Method for plasticizing rubber composition and plasticizer

Abstract

To prolong the service life of vulcanized rubber compositions.SOLUTION: At least one modified polyorganosiloxane is added to the rubber composition as a plasticizer for the rubber composition. The rubber is vulcanized with at least one crosslinkable resin. The polyorganosiloxane includes three or more siloxane units and at least one organic moiety R1 with at least one carbon-carbon multiple bond and at least four carbon atoms.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present invention relates to a rubber composition containing a polyorganosiloxane as a plasticizer (or softener).

[0002] More particularly, the present invention relates to the use of (meth)acrylate modified polyorganosiloxanes as plasticizers in rubber compositions used as bladders in tire manufacture.

[0003] The present invention further relates to rubber compositions suitable for the manufacture of and use in bladders, especially for the manufacture of tires. [Background technology]

[0004] Rubber compositions vulcanized by resin crosslinking are known and have a wide variety of applications in various industrial sectors: rubber products based thereon are used, for example, in the manufacture of bladders which are used in the manufacture of tires of all kinds.

[0005] During the tire manufacturing process itself, the uncrosslinked green tire material (Reifenrohling) is vulcanized. The process of vulcanization refers to the crosslinking of the rubber composition under pressure and high temperature, during which covalent bonds are formed between the polymers and an elastomeric network is established.

[0006] The vulcanization of rubber mixtures can be carried out via various mechanisms. The most frequently used type of vulcanization is sulfur vulcanization. Rubber mixtures can also be crosslinked or vulcanized by peroxides, amines or resins.

[0007] For the manufacture of vehicle tires, the green tire material is introduced into a tire press for shaping and vulcanization. The bladder has the task of giving the tire its profile (tread pattern) by forcing the green tire against the inner wall of the tire press during vulcanization under pressure and at elevated temperature. For this purpose, the bladder takes in a pressurized medium, such as hot water or steam.

[0008] The necessary bladder can be made from a rubber composition. The rubber composition for the bladder is generally composed of a polymer system, a filler, zinc oxide, a plasticizing oil (process oil) and a crosslinking resin. In addition, further processing additives, which are usual, are components of the rubber composition.

[0009] The polymer is often butyl rubber, but chloroprene rubber is sometimes added if the crosslinkable resin is not halogenated. Carbon black is often used as a filler. Zinc oxide acts as a catalyst for the resin crosslinking or helps to increase the thermal conductivity. In known bladders, castor oil is used as the plasticizing oil, as will be explained in more detail below. Formaldehyde-alkylphenol resins containing methylol groups and optionally halogenated are generally used as crosslinkable resins. Furthermore, further compatibilizers, such as homogenizers, can be added to the corresponding compositions. Bladders are also described which contain both butyl rubber and rubbers with units derived from α-methylstyrene as polymer systems.

[0010] During the vulcanization of a tire, the bladder undergoes a cycle consisting of a filling process, inflation with a pressurized medium, and then decompression and release of the pressurized medium, whereby the bladder is mechanically loaded, but in addition to this mechanical loading, the corresponding physical conditions also change significantly during the course of the cycle, with the significant changes in pressure and temperature being of particular importance here.

[0011] The material used for the bladder must take this special type of load into account, especially in the context of being able to manufacture as many tires as possible with one bladder. The bladder goes through a number of different cycles depending on various factors such as tire size and vulcanization conditions.

[0012] Nonetheless, after a certain amount of loading, all bladders will begin to show signs of fatigue and eventually fail, for example by the formation of cracks, and as a result, the bladder will need to be replaced.

[0013] This results in an undesirable interruption of the continuous manufacturing process of the tire. Moreover, replacement incurs additional costs. Therefore, there is a constant interest in giving the bladder the longest possible life, since this not only brings about significant efficiency gains and cost savings for the tire producers involved, but rather it also makes a significant contribution to ensuring a more environmentally friendly tire production in general.

[0014] In order to withstand the considerable loads expected during use, the presence of a plasticizer component in the rubber-based bladder is essential. In this connection, castor oil, among others, has already been used as a plasticizer component in rubber-based bladders since the 1950s, as described, for example, in DE 1 283 521.

[0015] Castor oil is considered in this case to be a particularly suitable plasticizer and has been recognized for the past decades because it has a relatively low volatility even at high temperatures and is generally suitable for reducing the tendency of resin-crosslinked mixtures to exhibit the so-called marching modulus during crosslinking. In this context, for castor oil-containing rubber compositions, WO 2013 / 052206 A1 describes a low modulus and good resistance to steam aging. In this document, in addition to castor oil, an attempt is made to further improve the durability of the bladder to be produced by adding a hydrocarbon resin (HPM: Hydrocarbon Polymer Modifiers). [Prior art documents] [Patent documents]

[0016] [Patent Document 1] DE 1 283 521 [Patent Document 2] WO 2013 / 052206 A1 [Patent Document 3] EP 2 354 154 A1 [Patent Document 4] EP 2 151 479 A1 [Patent Document 5] US 2011 / 0262573 A1 [Patent Document 6] US 4,710,541 Summary of the Invention [Problem to be solved by the invention]

[0017] Despite the advantages associated with the use of castor oil in the rubber compositions in question, bladders made from the corresponding compositions are damaged after a certain number of vulcanization cycles, and thus far the addition of castor oil has not been successful in achieving the desired long life of the bladders.

[0018] EP 2 354 154 A1 and EP 2 151 479 A1 relate to rubber compositions which are peroxidatively vulcanized and which contain polyorganosiloxanes, which are said to improve the tack of the rubber during processing, without impairing the relevant mechanical properties of the resulting vulcanizate (e.g. reducing the modulus). The polyorganosiloxanes have at least one organic moiety R with at least one carbon-carbon multiple bond and optionally further hydrocarbon moieties R2 with a chain length of 5 to 50 carbon atoms. It should be noted that the action of the additive during processing of the rubber, such as a reduction in the tack, cannot be inferred from the finished vulcanizate with respect to certain desired physical properties, such as those attributed to plasticizers, such as shape-changing ability, elastic properties or reduced hardness.

[0019] US 2011 / 0262573 A1 describes a method for producing a bladder (Heizbalg; in English "Bladder") for tire manufacturing. In this method, the surface of the bladder is modified by application of a layer. This layer takes over the function of a release agent, but in this case is fixedly bonded to the surface of the bladder facing the inside of the tire. Castor oil is used as plasticizer in the rubber composition for the bladder known from US 2011 / 0262573 A1.

[0020] The polyorganosiloxanes used in US 2011 / 0262573 A1 as replacements for release agents for surface coatings have high molecular weights (average molecular weight, number average) of up to 12,000.

[0021] US 4,710,541 describes a method for molding and vulcanizing rubber products such as tires, in which an improved bladder is used. The bladder described in US 4,710,541 is improved, for example by suitable surface modification, in order to improve its release properties from the tire material. The invention described in US 4,710,541 therefore seeks an alternative to conventional release agents. The polyorganosiloxane described in US 4,710,541 is in particular a polymeric polyorganosiloxane having a degree of polymerization of more than 1,000, for example 7,000 dimethylsiloxy units. It is used in large proportions, for example 30 parts by weight to 70 parts by weight of rubber.

[0022] Thus, despite various improvements in the field of rubber compositions, there is a great demand for new and improved rubber compositions which are not only suitable to be vulcanized for bladders which can be used in tire production, but rather have a longer life span, taking into account the high material loads which occur within the framework of the vulcanization cycle for tire production. [Means for solving the problem]

[0023] According to a first aspect, the present invention relates to the use of one or more modified polyorganosiloxanes as plasticizers in a rubber composition, the rubber being vulcanized with one or more crosslinking resins (crosslinkers), the polyorganosiloxanes containing three or more siloxane units and one or more organic moieties R having one or more carbon-carbon multiple bonds and at least four carbon atoms. 1 The present invention relates to a use comprising:

[0024] According to a second aspect, the present invention relates to a method for producing a bladder for manufacturing tires, characterized in that a rubber composition comprising one or more modified polyorganosiloxanes, one or more crosslinking resins for crosslinking and optionally further conventional additives is vulcanized by said crosslinking resins, said modified polyorganosiloxanes and said rubber composition being as defined herein.

