Modified conjugated diene polymer, molded article, rubber composition, and tire

Abstract

To provide a modified conjugated diene polymer and the like, which are produced by a continuous polymerization process, ensuring excellent processability, superior tensile properties and other physical characteristics, and a favorable balance between steering stability and wear resistance.SOLUTION: This modified conjugated diene polymer has residues of two types of alkoxysilane-based modifiers, the difference in the number of alkoxy groups between the modifiers being four or more, and satisfies the following conditions (i) to (iii). Condition (i): A molecular weight distribution curve obtained by gel permeation chromatography (GPC, Gel Permeation Chromatography) has a unimodal shape and includes a shoulder on the higher molecular weight side from the peak top. Condition (ii): The molecular weight distribution (PDI; MWD) is 1.45 or more and less than 1.7. Condition (iii): The Si content is 100 ppm or more and less than 300 ppm on a weight basis.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a modified conjugated diene polymer, and more particularly to a modified conjugated diene polymer produced by continuous polymerization, which has excellent processability, a narrow molecular weight distribution, and excellent physical properties, and a rubber composition containing the same. [Background technology]

[0002] In recent years, growing interest in energy conservation and environmental issues has led to demands for improved fuel efficiency in automobiles. Therefore, rubber materials used in automobile tires, particularly in tire treads that come into contact with the road surface, are required to have low rolling resistance and excellent abrasion resistance, as well as wet skid resistance and practically sufficient fracture properties from the viewpoint of safety.

[0003] Furthermore, in response to the trend toward lower fuel consumption in automobiles, progress is being made in reducing the weight of automobiles by using resin for automobile components and thinning tires. Thinning tires requires a reduction in the thickness of the tread, which requires high wear resistance.

[0004] One method for reducing the rolling resistance of tires is to reduce the hysteresis loss of vulcanized rubber, and the evaluation indexes for such vulcanized rubber include rebound resilience, tan δ, Goodrich heat buildup, etc. at 50°C to 80°C. That is, rubber materials with high rebound resilience or low tan δ and Goodrich heat buildup at the above temperatures are preferred.

[0005] Known rubber materials with low hysteresis loss include natural rubber, polyisoprene rubber, and polybutadiene rubber. However, these materials suffer from poor wet grip performance. Therefore, conjugated diene polymers or copolymers, such as styrene-butadiene rubber (SBR) or butadiene rubber (BR), have recently been produced by emulsion polymerization or solution polymerization and used as tire rubber. The greatest advantage of solution polymerization over emulsion polymerization is its ability to freely adjust the vinyl and styrene content, which determine the rubber's physical properties, and its ability to control molecular weight and physical properties through coupling and modification. Therefore, solution-polymerized SBR is widely used as a tire rubber material because the final SBR or BR can be easily modified, and chain end bonding or modification can reduce chain end movement and increase the bonding strength with fillers such as silica or carbon black.

[0006] When such solution-polymerized SBR is used as a rubber material for tires, increasing the vinyl content in the SBR raises the rubber's glass transition temperature, thereby enabling adjustment of tire properties such as rolling resistance and braking force. Furthermore, adjusting the glass transition temperature appropriately can reduce fuel consumption. The solution-polymerized SBR is produced using an anionic polymerization initiator, and the chain ends of the resulting polymer are bonded or modified using various modifiers. For example, Patent Document 1 (U.S. Pat. No. 4,397,994) proposes a technology in which active anions at the chain ends of a polymer obtained by polymerizing styrene-butadiene in a nonpolar solvent using a monofunctional alkyllithium initiator are bonded using a bonding agent such as a tin compound.

[0007] Meanwhile, the polymerization of SBR or BR is carried out by batch or continuous polymerization. Batch polymerization has the advantage of improving physical properties because the molecular weight distribution of the produced polymer is narrow, but it has the problems of low productivity and poor processability. Continuous polymerization, on the other hand, has the advantage of excellent productivity and improved processability because the polymerization is carried out continuously, but it has the problem of poor physical properties because the molecular weight distribution is broad. Therefore, there is a need for research into simultaneously improving productivity, processability, and physical properties during the production of SBR or BR. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] U.S. Patent No. 4,397,994 [Patent Document 2] Patent No. 7,227,136 Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention has been made to solve the above-mentioned problems of the conventional art, and an object of the present invention is to provide a modified conjugated diene-based polymer that is produced by continuous polymerization and has excellent processability, excellent physical properties such as tensile properties, and an excellent balance between handling stability and abrasion resistance, and a rubber composition containing the same.

[0010] However, in the case of the conjugated diene polymer disclosed in Patent Document 2, although the processability and the tensile and viscoelastic properties could be improved, there is a problem in that sufficient improvements in handling stability and abrasion resistance may not be obtained.

[0011] For example, if the molecular weight of the modified conjugated diene polymer is increased in order to improve handling stability and abrasion resistance, the viscosity of the composition increases during kneading, resulting in poor processability. On the other hand, if the Si content in the modified conjugated diene polymer is increased in order to improve tensile properties and viscoelastic properties, fillers such as silica and carbon become more dispersed in the compound, reducing the hardness of the compound and resulting in poor handling stability and abrasion resistance. [Means for solving the problem]

[0012] As a result of extensive research and investigation to solve the above-mentioned problems, the present inventors have found that a modified conjugated diene-based polymer using two types of modifiers, which has a molecular weight distribution curve of a specific shape as measured by gel permeation chromatography (GPC) and has a predetermined molecular weight distribution and Si content, can solve the above-mentioned problems, and have thus completed the present invention. That is, the present invention is as follows.

