 2022-03-21 | 2023-03-20 | Kautschukzusammensetzung enthaltend additiv und dessen verwendung |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20250206922A1 (de) |
| EP (1) | EP4496846A1 (de) |
| JP (1) | JP2025509983A (de) |
| KR (1) | KR20240162118A (de) |
| WO (1) | WO2023180263A1 (de) |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2705555A1 (de) * | 1977-02-10 | 1978-08-17 | Bayer Ag | Stabile waermesensible latexmischungen |
| DE10012407A1 (de) * | 2000-03-15 | 2001-09-20 | Bayer Ag | Polyether enthaltende Kautschukmischungen |
| DE10342870A1 (de) * | 2003-09-15 | 2005-05-12 | Clariant Gmbh | Flüssige Zusammensetzungen enthaltend oxalkylierte Polyglycerinester |
| DE102009060389A1 (de) * | 2009-12-24 | 2011-06-30 | Clariant International Ltd. | Kälteadditive mit verbesserter Fließfähigkeit |
| CN106459499B (zh) | 2014-04-30 | 2018-07-13 | 株式会社普利司通 | 轮胎用橡胶组合物、其制造方法和轮胎 |
| CN106536610B (zh) * | 2014-07-18 | 2019-07-05 | 横滨橡胶株式会社 | 橡胶组合物及使用了该橡胶组合物的充气轮胎 |
| JP7013264B2 (ja) * | 2018-01-31 | 2022-01-31 | 第一工業製薬株式会社 | フィラー用分散剤 |
| JP6997643B2 (ja) | 2018-01-31 | 2022-01-17 | Toyo Tire株式会社 | タイヤ用ゴム組成物及び空気入りタイヤ |
| JP6997644B2 (ja) * | 2018-01-31 | 2022-01-17 | Toyo Tire株式会社 | タイヤ用ゴム組成物及び空気入りタイヤ |
| EP3760669B1 (de) * | 2018-02-26 | 2022-06-29 | The Yokohama Rubber Co., Ltd. | Kautschukzusammensetzung und damit hergestellter luftreifen |
-
2023
- 2023-03-20 US US18/849,011 patent/US20250206922A1/en active Pending
- 2023-03-20 JP JP2024556178A patent/JP2025509983A/ja active Pending
- 2023-03-20 EP EP23713348.3A patent/EP4496846A1/de active Pending
- 2023-03-20 KR KR1020247034141A patent/KR20240162118A/ko active Pending
- 2023-03-20 WO PCT/EP2023/057104 patent/WO2023180263A1/de not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| JP2025509983A (ja) | 2025-04-11 |
| KR20240162118A (ko) | 2024-11-14 |
| WO2023180263A1 (de) | 2023-09-28 |
| US20250206922A1 (en) | 2025-06-26 |
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