[0025] Finally (according to a third aspect), the present invention relates to a bladder for the manufacture of tires, comprising a rubber composition vulcanizable by a crosslinkable resin, the rubber composition comprising a modified polyorganosiloxane and being vulcanized by the crosslinkable resin, the modified polyorganosiloxane and the rubber composition being as defined herein.

[0026] "Modified" means that the organic moiety R 1 This means that there is

[0027] Where a feature of the invention can be present in one or more distinct embodiments, the variations detailed below apply to all (different) embodiments, even if not explicitly stated to be used in more than one (embodiment).

[0028] According to a first aspect of the present invention, a method for plasticizing a rubber composition is provided. the method includes adding one or more modified polyorganosiloxanes to the rubber composition as a plasticizer for the rubber composition; The rubber is vulcanized with one or more crosslinking resins; Polyorganosiloxanes are made up of three or more siloxane units and one or more organic moieties R having one or more carbon-carbon multiple bonds and at least four carbon atoms. 1 Including (Form 1) According to a second aspect of the present invention, there is provided a plasticizer for plasticizing a rubber composition. the plasticizer comprises one or more modified polyorganosiloxanes; The rubber is vulcanized with one or more crosslinking resins; Polyorganosiloxanes are made up of three or more siloxane units and one or more organic moieties R having one or more carbon-carbon multiple bonds and at least four carbon atoms. 1 Including It is characterized by (Form 23). A preferred embodiment of the present invention can consist of the features disclosed below without the presence (including) of further components. [Brief description of the drawings]

[0029] [Figure 1] Results of the De Mattia flex test for vulcanized rubber compositions 1-4. [Diagram 2] De Mattia flex test results for vulcanized rubber compositions 1-4 after their steam aging (190°C for 48 hours). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0030] A preferred embodiment of the invention is now presented. (Mode 1) See the first aspect of the present invention above. (Mode 2) In the method according to mode 1, R1 Preferably, contains up to 15 carbon atoms. (Mode 3) In the method according to mode 2, R 1 is a monovalent unsaturated acyloxy group having up to 15 carbon atoms (i.e. a group of the RCOO-type); The acyl group preferably has a substituted or unsubstituted double bond at a terminal thereof and is bonded to a silicon atom in the main chain of the polyorganosiloxane via a hydrocarbon chain. (Mode 4) In the method according to mode 3, The hydrocarbon chain preferably includes at least one oxygen atom in the hydrocarbon chain. (Mode 5) In the method according to mode 4, The hydrocarbon chain is preferably substituted with at least one hydroxyl group. (Mode 6) In the method according to any one of Modes 1 to 5, The modified polyorganosiloxanes are those that contain two or more organic moieties R 1 and / or additionally one or more longer alkyl groups R 2 having R 2 It is preferred that the alkyl group has a chain length of 5 to 50 carbon atoms. (Mode 7) In the method according to any one of Modes 1 to 6, Preferably, the rubber comprises butyl rubber, a brominated copolymer of isobutylene and p-methylstyrene, or a mixture thereof, and the rubber composition comprises chloroprene rubber as a crosslinking coagent. (Mode 8) In the method according to any one of modes 1 to 7, It is preferred to add to the rubber composition one or more further plasticizers which are not polyorganosiloxanes in an amount greater than 0 and less than 5 parts by weight per 100 parts by weight of rubber (mixture). (Mode 9) In the method according to mode 8, As the further plasticizer, it is preferable to add castor oil and / or a hydrocarbon resin. (Mode 10) In the method according to any one of Modes 1 to 7, It is preferable that only the modified polyorganosiloxane is added as the plasticizer to the rubber composition. (Mode 11) In the method according to any one of Modes 1 to 10, The rubber composition preferably contains further additives and ingredients suitable for the manufacture of bladders for tire construction. (Mode 12) In the method according to any one of Modes 1 to 11, The rubber composition is preferably vulcanized for use as a bladder in making tires. (Form 13) In the method according to form 11 or 12, The rubber composition preferably contains, as further components, a filler and a catalyst for resin crosslinking. (Form 14) In the method according to Form 13, The rubber composition preferably comprises homogenizers. (Mode 15) In the method according to any one of Modes 1 to 14, The crosslinkable resin is preferably a halogenated formaldehyde-alkylphenol resin. (Mode 16) In the method according to mode 15, Alkyl groups are C1-C 10 It is preferably alkyl. (Mode 17) In the method according to any one of Modes 1 to 16, The amount of polyorganosiloxane in the rubber composition is preferably 3 to 8 parts by mass per 100 parts by mass of rubber (mixture). (Form 18) In the method according to Form 17, The rubber composition preferably contains the crosslinkable resin at a concentration of 2 to 12 parts by mass per 100 parts by mass of the rubber (mixture). (Mode 19) In the method according to any one of Modes 1 to 18, The total number of siloxane units in the polyorganosiloxane of the present invention is preferably 10-100. (Mode 20) In the method according to mode 19, The total number of siloxane units in the polyorganosiloxane of the present invention is preferably 15-70 or 20-50. (Mode 21) In the method according to any one of Modes 1 to 20, Preferably, the life of a bladder for tire construction made from said rubber composition, as determined by crack growth according to De Mattia, is extended by more than 1.2 times compared to a bladder for tire construction made with castor oil (at the same concentration) as plasticizer and with otherwise the same vulcanization mixture composition and process. (Mode 22) In the method according to any one of Modes 1 to 21, It is preferred that one or more of the following physical properties: Delta Torque, Modul, Compression Set are not adversely changed compared to a rubber composition containing a corresponding amount of castor oil as a plasticizer. (Mode 23) See the second aspect of the present invention above. (Form 24) The plasticizer according to Form 23, R 1 Preferably, contains up to 15 carbon atoms. (Form 25) The plasticizer according to Form 24, R 1 is a monovalent unsaturated acyloxy group having up to 15 carbon atoms (i.e. a group of the RCOO-type); The acyl group preferably has a substituted or unsubstituted double bond at a terminal thereof and is bonded to a silicon atom in the main chain of the polyorganosiloxane via a hydrocarbon chain. (Mode 26) The plasticizer according to Mode 25, The hydrocarbon chain preferably includes at least one oxygen atom in the hydrocarbon chain. (Mode 27) The plasticizer according to Mode 26, The hydrocarbon chain is preferably substituted with at least one hydroxyl group. (Mode 28) The plasticizer according to any one of Modes 23 to 27, The modified polyorganosiloxanes are those that contain two or more organic moieties R1 and / or additionally one or more longer alkyl groups R 2 having R 2 It is preferred that the alkyl group has a chain length of 5 to 50 carbon atoms.

[0031] The inventors have surprisingly found that the use of certain polyorganosiloxanes having functional groups ("modified polyorganosiloxanes") as plasticizers in rubber compositions usable in bladders for tire production solves the problems of the present invention. In particular, when the castor oil normally used in the basic rubber composition is partially or completely replaced by the polyorganosiloxanes according to the present invention, bladders for tire production can be produced that have a longer life span compared to known bladders.

[0032] The plasticizers according to the invention therefore act in the volume of the rubber composition which contains them. Materials which are present only on the surface of the rubber composition, for example layers (or coatings) which are temporarily or permanently bonded to said surface, are not suitable as plasticizers according to the invention.

[0033] Polyorganosiloxane

[0034] Polyorganosiloxane itself is a known substance. It has the formula (R2SiO) x where R is usually a hydrocarbon radical (usually methyl, rarely ethyl, propyl, phenyl, etc., see for example Roempp Chemie Lexikon 9th Edition 1992, Vol. 5, p. 4168).

[0035] The polyorganosiloxanes used according to the invention have three or more siloxane units and contain one or more organic moieties R 1 , in particular two or more organic moieties R 1 and preferably one or more hydrocarbon moieties R 2 The present invention is characterized by having the following.

[0036] The moiety R present in the polyorganosiloxane according to the invention 1 and R 2 may be the same or different.