[0013] [1] Contains residues of two types of alkoxysilane-based modifiers, the difference in the number of alkoxy groups in the modifying agents is 4 or more, A modified conjugated diene polymer that satisfies the following <condition (i)> to <condition (iii)>. <Condition (i)> The molecular weight distribution curve measured by gel permeation chromatography (GPC) shows a single peak, with a shoulder on the polymer side of the peak top. <Condition (ii)> The molecular weight distribution (PDI; MWD) is 1.45 or more and less than 1.7. <Condition (iii)> The Si content is 100 ppm or more and less than 300 ppm by weight. [2] The modified conjugated diene polymer according to [1], wherein the alkoxysilane-based modifier is a compound represented by a chemical formula selected from the group consisting of the following chemical formulas 1 to 9: [ka] (In the above Chemical Formula 1, R 1 is a single bond or an alkylene group having 1 to 10 carbon atoms, R 2 and R 3 are each independently an alkyl group having 1 to 10 carbon atoms, R 4 is hydrogen, an alkyl group having 1 to 10 carbon atoms, a divalent, trivalent, or tetravalent alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a heterocyclic group having 2 to 10 carbon atoms; R 21 is a single bond, an alkylene group having 1 to 10 carbon atoms, or -[R 42 O] j - and R 42 is an alkylene group having 1 to 10 carbon atoms, a and m are each independently an integer selected from 1 to 3, n is 0, 1, or 2, j is an integer selected from 1 to 30. [ka] (In the above Chemical Formula 2, R 5 , R 6 , and R 9 are each independently an alkylene group having 1 to 10 carbon atoms, R 7 , R 8 , R 10 , and R 11 are each independently an alkyl group having 1 to 10 carbon atoms, R 12 is hydrogen or an alkyl group having 1 to 10 carbon atoms, b and c are each independently 0, 1, 2, or 3, and b+c≧1; A is, [ka] or [ka] where the wavy line indicates the bond to the nitrogen adjacent to A, R 13 , R 14 , R 15 , and R 16 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms. [ka] (In the above Chemical Formula 3, A 1 and A 2 are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, which may or may not contain an oxygen atom, R 17 ~R 20 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, L 1 ~L 4 are each independently a divalent, trivalent, or tetravalent alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or L 1 and L 2 And, L 3 and L 4 are linked to each other to form a ring having 1 to 5 carbon atoms, and L 1 and L 2 And, L 3 and L 4 When are linked to each other to form a ring, the formed ring may contain 1 to 3 heteroatoms of one or more types selected from the group consisting of N, O, and S. [ka] (In the above Chemical Formula 4, R 22 and R 23 are each independently an alkylene group having 1 to 20 carbon atoms, or -R 28 [OR 29 ] f - and R 24 ~R 27are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 28 and R 29 are each independently an alkylene group having 1 to 20 carbon atoms, R 47 and R 48 are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms, d and e are each independently an integer selected from 0 to 3, and d+e is an integer of 1 or greater; f is an integer from 1 to 30. [ka] (In the above Chemical Formula 5, R 30 is a monovalent hydrocarbon group having 1 to 30 carbon atoms, R 31 ~R 33 are each independently an alkylene group having 1 to 10 carbon atoms, R 34 ~R 37 are each independently an alkyl group having 1 to 10 carbon atoms, g and h are each independently an integer selected from 0 to 3, and g+h is an integer of 1 or greater. [ka] (In the above Chemical Formula 6, A 3 and A 4 are each independently an alkylene group having 1 to 10 carbon atoms, R 38 ~R 41 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, i is an integer selected from 1 to 30. [ka] (In the above Chemical Formula 7, R 43 , R 45 , and R46 are each independently an alkyl group having 1 to 10 carbon atoms, R 44 is an alkylene group having 1 to 10 carbon atoms, k is an integer selected from 1 to 4, and l is an integer selected from 1 to 3. [ka] (In the above Chemical Formula 8, R b2 ~R b4 are each independently an alkylene group having 1 to 10 carbon atoms, R b5 ~R b8 are each independently an alkyl group having 1 to 10 carbon atoms, R b12 ~R b14 are each independently an alkylene group having 1 to 10 carbon atoms, R b15 ~R b18 are each independently an alkyl group having 1 to 10 carbon atoms, m1, m2, m3, and m4 are each independently an integer of 1 to 3. [ka] (In the above Chemical Formula 9, R1 to R8 each independently represent an alkyl group having 1 to 20 carbon atoms; L1 and L2 each independently represent an alkylene group having 1 to 20 carbon atoms; n is an integer from 2 to 4. [3] The modified conjugated diene polymer according to [2], wherein the compound represented by the chemical formula 4 is a compound represented by a chemical formula selected from the group consisting of the following chemical formulas 4a to 4c: [ka] [ka] [ka] (In the above Chemical Formula 4a, Chemical Formula 4b, and Chemical Formula 4c, R 22 ~R 27 , d and e are as defined above.) [4] Number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 1,000 or more, 200 x 10 4 and the weight average molecular weight (Mw) is 1,000 or more and 300 × 10 4 The modified conjugated diene-based polymer according to any one of [1] to [3] below: [5] The modified conjugated diene polymer according to any one of [1] to [4], having a Mooney viscosity measured at 100°C of 50 or more and less than 170, and a Mooney relaxation rate (MSR) measured at 100°C of 0.30 or more and 0.80 or less. [6] 100 parts by mass of the modified conjugated diene polymer according to any one of [1] to [5], less than 1 part by weight of a softener component; A molded body containing the above. [7] 100 parts by mass of rubber component, A filler is 5.0 parts by mass or more and 150 parts by mass or less, The rubber component contains 10 parts by mass or more of the modified conjugated diene polymer according to any one of [1] to [5] relative to 100 parts by mass of the total amount of the rubber component. Rubber composition. [8] A tire containing the rubber composition according to [7]. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a modified conjugated diene polymer that has an excellent balance between processability during kneading and breaking strength, viscoelasticity, handling stability, and abrasion resistance when vulcanized. DETAILED DESCRIPTION OF THE INVENTION

[0015] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail. It should be noted that the following embodiments are merely examples for explaining the present invention, and the present invention is not limited to the following embodiments. The present invention can be practiced by appropriately modifying it within the scope of its gist.

[0016] [Modified conjugated diene polymer] The modified conjugated diene polymer of the present embodiment satisfies the following <Condition (i)> to <Condition (iii)>: satisfy. <Condition (i)> The molecular weight distribution curve measured by gel permeation chromatography (GPC) shows a single peak, with a shoulder on the polymer side of the peak top. <Condition (ii)> The molecular weight distribution (PDI; MWD) is 1.45 or more and less than 1.7. <Condition (iii)> The Si content is 100 ppm or more and less than 300 ppm by weight.

[0017] The modified conjugated diene polymer of the present embodiment has an excellent balance between processability during kneading and breaking strength, viscoelasticity, handling stability, and abrasion resistance when vulcanized.

[0018] The modified conjugated diene polymer of the present embodiment may be any of a homopolymer of a single conjugated diene compound, a polymer (i.e., a copolymer) of different types of conjugated diene compounds, and a copolymer of a conjugated diene compound and a vinyl aromatic compound.

[0019] Examples of conjugated diene compounds include, but are not limited to, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene, and 1,3-heptadiene. Among these, 1,3-butadiene and isoprene are preferred from the viewpoint of effectively and reliably achieving the effects of the present embodiment. These conjugated diene compounds may be used alone or in combination of two or more.

[0020] Examples of vinyl aromatic compounds include, but are not limited to, one or more selected from the group consisting of styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, 1-vinyl-5-hexylnaphthalene, 3-(2-pyrrolidinoethyl)styrene, 4-(2-pyrrolidinoethyl)styrene, and 3-(2-pyrrolidino-1-methylethyl)-α-methylstyrene. Among these, styrene is preferred from the viewpoint of effectively and reliably achieving the effects of this embodiment. These vinyl aromatic compounds may be used alone or in combination of two or more.

[0021] The modified conjugated diene polymer may be a random copolymer or a block copolymer. Examples of random copolymers include, but are not limited to, random copolymers composed of two or more conjugated diene compounds such as butadiene-isoprene random copolymers, butadiene-styrene random copolymers, isoprene-styrene random copolymers, and random copolymers composed of conjugated dienes and vinyl aromatic compounds such as butadiene-isoprene-styrene random copolymers. The composition distribution of each monomer in the copolymer chain is not particularly limited, and examples thereof include a completely random copolymer having a statistically random composition and a tapered (gradient) random copolymer having a tapered composition distribution. The bonding mode of the conjugated diene, i.e., the composition of 1,4-bonds, 1,2-bonds, etc., may be uniform or may have a distribution.