[0037] organic part R 1

[0038] The polyorganosiloxanes used according to the invention contain one or more organic moieties R 1 where R 1 contains one or more carbon-carbon multiple bonds and has at least four carbon atoms.

[0039] R 1 The carbon-carbon multiple bond in is preferably a carbon-carbon double bond, for example in a carbon chain or in a ring of carbon atoms. In a preferred embodiment, the organic moiety R 1 is a monovalent group.

[0040] In all embodiments of the present invention, the R 1 However, polyorganosiloxanes having at least 5 carbon atoms, such as at least 6, especially at least 7 carbon atoms, are especially preferred.

[0041] The polyorganosiloxane according to the invention preferably has at least two carbon-carbon multiple bonds. This means that the group R 1 If has only one carbon-carbon multiple bond, then at least two groups R 1 This means that the group R 1 It is also possible for the polyorganosiloxanes to have at least two carbon-carbon multiple bonds, although this embodiment is less preferred since the preparation of the corresponding polyorganosiloxanes is more laborious.

[0042] R 1As examples of the monovalent radical R, cycloalkenyl, alkenyl, vinyl-containing radicals, allyl-containing radicals, norbornyl, (di)cyclopentenyl, or unsaturated acyloxy radicals such as radicals derived from methacrylate or acrylate come into consideration. 1 is derived from cyclohexene and (meth)acrylate, in particular a (meth)acrylate-derived group R which is bonded to the polyorganosiloxane backbone via a hydrocarbon chain which can be substituted by one or more heteroatoms, such as oxygen or sulfur, and / or can be interrupted by one or more heteroatoms, such as oxygen and sulfur. 1 It is.

[0043] According to a preferred embodiment, R 1 is a monovalent unsaturated acyloxy group (i.e. RCOO-type group) having up to 15 carbon atoms (the total number of carbon atoms includes possible substituents), which has a terminal (i.e. in the unit R) substituted or unsubstituted double bond and is bonded to the silicon atom of the polyorganosiloxane backbone via a hydrocarbon chain which preferably has at least one oxygen atom in the chain and is preferably substituted with at least one hydroxyl group. The substituent on the terminal double-bonded carbon atom is preferably a plurality of methyl groups, in particular a single methyl group (e.g. CH2=C(CH3)COO- in the case of a methacrylate-derived group).

[0044] R 1 A particularly preferred example of is the group: TIFF2025019323000002.tif4849

[0045] Above, the carbon atoms bonded to the silicon atom are each indicated with an arrow.

[0046] These functionalizations can be, for example, (A) allyl (meth)acrylate, (B) 4-vinylcyclohexene, or (C) Allyl glycidyl ether is reacted with (meth)acrylic acid to open the epoxide ring. This can be achieved by reaction of the SiH unit with a compound that has a double bond susceptible to hydrosilylation, such as

[0047] Particularly preferred is reaction (C), in which the above structure (c) is formed. Polyorganosiloxanes of this general type are known, for example, from EP 0 269 114 A2 and DE 30 44 237 A1.

[0048] base R 1 The number of carbon atoms between the silicon atom bearing the group and the carbon-carbon multiple bond is preferably 1 to 10, more preferably 2 to 7, such as for example 4. In the case of cyclic or ring-containing groups, the shortest path to the double bond is counted.

[0049] In a preferred embodiment, R 1 is present as part of the structural unit I in the polyorganosiloxane according to the invention: [R 1 x R a SiO [4-(x+a)] / 2 ] (I) where x is 1, 2 or 3, preferably 1, a is 0, 1 or 2, preferably 1 or 2, especially 2, and R is a linear or branched alkyl group, a cycloalkyl group or an aromatic group having up to 9 carbon atoms, especially up to 6 carbon atoms. R is preferably selected from methyl, ethyl, propyl, butyl, pentyl or phenyl, and R is especially preferably methyl.

[0050] Preferred structural units I with x=1 are bifunctional structural units I with a=1. D : [R 1 RSiO 2 / 2 ] (I D ) and a monofunctional structural unit I with x=1 and a=2. M : [R 1 R2SiO 1 / 2 ] (I M ) It is.

[0051] The preferred polyorganosiloxanes according to the invention are those which contain from 15 to 70, preferably from 20 to 40 or 50, in particular from 20 to 30, type I D which is a measure of the chain length of the polyorganosiloxane.

[0052] Hydrocarbon moiety R 2

[0053] The polyorganosiloxane according to the invention may optionally contain one or more longer alkyl groups R 2 where R 2 has a chain length of 5 to 50 carbon atoms.

[0054] R 2 According to one embodiment, is a branched or unbranched alkyl group having 5 to 30 carbon atoms, in particular n-C 30 Alkyl, preferably nC 10 ~C 26 Alkyl, more preferably, for example, nC 18 Alkyl-like nC 12 ~C 18 unbranched alkyl groups having 5 to 30 carbon atoms, such as alkyl.

[0055] Preferably, the alkyl group R 2 is included as part of the (structural) unit II in the polyorganosiloxane (according to the invention): [R 2 y R' b SiO [4-(y+b)] / 2 ] (II) wherein y is 1, 2 or 3, preferably 1, b is 0, 1 or 2, preferably 1 or 2, especially 1, and R' is a monovalent organic residue as defined for R in relation to structural unit (I) above, but selected independently of R. In this case, R' is preferably selected from methyl, ethyl, propyl, butyl, pentyl or phenyl, and R' is especially preferably methyl.

[0056] A preferred structural unit II where y=1 is a bifunctional structural unit II where b=1. D : [R 2 R'SiO 2 / 2 ] (II D ) and a monofunctional structural unit II, where y=1 and b=2. M : [R 2 R'2SiO 1 / 2 ] (II M ) It is.

[0057] Polyorganosiloxane structure

[0058] In addition to the structural units I and II already described and present as preferred, the polyorganosiloxanes according to the invention preferably contain difunctional structural units III D Also has: [R''2SiO 2 / 2 ] (III D ) wherein the radicals R" are the same or different (preferably identical) and are selected from linear alkyl groups, preferably alkyl groups, cycloalkyl groups or aromatic groups capable of bonding to the polyorganosiloxane via an oxygen atom, the radicals R" being preferably methyl, ethyl, propyl and phenyl, in particular methyl.

[0059] In one embodiment, the polyorganosiloxane according to the invention contains one (or two) monofunctional structural units III M Also exists: [R'''3SiO 1 / 2 ] (III M ) wherein the radicals R"' are the same or different and are selected from hydroxy and linear, branched, cycloalkyl or aromatic radicals, which can be bonded via an oxygen atom, the radicals R"' being preferably hydroxy, methyl, ethyl, propyl and phenyl, in particular hydroxy and methyl. In a particularly preferred embodiment, the radicals R"' are the same and are methyl radicals.

[0060] One preferred structure of the polyorganosiloxane according to the present invention is as follows: [I D ] m [I M ] n [II D ] o [II M ] p [III D ] q [III M ] (2-n-p) Where: (i) m and o are each independently (independently) in the range of 0 to 40, and n and p are each independently (independently) in the range of 0, 1, or 2; however, the sum (m+n) is at least 1, preferably the sum (o+p) is at least 1, - The sum (n+p) is at most 2, the sum (m+n+o+p) is preferably in the range up to 20, and (ii) q is in the range of 0 to 100.

[0061] where the bifunctional structural unit I D , IID and III D In the polyorganosiloxanes according to the invention, are typically and preferably not arranged as blocks, but are statistically distributed (arranged) along the polysiloxane chain. Furthermore, it will be clear to those skilled in the art that the parameters m, n, o, p and q are average values, since the polyorganosiloxanes according to the invention are not typically produced as single compounds during production.

[0062] In a preferred embodiment, n is 1 or 2, preferably 2, i.e., the functionalized R 1 represents (at least) monofunctional (terminal) structural units I in the polyorganosiloxane (according to the invention). M is also included in.

[0063] In a further preferred embodiment, n is 2 and m is zero (0), i.e., the functionalized R 1 represents a monofunctional (terminal) structural unit I in the polyorganosiloxane (according to the invention) M is included only in

[0064] In a further preferred embodiment, n is 1 or 2, preferably 2, and m is not zero (0), i.e., the functionalized R 1 In the polyorganosiloxane (according to the invention), as in the case of m=1 or 2, monofunctional (terminal) structural units I M Also, bifunctional (branched) structural units I D Also included.

[0065] In all embodiments of the present invention, the moiety R 1 is the part R 2 It is preferably bonded to a silicon atom different from that to which is bonded.

[0066] In a preferred embodiment, the total number of siloxane units (m+o+q+2) of the polyorganosiloxane according to the invention is from 10 to 100, preferably from 15 to 70, in particular from 20 to 50, such as from 20 to 30 or 40.

[0067] In a further preferred embodiment, the total number of functionalized siloxane units (m+n+o+p) of the polyorganosiloxane according to the invention is 2 to 15, preferably 2 to 6 or 10.

[0068] Difunctional siloxane unit I D and II D Functionalization in R 1 and R 2 The preferred ratio (i.e. m / o) is 10 / 90 to 99 / 1, more preferably 30 / 70 to 98 / 2, especially 50 / 50 to 97 / 3, such as 70 / 30 to 96 / 4 or 75 / 25 to 95 / 5.

[0069] Unsubstituted difunctional siloxane units in the polyorganosiloxanes according to the invention III D The number is preferably 5 to 60, more preferably 10 to 50, and particularly 15 to 40, such as 20 to 30.

[0070] The polyorganosiloxanes according to the invention exist as liquid compounds having a high viscosity at room temperature (25° C.). In particular, the length of the siloxane chain (i.e. the sum of the SiO units, sum (m+o+q+2), is about 30 or more) and, optionally, the hydrocarbon moiety R 2 length (approximately 20 or more carbon atoms) and the hydrocarbon portion R 2 Depending on the possible number of , the polyorganosiloxanes according to the invention may be solid at room temperature.

[0071] a) one or more rubbers, and b) one or more polyorganosiloxanes according to the invention It is also possible to use the polyorganosiloxanes according to the invention as masterbatches which contain

[0072] The masterbatch contains, per 100 parts by weight of rubber (phr, parts per hundred parts rubber), 0.5 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, and especially 0.5 to 10 parts by weight of the polyorganosiloxane according to the invention. Typically, as the rubber in the masterbatch, rubbers that can be crosslinked by a crosslinkable resin, such as, for example, butyl rubber and chloroprene rubber, are used.

[0073] The use of a masterbatch facilitates the incorporation of the polyorganosiloxane according to the invention into the rubber.

[0074] Furthermore, a) one or more solid support materials (preferably selected from inorganic fillers (such as, for example, silicic acid) or waxy materials (such as, for example, polyethylene wax), and b) one or more polyorganosiloxanes according to the invention It is also possible to use the polyorganosiloxanes according to the invention in the form of mixtures which contain

[0075] The weight ratio of a) carrier material to b) polyorganosiloxane according to the invention [a to b)] in the mixture is preferably 10 / 90 to 90 / 10, more preferably 20 / 80 to 80 / 20, particularly preferably about 60 / 40.Preferred materials for the mixture are silicic acid or other inorganic fillers such as chalk or waxy materials such as polyethylene wax.

[0076] The use of mixtures facilitates the handling of the polyorganosiloxanes according to the invention, especially when they are liquid at room temperature.

[0077] Method for producing polyorganosiloxane according to the present invention

[0078] A preferred method for producing the polyorganosiloxanes according to the present invention comprises: a) a polyorganosiloxane having two or more SiH groups and at least one group R 1 to react a compound having at least one group R 1 and optionally obtaining a polyorganosiloxane having one or more residual SiH groups; and b) optionally reacting the polyorganosiloxane having at least one residual SiH group obtained in step a) with an α-olefin to obtain the polyorganosiloxane according to the invention. Includes.

[0079] One particularly preferred method for preparing the polyorganosiloxanes according to the invention is: a) a polyorganosiloxane having at least two SiH groups and at least one hydrosilylatable group and further functional groups R different from said groups which are inert under standard hydrosilylation conditions, such as epoxides, especially glycidyl ethers, 3 to react a compound having at least one group R 3 Obtaining a polyorganosiloxane having the formula: b) reacting the polyorganosiloxane obtained in step a) with at least one group R 1 and optionally the group R 3 Suitable for forming bonds with R 1 Further functional groups R different from 4 to react a compound having at least one group R 1 and optionally one or more residual unreacted R 3 Obtaining a polyorganosiloxane having a group, and c) optionally, reacting the polyorganosiloxane obtained in step b) with at least one group R 2 and optionally the group R 3 Suitable for forming bonds with R 2 Further functional groups R different from 4 to obtain the polyorganosiloxane according to the present invention. Includes.

[0080] An alternative method for producing polyorganosiloxanes according to the invention comprises the steps of: a) providing a functional group R to a silane having one or more hydrosilylatable groups 1 To have b) Optionally, a functional group R is added to the silane having one or more hydrosilylatable groups. 2 and c) reacting the compound obtained in step a) and, optionally, the compound obtained in step b) together with a compound providing a siloxane backbone, such as octamethylcyclotetrasiloxane, in water under basic conditions. Includes.

[0081] Use and vulcanization

[0082] According to the present invention, the polyorganosiloxane is used as a plasticizer (or softener) in the rubber composition. In other words, the polyorganosiloxane according to the present invention acts (functions) in the volume (inside) of the rubber composition into which it is introduced, as opposed to a pure modification of the surface of the rubber composition (when it exists as a molded article with a defined surface). According to one embodiment of the present invention, the rubber composition is not modified on its surface with a coating (film).

[0083] Preferably, the rubber composition contains, per 100 parts by weight of rubber (phr, parts per hundred parts of rubber), 0.5 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, very preferably 1 to 15 parts by weight, and especially 2 to 8 parts by weight of the polyorganosiloxane according to the invention. Preferably, the rubber composition contains 1 to 10 phr of the polyorganosiloxane according to the invention. Preferably, the rubber composition contains 2 to 7 phr of the polyorganosiloxane according to the invention. Preferably, the rubber composition contains 2.5 to 6.5 phr of the polyorganosiloxane according to the invention. Preferably, the rubber composition contains 6 phr of the polyorganosiloxane according to the invention.

[0084] In a preferred embodiment, the rubber is a rubber that can be crosslinked by a crosslinking resin. In particular, such rubbers that can be crosslinked by a crosslinking resin are not vulcanizable by a peroxide crosslinking agent, because they decompose under the appropriate reaction conditions. In accordance with the present invention, in particular, rubbers that are suitable for the manufacture of bladders that can be used in the manufacture of tires are used.

[0085] Preferred rubbers which can be used within the framework of the use according to the invention are, for example, butyl rubber, brominated copolymers of isobutylene and p-methylstyrene, and mixtures thereof.

[0086] Suitable crosslinkable resins for use according to the invention are, in particular, those which are used for the vulcanization of rubber compositions in the context of the manufacture of bladders for tire production. Preferably, crosslinkable resins capable of forming three-dimensional network structures are used. Phenol-formaldehyde resins, in particular, are suitable in this case. The crosslinking ability of these compound groups is based on the reactivity of the phenol methylol groups in the phenol-formaldehyde resins, which under the action of heat and removal of water form exomethylene-containing α,β-unsaturated carbonyl compounds which then react with isoprene-based rubber units to form chroman ring systems. The phenol-formaldehyde resins used have at least two phenol methylol groups for the purpose of crosslinking. In accordance with the invention, in particular, alkylphenol-formaldehyde resins can be used for crosslinking, where the alkyl is preferably C4-C, in particular octyl. 10The crosslinkable resin can optionally be halogenated, e.g., brominated, such as Brominated Octylphenyl Formaldehyde Resin SP-1055 available from Akrochem. When a non-halogenated crosslinkable resin is used, such as Brominated Octylphenyl Formaldehyde Resin SP-1045 available from Akrochem, a suitable halogen-containing component, such as chloroprene rubber, is added. Acidic materials (e.g., Lewis acids such as SnCl2 or FeCl3) can also be used.