[0022] The modified conjugated diene polymer may be a copolymer further containing, in addition to the repeating units derived from the conjugated diene monomer, repeating units derived from a diene monomer having 1 to 10 carbon atoms. The repeating units derived from the diene monomer may be repeating units derived from a diene monomer different from the conjugated diene monomer. The diene monomer different from the conjugated diene monomer may be, for example, 1,2-butadiene. When the modified conjugated diene polymer is a copolymer further containing a diene monomer, the modified conjugated diene polymer may contain the repeating units derived from the diene monomer in an amount of more than 0% to 1% by weight, more than 0% to 0.1% by weight, more than 0% to 0.01% by weight, or more than 0% to 0.001% by weight. When the amount is within this range, gel formation is prevented.

[0023] The modified conjugated diene polymer has a vinyl content of butadiene units of preferably 20 mol % to 80 mol %, more preferably 20 mol % to 60 mol %, and even more preferably 20 mol % to 40 mol %. The content of repeating units of aromatic vinyl monomers is preferably more than 0 wt % to less than 15 wt %, and more preferably 5 wt % to less than 15 wt %.

[0024] (Molecular weight distribution curve of modified conjugated diene polymer) The modified conjugated diene polymer of this embodiment is specified so that the molecular weight distribution curve obtained by measurement using gel permeation chromatography (GPC) analysis has a single peak and a shoulder on the polymer side of the peak top. Here, "the molecular weight distribution curve has a single peak and a shoulder on the polymer side of the peak top" means that the molecular weight distribution curve has one peak top and three or more inflection points between the peak start point and the peak end point, and that there are two or more inflection points in the region from the peak top to the peak end point, i.e., the region from the peak top to the higher molecular weight side. When such a molecular weight distribution curve is shown, the following reasons may be cited as factors that improve the handling stability and abrasion resistance of the modified conjugated diene polymer, but the reasons are not limited to those listed below.

[0025] Generally, the handling stability and abrasion resistance of a polymer improve as the molecular weight of the polymer increases, but at the same time, the viscosity increases significantly during vulcanization, and the processability during vulcanization tends to deteriorate significantly. Therefore, in a polymer with a high molecular weight, even if a large number of functional groups are introduced into the polymer in order to improve the affinity and / or reactivity with silica blended as a filler, the silica cannot be sufficiently dispersed in the polymer during the kneading process.

[0026] On the other hand, the modified conjugated diene polymer of this embodiment is characterized in that its molecular weight distribution curve has a single peak shape with a shoulder on the polymer side of the peak top. By containing a high molecular weight component but using a component with a lower molecular weight than that component as the main component, the viscosity increase during vulcanization is suppressed, thereby improving processability. Furthermore, by containing a high molecular weight component, the handling stability and abrasion resistance of the vulcanized product are also excellent. Such a modified conjugated diene polymer having a single-peaked molecular weight distribution curve with a shoulder on the polymer side of the peak top can be obtained by forming it from polymers of different molecular weights, from the viewpoint of achieving an appropriate balance between molecular weight and viscosity. Specifically, it can be obtained by varying the molecular weights and branching degrees of the high-molecular weight and low-molecular weight components, as described below. This can improve the balance between the handling stability, abrasion resistance, fuel economy performance, and rupture characteristics of the vulcanizate without impairing the processability of the rubber composition of the conjugated diene polymer.

[0027] (Average molecular weight and molecular weight distribution of modified conjugated diene polymer) The modified conjugated diene polymer of the present embodiment preferably has a number average molecular weight (Mn) measured by GPC measurement method of 10,000 or more and 200 × 10 4 More preferably, it is 10,000 or more and 100×10 4 or less, and more preferably 10×10 4 Over 80 x 10 4 The weight average molecular weight (Mw) is preferably 10,000 or more and 300×10 4 More preferably, it is 10,000 or more and 200 × 10 4 or less, and more preferably 10×10 4 Over 200 x 10 4 If the value is within this range, the rolling resistance and wet grip are excellent. The number average molecular weight and weight average molecular weight may be within a range that combines any of the above upper and lower limits. The number average molecular weight and weight average molecular weight of the modified conjugated diene polymer can be measured by the method described in the examples below.

[0028] The modified conjugated diene polymer of the present embodiment has a ratio (Mw / Mn) (molecular weight distribution) of the weight average molecular weight (Mw) measured by GPC to the number average molecular weight (Mn) measured by GPC, of ​​1.45 or more and less than 1.7, preferably 1.45 or more and less than 1.65, and more preferably 1.45 or more and less than 1.60, from the viewpoint of the tensile properties and viscoelastic properties of the vulcanizate.

[0029] (Si content) The modified conjugated diene polymer of this embodiment may have a Si content of 100 ppm or more and less than 300 ppm, preferably 100 ppm to 280 ppm, and more preferably 100 ppm or more and less than 260 ppm by weight. Within this range, a rubber composition containing the modified conjugated diene polymer has excellent mechanical properties, such as tensile properties and viscoelastic properties. The Si content may refer to the content of Si atoms present in the modified conjugated diene polymer. Meanwhile, the Si atoms may be derived from functional groups derived from a modifier.

[0030] The Si content may be measured, for example, by ICP analysis. The ICP analysis may be performed by an acid decomposition pretreatment method using an inductively coupled plasma optical emission spectrometer (ICP-OES; Optima 7300DV). When using the inductively coupled plasma optical emission spectrometer, approximately 0.7 g of a sample is placed in a platinum crucible, and approximately 1 mL of concentrated sulfuric acid (98 wt %, electronic grade) is added. The sample is heated at 300°C for 3 hours, and the sample is ashed in an electric furnace (Thermo Scientific, Lindberg Blue M) according to the following steps 1 to 3: 1) Step 1: Initial temp 0℃, rate (temp / hr) 180℃ / hr, temp (hold time) 180℃ (1hr) 2) Step 2: Initial temperature 180℃, rate (temp / hr) 85℃ / hr, temperature (hold time) 370℃ (2hr) 3) Step 3: Initial temperature 370℃, rate (temp / hr) 47℃ / hr, temp (hold time) 510℃ (3 hr) To the residue, add 1 mL of concentrated nitric acid (48 wt%) and 20 μL of concentrated hydrofluoric acid (50 wt%), seal the platinum crucible, and shake for at least 30 minutes. Then, add 1 mL of boric acid to the sample and store at 0°C for at least 2 hours. Then, dilute with 30 mL of ultrapure water, and proceed with ashing before measurement.

[0031] (modifying group) The modified conjugated diene polymer of the present embodiment preferably has a modifying group. The term "modifying group" refers to a functional group that has affinity or bonding reactivity with the filler, and examples thereof include functional groups containing a nitrogen atom. The modified conjugated diene polymer of this embodiment has such a modifying group, which further improves the interaction with a filler, and therefore when a composition of the modified conjugated diene polymer containing the modified conjugated diene polymer and a filler is prepared, the breaking strength of the composition is further improved. From the same viewpoint, the modified conjugated diene polymer of this embodiment preferably has a modifying group having a nitrogen atom, and more preferably has a modifying group having a nitrogen atom and a silicon atom. It is not necessary for one modifying group or coupling modifier to contain both a nitrogen atom and a silicon atom; a modifying group containing only one atom or a coupling modifier having a modifying group may be combined so that the polymer contains both nitrogen and silicon.