[0087] Preferably, the rubber composition contains, per 100 parts by weight of rubber (phr, parts per hundred parts of rubber), 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight, especially preferably 2 to 15 parts by weight, and especially 2 to 12 parts by weight of crosslinkable resin.

[0088] The rubber composition preferably further contains, in the usual amounts, compatibilizers (additives) such as fillers (e.g. carbon black, silicic acid (silica), zinc oxide, calcium carbonate, barium sulfate, magnesium oxide, aluminum oxide, iron oxide, silicates), substances necessary for crosslinking (zinc oxide, accelerators, magnesium oxide, sulfur), catalysts / activators for resin crosslinking (e.g. chloroprene rubber, zinc oxide, stearic acid or salts derived therefrom), anti-aging agents, homogenizers.

[0089] The present invention further relates to a method for producing a bladder for tire production. In this method, a rubber composition comprising one or more modified polyorganosiloxanes according to the present invention, one or more crosslinking resins for crosslinking and optionally further conventional additives is vulcanized by the crosslinking resin. In this case, the components as disclosed in detail in the examples below are mixed sufficiently uniformly by suitable equipment and conditions. The mixing process and the equipment suitable for this are known to those skilled in the art.

[0090] The present invention further relates to a bladder for manufacturing tires, comprising a rubber composition vulcanizable with a crosslinkable resin, the rubber composition comprising the modified polyorganosiloxane according to the present invention and being vulcanized with a crosslinkable resin.

[0091] The inventors have surprisingly found that the use of the polyorganosiloxanes according to the invention as a plasticizer in a rubber composition significantly increases the lifespan of tire building bladders made from this rubber composition, as compared to tire building bladders made using castor oil (at the same concentration) as a plasticizer, with otherwise identical vulcanization mixture composition and processing.

[0092] In the context of the present invention, the life of a bladder is determined using test specimens in a De Mattia flex test after steam aging (48 hours at 190° C.), where the crack growth of test specimens of different compounds is compared with one another. The smaller the value for crack growth for a given number of stress (load) cycles, the longer the life of the bladder.

[0093] If a possible decrease in crosslink density is observed depending on the exact composition of the rubber composition, this decrease can be easily compensated for by increasing the concentration of the crosslinkable resin in the rubber composition, in which case the improved durability (stability) of the rubber composition according to the invention is not significantly impaired in the relevant use in the bladder.

[0094] Further aspects of the present invention are disclosed in the following items A to P.

[0095] A. Use of one or more modified polyorganosiloxanes as plasticizers in rubber compositions. The polyorganosiloxanes are those that contain three or more siloxane units and one or more organic moieties R having one or more carbon-carbon multiple bonds and at least four carbon atoms. 1 Includes.

[0096] B. In using item A, R1 contains up to 15 carbon atoms, R 1 is characterized in particular by being a monovalent unsaturated acyloxy group having up to 15 carbon atoms (i.e. a group of the RCOO-type), the acyl group having a substituted or unsubstituted double bond at the end and being linked to a silicon atom of the polyorganosiloxane backbone via a hydrocarbon chain which preferably contains at least one oxygen atom in the hydrocarbon chain and is preferably substituted with at least one hydroxyl group.

[0097] C. In the use of item A or B, the modified polyorganosiloxane comprises two or more organic moieties R 1 and / or additionally one or more longer alkyl groups R 2 Having R 2 is characterized by having a chain length of 5 to 50 carbon atoms.

[0098] D. The use of item A or B is characterized in that the rubber is vulcanized with one or more crosslinking resins (resinous crosslinkers), the rubber contains, inter alia, butyl rubber, brominated copolymer of isobutylene and p-methylstyrene or a mixture thereof, and chloroprene rubber can be used as a crosslinking coagent.

[0099] E. In the use of any of items A to D, the rubber composition containing polyorganosiloxane is characterized in that it contains one or more additional plasticizers that are not polyorganosiloxanes in an amount of less than 5 parts by weight per 100 parts by weight of rubber (mixture).

[0100] F. In the use of item E, the further plasticizer different from the polyorganosiloxane is characterized in that it comprises castor oil and / or a hydrocarbon resin, preferably it comprises castor oil, in particular it is castor oil and / or a hydrocarbon resin, preferably it is castor oil.

[0101] G. In the use of any one of items A to C, the rubber composition is characterized in that it does not contain any further plasticizer other than the modified polyorganosiloxane.

[0102] H. In the use of any of items A to G, the rubber composition is characterized in that it contains further additives and components suitable for the manufacture of bladders for tire manufacture.

[0103] I. In the use of any one of items A to H, the rubber composition is characterized in that after vulcanization, it is suitable for use as a bladder in manufacturing a tire.

[0104] J. In the use of item G or H, the rubber composition is characterized in that it comprises as further components fillers, catalysts for the resin crosslinking and optionally further compatibilizers, especially homogenizers.

[0105] K. In the use of any of items D to J, the crosslinkable resin is an optionally halogenated formaldehyde-alkylphenol resin, the alkyl group being preferably C1 to C 10 It is characterized in that it is alkyl.

[0106] L. In the use of any of items A to K, the amount of polyorganosiloxane in the rubber composition is 3 to 8 parts by mass per 100 parts by mass of rubber (mixture), and in particular, the rubber composition is characterized in that it contains a crosslinkable resin at a concentration of 2 to 12 parts by mass per 100 parts by mass of rubber (mixture).

[0107] M. The use of any of items A to L is characterized in that the life of a bladder for the manufacture of tires made from said rubber composition, as determined by crack growth according to De Mattia, is extended by more than 1.2 times compared to a bladder for the manufacture of tires made with castor oil (in the same concentration) as plasticizer and with otherwise the same composition and process of the vulcanization mixture.

[0108] N. In the use of any of items A to M, one or more of the following physical properties: Delta Torque, Modulus, and Compression Set are not adversely changed compared to a rubber composition containing an appropriate amount of castor oil as a plasticizer.

[0109] O. A method for manufacturing a bladder for tire manufacturing, in which a rubber composition containing one or more modified polyorganosiloxanes, one or more crosslinking resins for crosslinking, and optionally further conventional additives, is vulcanized with the crosslinking resin. The modified polyorganosiloxane and the rubber composition are as defined in any of the above items A to N.

[0110] P. A bladder for manufacturing a tire, comprising a rubber composition vulcanizable with a crosslinkable resin. The rubber composition comprises a modified polyorganosiloxane and is vulcanized with the crosslinkable resin. The modified polyorganosiloxane and the rubber composition are as defined in any one of items A to N above.

[0111] The advantages of the present invention will become apparent, inter alia, from the following examples. Unless otherwise specified, all amounts stated relate to weight. EXAMPLES

[0112] Preparation of polyorganosiloxanes according to the present invention

[0113] The synthesis of polyorganosiloxanes according to the present invention will now be described with reference to a selected example ("POS").

[0114] In the first reaction step, 7.63 g (0.057 mol) of tetramethyldisiloxane, 14.8 g (0.006 mol) of polymethylhydrogensiloxane, and 76.3 g (0.26 mol) of octamethylcyclotetrasiloxane were reacted in a three-neck flask in the presence of a calcium bentonite catalyst (3%) to produce hydrogendimethylpolysiloxane (MH 2D H 4D 18 ) is obtained [i.e., for a total of 24 (average) silicon atoms of siloxane units in the compound, both end groups (M H ) and four side groups (D H ) are each replaced with a hydrogen atom and available for subsequent functionalization.

[0115] In the second reaction step, 64.63 g (0.038 moles) of hydrogendimethylpolysiloxane is provided and heated to 80° C. Then, a catalyst (10 ppm Speier catalyst) is added, and 8.38 g (0.033 moles) of α-olefin (chain length C 14 ~C 22 ) is added slowly (gently). The reaction is carried out at 90°C.

[0116] In the third reaction step, 26.89 g (0.236 mol) of allyl glycidyl ether is added slowly at 80° C. The reaction rate is monitored by infrared spectroscopy HSi measurement. When HSi is no longer detectable, the reaction is complete and the excess components are distilled.

[0117] In the fourth reaction step, 83.91 g (0.034 mol) of the product produced in the third reaction step is heated at 80° C. with a catalyst (0.5% triethylamine or 1,4-diazabicyclo[2.2.2]octane) and an inhibitor (0.2% butylhydroxytoluene) and 15.09 g (0.175 mol) of methacrylic acid is slowly added dropwise. The reaction is then carried out at 95° C. and monitored for acid value.

[0118] POS is a short polyorganosiloxane that is di-terminally and poly-laterally functionalized.

[0119] chemicals

[0120] The following chemicals were used (Table 1).

[0121] Table 1 Chemical substances TIFF2025019323000003.tif130139

[0122] Furthermore, the following polyorganosiloxanes can be used according to the invention: Modified polydimethylsiloxane POS prepared as described above.

[0123] Test Method

[0124] The following test methods were used:

[0125] Mooney Viscosity: ISO 289-1 Determination of Unvulcanized Rubber Using a Shear Disc Viscometer - Part 1: Determination of Mooney Viscosity.

[0126] Shore A hardness: DIN ISO 7619-1:2012-02 Elastomers or thermoplastic elastomers - Determination of indentation hardness - Part 1: Durometer method (Shore hardness).

[0127] Tensile strength / stress values / elongation at break: DIN 53504 Testing of rubber and elastomers - Tensile strength, tensile strength, elongation at break and stress values ​​in tensile tests.

[0128] Tear resistance (strength): DIN ISO 34-1 DIN Elastomers or thermoplastic elastomers - Determination of tear resistance - Part 1: Trouser, angle and crescent specimens.

[0129] Crack growth: DIN ISO 132 Elastomers or thermoplastic elastomers - Determination of crack initiation and crack growth (DeMacha).

[0130] Crosslinking: DIN 53529 Part 2 - Testing of rubber and elastomers; Determination of the vulcanization course (characteristics) and kinetic evaluation of the crosslinking isotherm.

[0131] Rubber composition

[0132] The following rubber compositions 1 to 4 containing the following components were produced. All amounts are given in parts by mass (Table 2).

[0133] Table 2 - Amounts of components of rubber composition TIFF2025019323000004.tif57144

[0134] Rubber compositions 1 to 4 were produced as described below.

[0135] Rubber composition 1

[0136] A mixture of 50 parts by weight of carbon black (Luvomaxx BC N-330), 5 parts by weight of zinc oxide (Harzsiegel GR), 5 parts by weight of Struktol 40 MS Flakes, 6 parts by weight of castor oil, and 100 parts by weight of butyl rubber (Butyl RB 301) and 5 parts by weight of chloroprene rubber (Neoprene WRT) was mixed in a laboratory internal mixer by upside-down mixing method at a starting temperature of 80° C. and 70 revolutions per minute.

[0137] After 30 seconds the ram (Stempel) was lifted and brushed off and after 180 seconds the mixture was drained.

[0138] After 24 hours, 8 parts by weight of an octylphenol crosslinking resin (SP 1045) was introduced into the composition obtained by means of a (roller) mixer (mill) (Walzwerk) at 100° C. Mixing was continued for a total of 10 minutes.

[0139] Rubber composition 2

[0140] A mixture of 50 parts by weight of carbon black (Luvomaxx BC N-330), 5 parts by weight of zinc oxide (Harzsiegel GR), 5 parts by weight of Struktol 40 MS Flakes, 3 parts by weight of castor oil, and 3 parts by weight of POS, as well as 100 parts by weight of butyl rubber (Butyl RB 301) and 5 parts by weight of chloroprene rubber (Neoprene WRT) were mixed in a laboratory internal mixer by upside-down mixing method at a starting temperature of 80° C. and 70 revolutions per minute.

[0141] After 30 seconds the ram was lifted and brushed off and after 180 seconds the mixture was drained.

[0142] After 24 hours, 8 parts by weight of an octylphenol crosslinking resin (SP 1045) was introduced into the composition obtained by means of a (roller) mixer (mill) at 100° C. The total was mixed for 10 minutes.

[0143] Rubber composition 3

[0144] A mixture of 50 parts by weight of carbon black (Luvomaxx BC N-330), 5 parts by weight of zinc oxide (Harzsiegel GR), 5 parts by weight of Struktol 40 MS Flakes, 6 parts by weight of POS, and 100 parts by weight of butyl rubber (Butyl RB 301) and 5 parts by weight of chloroprene rubber (Neoprene WRT) was mixed in a laboratory internal mixer by upside-down mixing method at a starting temperature of 80° C. and 70 revolutions per minute.

[0145] After 30 seconds the ram was lifted and brushed off and after 180 seconds the mixture was drained.

[0146] After 24 hours, 8 parts by weight of an octylphenol crosslinking resin (SP 1045) was introduced into the composition obtained by means of a (roller) mixer (mill) at 100° C. The total was mixed for 10 minutes.

[0147] Rubber composition 4

[0148] A mixture of 50 parts by weight of carbon black (Luvomaxx BC N-330), 5 parts by weight of zinc oxide (Harzsiegel GR), 5 parts by weight of Struktol 40 MS Flakes, 6 parts by weight of POS, and 100 parts by weight of butyl rubber (Butyl RB 301) and 5 parts by weight of chloroprene rubber (Neoprene WRT) was mixed in a laboratory internal mixer by upside-down mixing method at a starting temperature of 80° C. and 70 revolutions per minute.

[0149] After 30 seconds the ram was lifted and brushed off and after 180 seconds the mixture was drained.

[0150] After 24 hours, 10 parts by weight of an octylphenol crosslinking resin (SP 1045) was introduced into the composition obtained by means of a (roller) mixer (mill) at 100° C. The whole was mixed for 10 minutes.

[0151] Crosslinking of Rubber Compositions 1 to 4

[0152] Using an RPA2000 device, the torque of rubber compositions 1 to 4 was measured by isothermal measurement at 210° C. as an evaluation criterion (scale) of crosslinking (Table 3).

[0153] Table 3 - Crosslinking at 210℃ RPA2000 TIFF2025019323000005.tif41125

[0154] Vulcanization of rubber compositions 1 to 4

[0155] 2 mm test plates and 6 mm test pieces were prepared from rubber compositions 1 to 4, respectively. For vulcanization, the 2 mm test plates were vulcanized at 210°C for 13 minutes, and the 6 mm test pieces were vulcanized under the same conditions for 14 minutes. The following physical properties of the vulcanized rubber compositions 1 to 4 were measured (Table 4).

[0156] Table 4 - Properties of vulcanized rubber compositions 1 to 4 TIFF2025019323000006.tif93145

[0157] Vulcanized rubber compositions 1-4 were further tested in a DeMatia flex endurance test (Table 5 and FIG. 1).

[0158] Table 5 - Dematcha flex test of vulcanized rubber compositions 1 to 4 TIFF2025019323000007.tif73135

[0159] Steam aging of vulcanized rubber compositions 1 to 4

[0160] The vulcanized rubber compositions 1 to 4 were subjected to steam aging at 190°C for 48 hours. The following physical properties of the vulcanized rubber compositions 1 to 4 were measured according to the steam aging. In addition, the changes in the related physical properties caused by the steam aging are also shown below (Table 6).

[0161] Table 6 - Physical properties of vulcanized rubber compositions 1 to 4 after steam aging (190°C, 48 hours) and corresponding changes in physical properties due to steam aging TIFF2025019323000008.tif93145

[0162] The vulcanized rubber compositions 1 to 4 were further subjected to steam aging (190° C., 48 hours) and then to a DeMatcha flex resistance test (Table 7 and FIG. 2).

[0163] Table 7 - Dematcha flex test of vulcanized rubber compositions 1 to 4 after steam aging (190°C, 48 hours) [%] TIFF2025019323000009.tif73135

[0164] Evaluation of measurement data

[0165] Rubber composition 1 represents the prior art and is used as a control. By using 3 phr POS in combination with 3 phr castor oil in rubber composition 2 or 6 phr POS in rubber composition 3, the Vulkameter curve decreases depending on the amount of POS used. By using 6 phr POS in combination with the use of 2 phr more crosslinking resin SP1045, the Vulkameter curve for rubber composition 4 is at a similar level to that for rubber composition 1.