[0032] A specific example of the modifier according to the present invention may be an alkoxysilane-based modifier containing a nitrogen atom. When the alkoxysilane-based modifier is used, a substitution reaction between an anionic active site located at one end of the activated polymer and an alkoxy group of the alkoxysilane-based modifier can occur, resulting in modification of one end of the activated polymer to a form in which the activated polymer is bonded to a silyl group. In this specification, unless otherwise specified or clearly distinguished, such as when used in parallel as "conjugated diene-based polymer or modified conjugated diene-based polymer," the term "conjugated diene-based polymer" encompasses unmodified conjugated diene-based polymers and modified conjugated diene-based polymers. In addition, when the terms "conjugated diene polymer or modified conjugated diene polymer" are used in parallel, the term "conjugated diene polymer" means an unmodified conjugated diene polymer. Furthermore, the term "residue of a modifier" refers to the remainder of the modifier that is bonded to the conjugated diene polymer as a result of the reaction between the modifier and the conjugated diene polymer.

[0033] (Number of alkoxy groups in the modifier) The number of alkoxy groups in the modifier according to the present invention refers to the number of alkoxy groups bonded to the modifier when an alkoxysilane modifier is used. When comparing the number of alkoxy groups between two types of modifiers according to the present invention, the difference in the number of alkoxy groups is 4 or more, preferably 6 or more, more preferably 8 or more, and even more preferably 9 or more. This difference leaves many functional groups that interact with silica, improving fuel economy, wear resistance, and handling stability.

[0034] According to one embodiment of the present invention, the denaturant may include a compound represented by the following Chemical Formula 1:

[0035] [ka]

[0036] In the above chemical formula 1, R 1 is a single bond or an alkylene group having 1 to 10 carbon atoms, and R 2 and R 3 are each independently an alkyl group having 1 to 10 carbon atoms, and R 4 is hydrogen, an alkyl group having 1 to 10 carbon atoms, a divalent, trivalent, or tetravalent alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a heterocyclic group having 2 to 10 carbon atoms; R 21 is a single bond, an alkylene group having 1 to 10 carbon atoms, or -[R 42 O] j - and R 42is an alkylene group having 1 to 10 carbon atoms, a and m are each independently an integer selected from 1 to 3, n is an integer of 0, 1, or 2, and j may be an integer selected from 1 to 30.

[0037] Specific examples include R 1 is a single bond or an alkylene group having 1 to 5 carbon atoms, and R 2 and R 3 are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms, and R 4 is hydrogen, an alkyl group having 1 to 5 carbon atoms, a tetravalent alkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms, or a heterocyclic group having 2 to 5 carbon atoms; R 21 is a single bond, an alkylene group having 1 to 5 carbon atoms, or -[R 42 O] j - and R 42 is an alkylene group having 1 to 5 carbon atoms, a is an integer of 2 or 3, m is an integer selected from 1 to 3, n is an integer of 0, 1, or 2, where m+n=3, and j may be an integer selected from 1 to 10.

[0038] In the above chemical formula 1, R 4 is a heterocyclic group, the heterocyclic group may or may not be substituted with a tri-substituted alkoxysilyl group, and when the heterocyclic group is substituted with a tri-substituted alkoxysilyl group, the tri-substituted alkoxysilyl group may be substituted by being linked to the heterocyclic group via an alkylene group having 1 to 10 carbon atoms. The tri-substituted alkoxysilyl group may refer to an alkoxysilyl group substituted with an alkoxy group having 1 to 10 carbon atoms.

[0039] More specific examples of the compound represented by Chemical Formula 1 include 3-aminopropylethoxysilane, N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine, N,N-bis(3-(diethoxy(methyl)silyl)propyl)-methyl-1-amine, and N,N-bis(3-(diethoxy(methyl)silyl)propyl)-methyl-1-amine. -1-amine), N,N-bis(3-(trimethoxysilyl)propyl)-methyl-1-amine, N,N-bis(3-(triethoxysilyl)propyl)-methyl-1-amine, N,N-bis(3-(triethoxysilyl)propyl)-methyl-1-amine, N,N-diethyl-3-(trimethoxysilyl)propan-1-amine N,N-diethyl-3-(triethoxysilyl)propan-1-amine, tri(trimethoxysilyl)amine, tri(3-(trimethoxysilyl)propyl)amine, N,N-bis(3-(diethoxy( N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1,1-trimethlysilanamine, N,N-bis(3-(1H-imidazol-1-yl)propyl)-(triethoxysilyl)methan-1-amine, N-(3-(1H-1,2,N-(3-(1H-1,2,4-triazole-1-yl)propyl)-3-(trimethoxysilyl)-N-(trimethoxysilyl)propyl)propan-1-amine, 3-(trimethoxysilyl)-N-(3-trimethoxysilyl)propyl)-N-(3-(1-(3-(trimethoxysilyl)propyl)-1H-1,2,4-triazole-3-yl)propyl 3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)-N-(3-(1-(3-(trimethoxysilyl)propyl)-1H-1,2,4-triazol-3-yl)propyl)propan-1-amine, N,N-bis(2-(2-methoxyethoxy)ethyl)-3-(triethoxysilyl)propan-1-amine, lyl)propan-1-amine), N,N-bis(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecan-16-amine), N-(2,5,8,11,14-pentaoxahexadecan-16-yl)-N-(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecan-16-amine ,8,11,14-pentaoxahexadecan-16-yl)-N-(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecan-16-amine), and N-(3,6,9,12-tetraoxahexadecyl)-N-(3-(triethoxysilyl)propyl)-3,6,9,12-tetraoxahexadecan-1-amine (N-(3,6,9,12-tetraoxahexadecyl)-N-(3-(triethoxysilyl)propyl)-3,6,9,12-tetraoxahexadecan-1-amine).

[0040] As yet another example, the denaturant may include a compound represented by the following Chemical Formula 2:

[0041] [ka]

[0042] In the above chemical formula 2, R 5 , R 6 , and R 9 are each independently an alkylene group having 1 to 10 carbon atoms, and R 7 , R 8 , R 10 , and R 11 are each independently an alkyl group having 1 to 10 carbon atoms, and R 12 is hydrogen or an alkyl group having 1 to 10 carbon atoms, b and c are each independently 0, 1, 2, or 3, and b+c≧1; A is

[0043] [ka]

[0044] or

[0045] [ka]

[0046] where the wavy line indicates the bond to the nitrogen adjacent to A, where R 13 , R 14 , R 15 , and R 16 may each independently be hydrogen or an alkyl group having 1 to 10 carbon atoms.

[0047] Specific examples of the compound represented by Chemical Formula 2 include one selected from the group consisting of N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine and 3-(4,5-dihydro-1H-imidazol-1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine.

[0048] As yet another example, the denaturant may include a compound represented by the following Chemical Formula 3:

[0049] [ka]

[0050] In the above chemical formula 3, A 1 and A 2 are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, which may or may not contain an oxygen atom, and R 17 ~R 20 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, and L 1 ~L 4 are each independently a divalent, trivalent, or tetravalent alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms; 1 and L 2 And, L 3 and L 4 may be linked to each other to form a ring having 1 to 5 carbon atoms, and L 1 and L 2 And, L 3 and L 4When are linked to each other to form a ring, the ring formed may contain 1 to 3 heteroatoms of one or more kinds selected from the group consisting of N, O, and S.