[0166] A similar trend is observed when considering the results after steam aging in an autoclave (48 hours at 190°C). It should be noted here that the test pieces of vulcanized rubber composition 3 swelled significantly, so that physical properties could not be measured. The reason for this may be that vulcanized rubber composition 3 was too little crosslinked.

[0167] However, vulcanized rubber composition 4 has a much more balanced property profile. It is noteworthy that vulcanized rubber composition 4 now deviates significantly from the control (rubber composition 1) in the DeMatia crack growth test and thus has significantly improved crack resistance.

[0168] Furthermore, rubber composition 1 exhibits poorer flexibility of the vulcanizate, as evidenced by a significant increase in Shore hardness, tensile strength and modulus.

[0169] The use of only 3 phr of POS in combination with 3 phr of castor oil (rubber composition 2) likewise gives good results in the flex resistance test (De Mattha test).

[0170] Possible embodiments of the present invention are now described. [Appendix 1] Use of one or more modified polyorganosiloxanes as plasticizers in a rubber composition. The rubber has been vulcanized with one or more crosslinking resins; Polyorganosiloxanes are made up of three or more siloxane units and one or more organic moieties R having one or more carbon-carbon multiple bonds and at least four carbon atoms. 1 Includes: [Note 2] In the above usage, R 1 contains up to 15 carbon atoms; R 1 is in particular a monovalent unsaturated acyloxy radical having up to 15 carbon atoms (i.e. a radical of the RCOO-type); The acyl group has a substituted or unsubstituted double bond at the end and is bonded to a silicon atom of the main chain of the polyorganosiloxane via a hydrocarbon chain which preferably contains at least one oxygen atom in the hydrocarbon chain and is preferably substituted with at least one hydroxyl group. [Appendix 3] In the above use, particularly as described in appendix 1 or 2, The modified polyorganosiloxanes are those that contain two or more organic moieties R 1and / or additionally one or more longer alkyl groups R 2 having; R 2 has a chain length of 5 to 50 carbon atoms. [Appendix 4] In the above use, particularly as described in appendix 1 or 2, Rubbers including butyl rubber, brominated copolymers of isobutylene and p-methylstyrene or mixtures thereof, and chloroprene rubber can be used as crosslinking coagents. [Appendix 5] In the above use, particularly in any of Appendices 1 to 4, The rubber composition containing polyorganosiloxanes contains one or more further plasticizers which are not polyorganosiloxanes in an amount of less than 5 parts by weight per 100 parts by weight of rubber (mixture). [Appendix 6] In the above uses, particularly those described in appendix 5, The further plasticizer different from the polyorganosiloxane comprises castor oil and / or a hydrocarbon resin, preferably comprises castor oil, in particular is castor oil and / or a hydrocarbon resin, preferably is castor oil. [Appendix 7] In the above use, particularly in any of Appendices 1 to 3, The rubber composition does not contain any further plasticizers besides the modified polyorganosiloxane. [Appendix 8] In the above use, particularly in any of Appendices 1 to 7, The rubber composition contains further additives and ingredients suitable for the manufacture of bladders for tire construction. [Appendix 9] In the above use, particularly in any of Appendices 1 to 8, The rubber composition, after vulcanization, is suitable for use as a bladder in making tires. [Appendix 10] In the above use, particularly as described in appendix 7 or 8, The rubber composition comprises as further components fillers, catalysts for the resin crosslinking and, optionally, further compatibilizers, especially homogenizers. [Appendix 11] In the above use, particularly in any of Appendices 1 to 9, The crosslinkable resin is an optionally halogenated formaldehyde-alkylphenol resin; Alkyl groups are particularly C1-C 10 It is an alkyl. [Appendix 12] In the above use, particularly in any of Appendices 1 to 11, The amount of polyorganosiloxane in the rubber composition is 3 to 8 parts by mass per 100 parts by mass of rubber (mixture); In particular, the rubber composition contains a crosslinkable resin in a concentration of 2 to 12 parts by weight per 100 parts by weight of rubber (mixture). [Appendix 13] In the above use, particularly in any of Appendices 1 to 12, The total number of siloxane units in the polyorganosiloxane of the present invention is 10-100, preferably 15-70, and particularly preferably 20-50. [Appendix 14] In the above use, particularly in any of Appendices 1 to 13, The life of a bladder for tire construction made from said rubber composition, as determined by crack growth according to De Mattia, is extended by more than 1.2 times compared to a bladder for tire construction made with castor oil (at the same concentration) as plasticizer, with otherwise the same vulcanization mixture composition and process. [Appendix 15] In the above use, particularly in any of Appendices 1 to 14, One or more of the following physical properties: Delta Torque, Modul, Compression Set are not adversely altered compared to rubber compositions containing a corresponding amount of castor oil as a plasticizer. [Appendix 16] A method for manufacturing a bladder for manufacturing a tire. A rubber composition comprising one or more modified polyorganosiloxanes, one or more crosslinking resins for crosslinking, and optionally further conventional additives, is vulcanized by the crosslinking resin; The modified polyorganosiloxane and the rubber composition are those of the present invention, particularly those defined in any one of Appendices 1 to 14. [Appendix 17] A bladder for manufacturing a tire, comprising a rubber composition vulcanizable by a crosslinkable resin. The rubber composition contains a modified polyorganosiloxane and is vulcanized with the crosslinkable resin; The modified polyorganosiloxane and the rubber composition are as defined in any one of Appendices 1 to 14. [Appendix 1'] A method for plasticizing a rubber composition. The method includes adding one or more modified polyorganosiloxanes to the rubber composition as a plasticizer for the rubber composition; The rubber has been vulcanized with one or more crosslinking resins; Polyorganosiloxanes are made up of three or more siloxane units and one or more organic moieties R having one or more carbon-carbon multiple bonds and at least four carbon atoms. 1 Includes: [Appendix 2'] In the method according to appendix 1', R 1 contains up to 15 carbon atoms. [Appendix 3'] In the method according to appendix 2', R 1 is a monovalent unsaturated acyloxy group having up to 15 carbon atoms (i.e. a group of the RCOO-type); The acyl group has a substituted or unsubstituted double bond at the end and is bonded to a silicon atom of the main chain of the polyorganosiloxane via a hydrocarbon chain. [Appendix 4'] In the method according to appendix 3', The hydrocarbon chain includes at least one oxygen atom in the hydrocarbon chain. [Appendix 5'] In the method according to appendix 4', The hydrocarbon chain is substituted with at least one hydroxyl group. [Appendix 6'] In the method according to any one of appendices 1' to 5', The modified polyorganosiloxanes are those that contain two or more organic moieties R 1 and / or additionally one or more longer alkyl groups R 2 having; R 2has a chain length of 5 to 50 carbon atoms. [Appendix 7'] In the method according to any one of appendices 1' to 6', The rubber comprises butyl rubber, a brominated copolymer of isobutylene and p-methylstyrene, or a mixture thereof, and the rubber composition comprises chloroprene rubber as a crosslinking coagent. [Appendix 8'] In the method according to any one of appendices 1' to 7', One or more further plasticizers which are not polyorganosiloxanes are added to the rubber composition in an amount greater than 0 and less than 5 parts by weight per 100 parts by weight of rubber (mixture). [Appendix 9'] In the method according to appendix 8', As said further plasticizers castor oil and / or hydrocarbon resins are added. [Appendix 10'] In the method according to any one of appendices 1' to 7', Only the modified polyorganosiloxane is added as a plasticizer to the rubber composition. [Appendix 11'] In the method according to any one of appendices 1' to 10', The rubber composition contains further additives and ingredients suitable for the manufacture of bladders for tire construction. [Appendix 12'] In the method according to any one of appendices 1' to 11', The rubber composition is vulcanized for use as a bladder in making tires. [Appendix 13'] In the method according to appendix 11' or 12', The rubber composition contains, as further components, a filler and a catalyst for resin crosslinking. [Appendix 14'] In the method according to appendix 13', The rubber composition comprises a homogenizer. [Appendix 15'] In the method according to any one of appendices 1' to 14', The crosslinkable resin is a halogenated formaldehyde-alkylphenol resin. [Appendix 16'] In the method according to appendix 15', Alkyl groups are C1-C 10 It is an alkyl. [Appendix 17'] In the method according to any one of appendices 1' to 16', The amount of polyorganosiloxane in the rubber composition is 3 to 8 parts by mass per 100 parts by mass of rubber (mixture). [Appendix 18'] In the method according to appendix 17', The rubber composition contains the crosslinkable resin at a concentration of 2 to 12 parts by mass per 100 parts by mass of rubber (mixture). [Appendix 19'] In the method according to any one of appendices 1' to 18', The total number of siloxane units in the polyorganosiloxane of the present invention is 10-100. [Appendix 20'] In the method according to appendix 19', The total number of siloxane units in the polyorganosiloxane of the present invention is 15-70 or 20-50. [Appendix 21'] In the method according to any one of appendices 1' to 20', The life of a bladder for tire construction made from said rubber composition, as determined by crack growth according to De Mattia, is extended by more than 1.2 times compared to a bladder for tire construction made with castor oil (at the same concentration) as plasticizer, with otherwise the same vulcanization mixture composition and process. [Appendix 22'] In the method according to any one of appendices 1' to 21', One or more of the following physical properties: Delta Torque, Modul, Compression Set are not adversely altered compared to rubber compositions containing a corresponding amount of castor oil as a plasticizer. [Appendix 23'] A plasticizer for plasticizing a rubber composition. The plasticizer comprises one or more modified polyorganosiloxanes; The rubber has been vulcanized with one or more crosslinking resins; Polyorganosiloxanes are made up of three or more siloxane units and one or more organic moieties R having one or more carbon-carbon multiple bonds and at least four carbon atoms. 1 Includes: [Appendix 24'] The plasticizer according to appendix 23', R 1 contains up to 15 carbon atoms. [Appendix 25'] The plasticizer according to appendix 24', R 1 is a monovalent unsaturated acyloxy group having up to 15 carbon atoms (i.e. a group of the RCOO-type); The acyl group has a substituted or unsubstituted double bond at the end and is bonded to a silicon atom of the main chain of the polyorganosiloxane via a hydrocarbon chain. [Appendix 26'] The plasticizer according to appendix 25', The hydrocarbon chain includes at least one oxygen atom in the hydrocarbon chain. [Appendix 27'] The plasticizer according to appendix 26', The hydrocarbon chain is substituted with at least one hydroxyl group. [Appendix 28'] The plasticizer according to any one of Appendices 23' to 27', The modified polyorganosiloxanes are those that contain two or more organic moieties R 1 and / or additionally one or more longer alkyl groups R 2 having; R 2 has a chain length of 5 to 50 carbon atoms.