[0051] As a specific example, in the above Chemical Formula 3, A 1 and A 2 are each independently an alkylene group of 1 to 10 carbon atoms, and R 17 ~R 20 are each independently an alkyl group having 1 to 10 carbon atoms, and L 1 ~L 4 are each independently a tetravalent alkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or L 1 and L 2 And, L 3 and L 4 may be linked to each other to form a ring having 1 to 3 carbon atoms, and L 1 and L 2 And, L 3 and L 4 When are linked to each other to form a ring, the ring formed may contain 1 to 3 heteroatoms of one or more kinds selected from the group consisting of N, O and S.

[0052] More specific examples of the compound represented by Chemical Formula 3 include 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), xydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine) (3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine) ( 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine),3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine) (3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diprop ylpropan‐1‐amine), 3,3′‐(1,1,3,3‐tetramethoxydisiloxane‐1,3‐diyl)bis(N,N‐diethylmethan‐1‐amine), 3,3′‐(1,1,3,3‐tetramethoxydisiloxane‐1,3‐diyl)bis(N,N‐diethylmethan‐1‐amine), 3,3′‐(1,1,3,3‐tetraethoxydisiloxane‐1,3‐diyl)bis(N,N‐diethylmethan‐1‐amine) -1,3-diyl)bis(N,N-diethylmethan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine) ,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine),3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine) ,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine) (3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethane-1-amine) ( N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine), N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine), N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine), N,N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-Trimethyl-N-(trimethylsilyl)silanamine (N,N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine), N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine) ethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine), N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine) imethyl-N-phenylsilanamine), N,N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine), 1,3-bis(3-(1H-imidazol-1-yl)propyl) ) 1,1,3,3-tetramethoxydisiloxane (1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetramethoxydisiloxane), 1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetraethoxydisiloxane (1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetraethoxydisiloxane), and 1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,One selected from the group consisting of 3-tetrapropoxydisiloxane (1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetrapropoxydisiloxane) is mentioned.

[0053] As yet another example, the denaturant may include a compound represented by the following Chemical Formula 4:

[0054] [ka]

[0055] In the above chemical formula 4, R 22 and R 23 are each independently an alkylene group having 1 to 20 carbon atoms, or -R 28 [OR 29 ] f - and R 24 ~R 27 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R 28 and R 29 are each independently an alkylene group having 1 to 20 carbon atoms, and R 47 and R 48 are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms, d and e are each independently an integer selected from 0 to 3, d+e is an integer of 1 or more, and f may be an integer of 1 to 30.

[0056] Specifically, in the above-mentioned Chemical Formula 4, R 22 and R 23 are each independently an alkylene group having 1 to 10 carbon atoms, or -R 28 [OR 29 ] f - and R 24 ~R 27 are each independently an alkyl group having 1 to 10 carbon atoms, and R 28 and R 29are each independently an alkylene group having 1 to 10 carbon atoms, d and e are each independently an integer selected from 0 to 3, d+e is an integer of 1 or more, and f may be an integer selected from 1 to 30.

[0057] More specifically, the compound represented by Chemical Formula 4 may be a compound represented by the following Chemical Formula 4a, Chemical Formula 4b, or Chemical Formula 4c.

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] In the above Chemical Formula 4a, Chemical Formula 4b, and Chemical Formula 4c, R 22 ~R 27 , d and e are as described above.

[0062] More specifically, examples of the compound represented by Chemical Formula 4 include 1,4-bis(3-(3-(triethoxysilyl)propoxy)propyl)piperazine, 1,4-bis(3-(triethoxysilyl)propyl)piperazine, 1,4-bis(3-(triethoxysilyl)propyl)piperazine, 1,4-bis(3-(trimethoxysilyl)propyl)piperazine, and the like. 1,4-bis(3-(dimethoxymethylsilyl)propyl)piperazine), 1-(3-(ethoxydimethylsilyl)propyl)-4-(3-(triethoxysilyl)propyl)piperazine), 1-( 1-(3-(ethoxydimethyl)propyl)-4-(3-(triethoxysilyl)methyl)piperazine, 1-(3-(ethoxydimethyl)methyl)-4-(3-(triethoxysilyl)propyl)piperazine, 1,3-bis(3-(triethoxysilyl)propyl)piperazine 1,3-bis(3-(triethoxysilyl)propyl)imidazolidine, 1,3-bis(3-(dimethoxyethylsilyl)propyl)imidazolidine, 1,3-bis(3-(trimethoxysilyl)propyl)hexahydropyrimidine, 1,3-bis(3-(trimethoxysilyl)propyl)hexahydropyrimidine,One selected from the group consisting of 1,3-bis(3-(triethoxysilyl)propyl)hexahydropyrimidine and 1,3-bis(3-(tributoxysilyl)propyl)-1,2,3,4-tetrahydropyrimidine is exemplified.

[0063] As yet another example, the denaturant may include a compound represented by the following Chemical Formula 5:

[0064] [ka]

[0065] In the above chemical formula 5, R 30 is a monovalent hydrocarbon group having 1 to 30 carbon atoms, and R 31 ~R 33 are each independently an alkylene group having 1 to 10 carbon atoms, and R 34 ~R 37 are each independently an alkyl group having 1 to 10 carbon atoms, g and h are each independently an integer selected from 0 to 3, and g+h may be an integer of 1 or greater.

[0066] As yet another example, the denaturant may include a compound represented by the following Chemical Formula 6:

[0067] [ka]

[0068] In the above chemical formula 6, A 3 and A 4 are each independently an alkylene group of 1 to 10 carbon atoms, and R 38 ~R 41are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and i may be an integer selected from 1 to 30.

[0069] As yet another example, the modifier may be 3,4-bis(2-methoxyethoxy)-N-(4-(trimethylsilyl)butyl)aniline, N,N-diethyl-3-(7-methyl-3,6,8,11-tetraoxa-7-silatridecan-7-yl)propan-1-amine, 2,4-bis(2-methoxyethoxy) The silane derivative may contain one or more selected from the group consisting of 2,4-bis(2-methoxyethoxy)-6-((trimethylsilyl)methyl)-1,3,5-triazine, and 3,14-dimethoxy-3,8,8,13-tetramethyl-2,14-dioxa-7,9-dithia-3,8,13-trisilapentadecane.

[0070] As yet another example, the denaturant may include a compound represented by the following Chemical Formula 7:

[0071] [ka]

[0072] In the above chemical formula 7, R 43 , R 45 , and R 46 are each independently an alkyl group having 1 to 10 carbon atoms, and R 44is an alkylene group having 1 to 10 carbon atoms, k is an integer selected from 1 to 4, and l is an integer selected from 1 to 3.

[0073] More specifically, the compound represented by Chemical Formula 7 includes 8,8-dibutyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane (8,8-dibutyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane). decane), 8,8-dimetyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane, 8,8-dibutyl-3,3,13 , 8,8-dibutyl-3,3,13,13-tetramethoxy-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane, and 8-butyl-3,3,13,13-tetramethoxy-8-((3-(trimethoxysilyl)propyl)thio)-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane.

[0074] As yet another example, the denaturant may include a compound represented by the following Chemical Formula 8.

[0075] [ka]

[0076] In the above Chemical Formula 8, R b2 ~R b4 are each independently an alkylene group having 1 to 10 carbon atoms, R b5 ~R b8 are each independently an alkyl group having 1 to 10 carbon atoms, R b12 ~R b14 are each independently an alkylene group having 1 to 10 carbon atoms, R b15 ~R b18 are each independently an alkyl group having 1 to 10 carbon atoms, m1, m2, m3, and m4 may each independently be an integer of 1 to 3.

[0077] As a more specific example, the compound represented by Chemical Formula 8 may be 3,3′-(piperazine-1,4-diyl)bis(N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine).

[0078] As yet another example, the denaturant may include a compound represented by the following Chemical Formula 9:

[0079] [ka] (In the above Chemical Formula 9, R1 to R8 are each independently an alkyl group having 1 to 20 carbon atoms; L1 and L2 are each independently an alkylene group having 1 to 20 carbon atoms; and n is an integer of 2 to 4.

[0080] Specifically, in the above Chemical Formula 9, R1 to R4 may each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. When R1 to R4 are substituted, they may each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkoxy group having 4 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an alkanoyloxy group having 2 to 12 carbon atoms (alkanoyl, R a COO-, at this time, R a may be substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 9 carbon atoms, an aralkyloxy group having 7 to 13 carbon atoms, an arylalkyl group having 7 to 13 carbon atoms, and an alkylaryl group having 7 to 13 carbon atoms. More specifically, R1 to R4 may be a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and even more specifically, R1 to R4 may each independently be a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.

[0081] In addition, in the above chemical formula 9, R5 to R8 are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, specifically a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, more specifically a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and when substituted, may be substituted with the substituents described above for R1 to R4.

[0082] More specifically, the compound represented by Chemical Formula 9 may be one in which R1 to R4 are methyl groups or ethyl groups, and R5 to R8 are alkyl groups having 1 to 10 carbon atoms.

[0083] In the present invention, the amino groups contained in the above Chemical Formula 9, that is, —NR5R6 and —NR7R8, are preferably tertiary amino groups.

[0084] In addition, in the above chemical formula 9, L1 and L2 may each independently be a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms. More specifically, L1 and L2 may each independently be an alkylene group having 1 to 10 carbon atoms, and more specifically, an alkylene group having 1 to 6 carbon atoms, such as a methylene group, an ethylene group, or a propylene group.

[0085] More specifically, the compound represented by Chemical Formula 9 may be a compound represented by any one of Chemical Formulas 9a to 9e below.

[0086] [ka]

[0087] [ka]

[0088] [ka]

[0089] [ka]

[0090] [ka]

[0091] In the present invention, the term "monovalent hydrocarbon group" can refer to a monovalent atomic group in which carbon and hydrogen are bonded, such as a monovalent alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkyl group containing one or more unsaturated bonds, and an aryl group. The minimum number of carbon atoms in a substituent represented by a monovalent hydrocarbon can be determined depending on the type of each substituent.

[0092] In the present invention, the term "divalent hydrocarbon group" can refer to a divalent atomic group in which carbon and hydrogen are bonded, such as a divalent alkylene group, alkenylene group, alkynylene group, cycloalkylene group, cycloalkylene group containing one or more unsaturated bonds, and arylene group. The minimum number of carbon atoms in a substituent represented by a divalent hydrocarbon can be determined depending on the type of each substituent.

[0093] As used herein, the term "alkyl group" means a monovalent aliphatic saturated hydrocarbon group and may be intended to include both straight-chain alkyl groups such as methyl, ethyl, propyl, and butyl, and branched alkyl groups such as isopropyl, sec-butyl, tert-butyl, and neo-pentyl.

[0094] In the present invention, the term "alkylene group" may mean a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene, butylene, and the like.

[0095] In the present invention, the term "alkenyl group" may refer to an alkyl group containing one or more double bonds.

[0096] In the present invention, the term "alkynyl group" can mean an alkyl group containing one or more triple bonds.

[0097] In the present invention, the term "cycloalkyl group" can be meant to include both a cyclic saturated hydrocarbon and a cyclic unsaturated hydrocarbon containing one or more unsaturated bonds.

[0098] In the present invention, the term "aryl group" means a cyclic aromatic hydrocarbon, and may include both a monocyclic aromatic hydrocarbon formed by one ring and a polycyclic aromatic hydrocarbon formed by combining two or more rings.

[0099] The present invention provides a method for producing the modified conjugated diene polymer, which includes the steps of: (S1) polymerizing or copolymerizing a conjugated diene monomer, or a conjugated diene monomer and an aromatic vinyl monomer, in a hydrocarbon solvent in the presence of an organometallic compound to produce an activated polymer having an organometallic bond; and (S2) reacting or coupling the activated polymer produced in step (S1) with a modifier. Step (S1) may be carried out continuously in two or more polymerization reactors, and a polymerization conversion rate in a first reactor of the polymerization reactors may be 50% or less. Alternatively, two or more types of modified conjugated diene polymers produced through steps (S1) and (S2) may be solution-mixed using two or more polymerization reactors.

[0100] The hydrocarbon solvent is not particularly limited, but examples thereof include one or more selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene.

[0101] According to one embodiment of the present invention, the organometallic compound may be used in an amount of 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, 0.1 mmol to 1 mmol, or 0.15 to 0.8 mmol, based on a total of 100 g of the monomers. Examples of the organometallic compound include one or more compounds selected from the group consisting of methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthylsodium, naphthylpotassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, and lithium isopropylamide.

[0102] The organometallic compound may be a modified initiator prepared by reacting with a nitrogen-containing compound, specifically a styrene-based compound containing an amino group, an amido group, an imino group, an imidazole group, a pyrimidyl group, or a cyclic amino group, which may be substituted or unsubstituted with a substituent in the molecule. Here, the substituent may be an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or an alkoxysilyl group having 1 to 10 carbon atoms.

[0103] For example, the nitrogen-containing compound may be a compound represented by the following Chemical Formula 10:

[0104] [ka]

[0105] In the above Chemical Formula 10, R1 to R3 are each independently hydrogen; an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; a heteroalkyl group having 1 to 30 carbon atoms, a heteroalkenyl group having 2 to 30 carbon atoms; a heteroalkynyl group having 2 to 30 carbon atoms; a cycloalkyl group having 5 to 30 carbon atoms; an aryl group having 6 to 30 carbon atoms; or a heterocyclic group having 3 to 30 carbon atoms.

[0106] R4 is a single bond; a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted cycloalkylene group having 5 to 20 carbon atoms; or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0107] R5 is an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; a heteroalkyl group having 1 to 30 carbon atoms; a heteroalkenyl group having 2 to 30 carbon atoms; a heteroalkynyl group having 2 to 30 carbon atoms; a cycloalkyl group having 5 to 30 carbon atoms; an aryl group having 6 to 30 carbon atoms; a heterocyclic group having 3 to 30 carbon atoms; or a functional group represented by the following chemical formula 10a or 10b.