Claims

1. 1. A method for plasticizing a rubber composition, comprising: the method includes adding one or more modified polyorganosiloxanes to the rubber composition as a plasticizer for the rubber composition; the rubber is vulcanized with one or more crosslinking resins; Polyorganosiloxanes are made up of three or more siloxane units and one or more organic moieties R having one or more carbon-carbon multiple bonds and at least four carbon atoms. １ Including A method comprising:

2. 10. The method of claim 1 , R １ Contains up to 15 carbon atoms A method comprising:

3. 3. The method of claim 2, R １ is a monovalent unsaturated acyloxy group having up to 15 carbon atoms (i.e. a group of the RCOO-type); The acyl group has a substituted or unsubstituted double bond at the terminal and is bonded to a silicon atom of the main chain of the polyorganosiloxane via a hydrocarbon chain. A method comprising:

4. 4. The method of claim 3, The hydrocarbon chain includes at least one oxygen atom in the hydrocarbon chain. A method comprising:

5. 5. The method of claim 4, The hydrocarbon chain is substituted with at least one hydroxyl group. A method comprising:

6. In the method according to any one of claims 1 to 5, The modified polyorganosiloxane comprises two or more organic moieties R １ and / or additionally one or more longer alkyl groups R ２ having R ２ has a chain length of 5 to 50 carbon atoms A method comprising:

7. The method according to any one of claims 1 to 6, The rubber comprises butyl rubber, a brominated copolymer of isobutylene and p-methylstyrene, or a mixture thereof, and the rubber composition comprises chloroprene rubber as a crosslinking aid. A method comprising:

8. The method according to any one of claims 1 to 7, Adding to the rubber composition one or more additional plasticizers that are not polyorganosiloxanes in an amount greater than 0 parts by weight and less than 5 parts by weight per 100 parts by weight of rubber (mixture). A method comprising:

9. 9. The method of claim 8, Adding castor oil and / or hydrocarbon resin as the further plasticizer. A method comprising:

10. The method according to any one of claims 1 to 7, The rubber composition contains only modified polyorganosiloxane as a plasticizer. A method comprising:

11. The method according to any one of claims 1 to 10, The rubber composition may contain further additives and components suitable for the manufacture of bladders for tire manufacture. A method comprising:

12. The method according to any one of claims 1 to 11, The rubber composition is vulcanized for use as a bladder in manufacturing tires. A method comprising:

13. 13. The method according to claim 11 or 12, The rubber composition may further include a filler and a catalyst for resin crosslinking. A method comprising:

14. 14. The method of claim 13, The rubber composition may contain a homogenizer. A method comprising:

15. The method according to any one of claims 1 to 14, The crosslinkable resin is a halogenated formaldehyde-alkylphenol resin. A method comprising:

16. 16. The method of claim 15, The alkyl group is C １ ~C １０ Being alkyl A method comprising:

17. The method according to any one of claims 1 to 16, The amount of polyorganosiloxane in the rubber composition is 3 to 8 parts by mass per 100 parts by mass of rubber (mixture). A method comprising:

18. 18. The method of claim 17, The rubber composition contains a crosslinkable resin at a concentration of 2 to 12 parts by mass per 100 parts by mass of rubber (mixture). A method comprising:

19. The method according to any one of claims 1 to 18, The total number of siloxane units in the polyorganosiloxane of the present invention is 10 to 100. A method comprising:

20. 20. The method of claim 19, The total number of siloxane units in the polyorganosiloxane of the present invention is 15 to 70 or 20 to 50. A method comprising:

21. The method according to any one of claims 1 to 20, The life of a bladder for the manufacture of tires made from said rubber composition, as determined by crack growth according to De Mattia, is extended by more than 1.2 times compared to a bladder for the manufacture of tires made with castor oil (at the same concentration) as a plasticizer, but with an otherwise identical composition and process of vulcanization mixture. A method comprising:

22. The method according to any one of claims 1 to 21, One or more of the following physical properties: delta torque, modulus, compression set are not adversely altered compared to a rubber composition containing a corresponding amount of castor oil as a plasticizer. A method comprising:

23. A plasticizer for plasticizing a rubber composition, comprising: the plasticizer comprises one or more modified polyorganosiloxanes; the rubber is vulcanized with one or more crosslinking resins; Polyorganosiloxanes are made up of three or more siloxane units and one or more organic moieties R having one or more carbon-carbon multiple bonds and at least four carbon atoms. １ Including A plasticizer characterized by:

24. 24. The plasticizer of claim 23, R １ Contains up to 15 carbon atoms A plasticizer characterized by:

25. 25. The plasticizer of claim 24, R １ is a monovalent unsaturated acyloxy group having up to 15 carbon atoms (i.e. a group of the RCOO-type); The acyl group has a substituted or unsubstituted double bond at the terminal and is bonded to a silicon atom of the main chain of the polyorganosiloxane via a hydrocarbon chain. A plasticizer characterized by:

26. 26. The plasticizer of claim 25, The hydrocarbon chain includes at least one oxygen atom in the hydrocarbon chain. A plasticizer characterized by:

27. 27. The plasticizer of claim 26, The hydrocarbon chain is substituted with at least one hydroxyl group. A plasticizer characterized by:

28. The plasticizer according to any one of claims 23 to 27, The modified polyorganosiloxane comprises two or more organic moieties R １ and / or additionally one or more longer alkyl groups R ２ having R ２ has a chain length of 5 to 50 carbon atoms A plasticizer characterized by:

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