[0108] n is an integer of 1 to 5, and at least one of R5 is a functional group represented by the following chemical formula 10a or chemical formula 10b, and when n is an integer of 2 to 5, multiple R5 may be the same or different.

[0109] [ka]

[0110] In the above Chemical Formula 10a, R6 is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted cycloalkylene group having 5 to 20 carbon atoms; or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0111] R7 and R8 are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted with an aryl group having 6 to 20 carbon atoms.

[0112] R9 is hydrogen; an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; a heteroalkyl group having 1 to 30 carbon atoms; a heteroalkenyl group having 2 to 30 carbon atoms; a heteroalkynyl group having 2 to 30 carbon atoms; a cycloalkyl group having 5 to 30 carbon atoms; an aryl group having 6 to 30 carbon atoms; or a heterocyclic group having 3 to 30 carbon atoms; and Z is an N, O, or S atom, and when Z is O or S, R9 does not exist.

[0113] [ka]

[0114] In the above chemical formula 10b, R 10 represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted cycloalkylene group having 5 to 20 carbon atoms; or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0115] R 11 and R 12are each independently an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; a heteroalkyl group having 1 to 30 carbon atoms; a heteroalkenyl group having 2 to 30 carbon atoms; a heteroalkynyl group having 2 to 30 carbon atoms; a cycloalkyl group having 5 to 30 carbon atoms; an aryl group having 6 to 30 carbon atoms; or a heterocyclic group having 3 to 30 carbon atoms.

[0116] Specifically, in the compound represented by Chemical Formula 10, R1 to R3 are each independently hydrogen; an alkyl group having 1 to 10 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; or an alkynyl group having 2 to 10 carbon atoms; R4 is a single bond; or an unsubstituted alkylene group having 1 to 10 carbon atoms; and R5 is an alkyl group having 1 to 10 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; an alkynyl group having 2 to 10 carbon atoms; or The functional group is represented by Chemical Formula 10a or Chemical Formula 10b, wherein in Chemical Formula 10a, R6 is an unsubstituted alkylene group having 1 to 10 carbon atoms, R7 and R8 are each independently an unsubstituted alkylene group having 1 to 10 carbon atoms, R9 is an alkyl group having 1 to 10 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; or a heterocyclic group having 3 to 20 carbon atoms, and in Chemical Formula 10b, R 10 is an unsubstituted alkylene group having 1 to 10 carbon atoms, and R 11 and R 12 may be, independently of each other, an alkyl group having 1 to 10 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; or a heterocyclic group having 3 to 20 carbon atoms.

[0117] The polymerization in step (S1) may be, for example, anionic polymerization, specifically, living anionic polymerization in which an anionic active site is formed at the polymerization end through an anionic propagation polymerization reaction. The polymerization in step (S1) may also be temperature-rising polymerization, isothermal polymerization, or constant-temperature polymerization (adiabatic polymerization). The constant-temperature polymerization refers to a polymerization method that involves polymerizing an organometallic compound using its own reaction heat without adding heat after the compound is added. The temperature-rising polymerization refers to a polymerization method that involves adding heat after the compound is added to increase the temperature. The isothermal polymerization refers to a polymerization method that involves adding heat after the compound is added to increase the temperature, or removing heat to maintain a constant temperature of the polymer.

[0118] According to one embodiment of the present invention, the polymerization in step (S1) may further include a diene monomer having 1 to 10 carbon atoms in addition to the conjugated diene monomer, which has the effect of preventing gel formation on the reactor wall during long-term operation. The diene monomer may be, for example, 1,2-butadiene.

[0119] The polymerization in step (S1) may be carried out at a temperature in the range of preferably 80° C. or lower, more preferably −20° C. to 80° C., even more preferably 0° C. to 80° C., even more preferably 0° C. to 70° C., and still more preferably 10° C. to 70° C. Within this range, it is possible to control the molecular weight distribution of the polymer to 1.45 or more and less than 1.70, which is highly effective in improving physical properties.

[0120] The activated polymer prepared in step (S1) may refer to a polymer in which a polymer anion and an organometallic cation are bonded.

[0121] According to one embodiment of the present invention, the activated polymer produced by polymerization in step (S1) may be a random copolymer, which has an excellent balance of physical properties. The random copolymer may mean a copolymer in which repeating units constituting the copolymer are randomly arranged.

[0122] According to one embodiment of the present invention, the method for producing the modified conjugated diene-based polymer may be carried out by a continuous polymerization method using a plurality of reactors, including two or more polymerization reactors and a modification reactor. As a specific example, step (S1) may be carried out continuously using two or more polymerization reactors, and the number of polymerization reactors may be flexibly determined depending on the reaction conditions and environment. The continuous polymerization method may refer to a reaction process in which reactants are continuously supplied to a reactor and the resulting reaction product is continuously discharged. The continuous polymerization method has the advantages of excellent productivity and processability, as well as excellent uniformity of the produced polymer.

[0123] Furthermore, according to one embodiment of the present invention, when continuously producing an activated polymer in the polymerization reactor, the polymerization conversion rate in the first reactor may be preferably 50% or less, more preferably 10% to 50%, and even more preferably 20% to 50%. When the polymerization conversion rate is within this range, side reactions that occur during polymer formation after the polymerization reaction is initiated can be suppressed, and a polymer with a linear structure can be induced during polymerization. As a result, the molecular weight distribution of the polymer can be controlled to 1.45 or more and less than 1.70, which has an excellent effect of improving physical properties.

[0124] In this case, the pre-polymerization conversion rate can be controlled by the reaction temperature, the residence time in the reactor, etc.

[0125] The polymerization conversion rate may be determined, for example, by measuring the solid concentration in a polymer solution containing the polymer during polymerization of the polymer. As a specific example, in order to secure the polymer solution, a cylindrical container is attached to the outlet of each polymerization reactor, and a certain amount of polymer solution is filled into the cylindrical container. The cylindrical container is separated from the reactor, and the weight (A) of the cylinder filled with the polymer solution is measured. The polymer solution filled in the cylindrical container is then transferred to an aluminum container, for example, an aluminum dish, and the weight (B) of the cylindrical container from which the polymer solution has been removed is measured. The aluminum container containing the polymer solution is dried in an oven at 140°C for 30 minutes, and the weight (C) of the dried polymer is measured, and the polymerization conversion rate may be calculated using the following mathematical formula 1:

[0126]

number

[0127] Meanwhile, the polymer polymerized in the first reactor may be transferred in sequence to the polymerization reactor upstream of the modification reactor, and polymerization may be continued until a final polymerization conversion rate of 95% or more is reached. After polymerization in the first reactor, the polymerization conversion rate of each reactor from the second reactor to the polymerization reactor upstream of the modification reactor may be appropriately adjusted for each reactor in order to adjust the molecular weight distribution.

[0128] Meanwhile, in the step (S1), during the production of the activated polymer, the residence time of the polymer in the first reactor may be preferably 1 to 40 minutes, more preferably 1 to 30 minutes, and even more preferably 5 to 30 minutes. When the residence time is within this range, the polymerization conversion rate can be easily controlled, and the molecular weight distribution of the polymer can be controlled to 1.45 or more and less than 1.70, thereby achieving excellent effects in improving physical properties.

[0129] In the present invention, the term "polymer" may refer to an intermediate in the form of a polymer undergoing polymerization in each reactor during step (S1) before step (S1) or step (S2) is completed to obtain an activated polymer or a modified conjugated diene-based polymer, or may refer to a polymer undergoing polymerization in a reactor with a polymerization conversion rate of less than 99%.

[0130] According to one embodiment of the present invention, the molecular weight distribution (Mw / Mn) of the activated polymer produced in step (S1) may be less than 1.5, preferably 1.0 to less than 1.5, and more preferably 1.1 to less than 1.5. When the molecular weight distribution is within this range, the modified conjugated diene-based polymer produced by the modification reaction or coupling with the modifier has a narrow molecular weight distribution, which has an excellent effect of improving physical properties.

[0131] Meanwhile, the polymerization in step (S1) may be carried out in the presence of a polar additive, and the polar additive may be added in an amount of 0.001 g to 50 g, 0.001 g to 10 g, or 0.005 g to 0.1 g, based on a total of 100 g of the monomers. As yet another example, the polar additive may be added in an amount of 0.001 g to 10 g, 0.005 g to 5 g, or 0.005 g to 4 g, based on a total of 1 mmol of the organometallic compound.

[0132] Examples of the polar additive include, but are not limited to, ethers such as tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, and 2,2-bis(2-oxolanyl)propane; tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, and quinuclidine; alkali metal alkoxide compounds such as potassium tert-amylate, potassium tert-butylate, sodium tert-butylate, and sodium tert-butylate; and phosphine compounds such as triphenylphosphine. The polar additives complement the difference in reaction rate between conjugated diene monomers or between conjugated diene monomers and aromatic vinyl monomers, thereby facilitating the formation of random copolymers. These polar additives may be used alone or in combination.

[0133] According to one embodiment of the present invention, the reaction or coupling in step (S2) may be carried out in a modification reactor. In this case, the modifier may be used in an amount of 0.01 mmol to 5 mmol based on 100 g of the total monomers. Furthermore, the modifier may be used in a molar ratio of preferably 1:0.1 to 5, more preferably 1:0.1 to 1, and even more preferably 1:0.3 to 1:0.8, based on 1 mole of the organometallic compound in step (S1). When the amount of modifier is within this range, the Si content of the modified conjugated diene copolymer can be 100 ppm or more but less than 300 ppm, resulting in excellent fuel economy and tensile properties. Furthermore, the hardness of the blend is not reduced, and handling stability and abrasion resistance are improved.

[0134] According to one embodiment of the present invention, the modifying agent may be added to a modification reactor, and step (S2) may be performed in the modification reactor. As another example, the modifying agent may be added to a transfer section for transferring the activated polymer produced in step (S1) to a modification reactor for performing step (S2), and reaction or coupling may occur in the transfer section by mixing the activated polymer and the modifying agent.

[0135] (Mooney viscosity of modified conjugated diene polymer) Mooney viscosity is an index that shows the overall characteristics of a conjugated diene polymer, including information on its molecular weight, molecular weight distribution, and softener content. The method for measuring Mooney viscosity is specified in ISO 289, and the measurement error due to instrumental differences is small, making it extremely effective in controlling the performance of conjugated diene polymers. The conjugated diene polymer of the present embodiment preferably has a Mooney viscosity (hereinafter also simply referred to as "Mooney viscosity" or "ML") measured at 100°C of 50 or more, more preferably 60 or more, and even more preferably 70 or more, from the viewpoints of handling stability, breaking strength, and abrasion resistance when a rubber composition for crosslinking containing the conjugated diene polymer of the present embodiment is used in a tire. On the other hand, the upper limit is preferably less than 170, and from the viewpoints of moldability and productivity of molded articles of various shapes such as sheet or block shapes, and rubber compositions containing the conjugated diene polymer of this embodiment, and processability of rubber compositions blended with fillers, etc., it is more preferably 160 or less, even more preferably 150 or less, even more preferably 145 or less, and most preferably 140 or less.

[0136] The Mooney viscosity of a conjugated diene polymer was measured by using a sample of the conjugated diene polymer formed into a plate shape using a pressure press, setting it in the measuring device, preheating the sample to 100°C for 1 minute, rotating the rotor at 2 rpm, and measuring the torque after 4 minutes, and the measured value was taken as the Mooney viscosity (ML (1+4) More specifically, it can be measured by the method described in the Examples below.

[0137] (Mooney Relaxation Rate of Conjugated Diene Polymer) The conjugated diene polymer of this embodiment preferably has a Mooney relaxation rate (hereinafter also simply referred to as "Mooney relaxation rate" or "MSR") measured at 100°C of 0.8 or less, and from the viewpoint of processability of a rubber composition obtained by blending a filler or the like with the conjugated diene polymer, it is more preferably 0.75 or less, even more preferably 0.70 or less, even more preferably 0.65 or less, and most preferably 0.60 or less. On the other hand, the Mooney relaxation rate is preferably 0.25 or more, and from the viewpoint of handling stability and breaking strength when the conjugated diene polymer of this embodiment is used as a tire material, it is more preferably 0.30 or more, even more preferably 0.32 or more, even more preferably 0.34 or more, and particularly preferably 0.36 or more. Like the Mooney viscosity, the Mooney relaxation coefficient is also affected by the molecular weight, molecular weight distribution and softener content of the conjugated diene polymer, and serves as an index showing the overall characteristics of the conjugated diene polymer.

[0138] The MSR can be measured using a Mooney viscometer as follows. The Mooney relaxation rate was measured by first preheating the sample at 100°C for 1 minute, then rotating the rotor at 2 rpm, and calculating the Mooney viscosity (ML) from the torque after 4 minutes. (1+4) ) is measured, the rotation of the rotor is immediately stopped, and the torque is recorded in Mooney units every 0.1 seconds for 1.6 to 5 seconds after stopping. The torque versus time (seconds) is plotted logarithmically, and the slope of the line is determined. The absolute value of this slope is the Mooney Relaxation Rate (MSR). More specifically, it can be measured by the method described in the Examples below.

[0139] [Molded body] The molded article of this embodiment is a molded article containing the conjugated diene-based polymer of this embodiment described above. From the viewpoint of handleability, it is preferably a sheet-like or block-like molded article. The size and thickness of the sheet-shaped or block-shaped molded product are not particularly limited. For example, a sheet-shaped molded product having a thickness of about 1 cm, a block-shaped molded product having a thickness of 1,000 cm, 3 Examples of the molded body include a rectangular parallelepiped or cubic block. The molded body of this embodiment is more preferably a block-shaped molded body, and the shape of the block is preferably a roughly rectangular parallelepiped. 3 The above-mentioned block-shaped (bale) molded bodies are more preferable, and rectangular parallelepiped bales weighing 17.5 kg to 35 kg are even more preferable.

[0140] The molding method is to use a material with a specific surface area of ​​0.7m 2 / g~3.2m 2 In view of moldability, it is preferable to further carry out a step of sieving the crumbs before molding. Since the crumbs adhere to each other when they are compression molded, the specific surface area of ​​the molded body becomes smaller than the specific surface area of ​​the crumbs. The adhesion of the crumbs during compression molding can be adjusted by the molecular weight, composition, and structure of the conjugated diene polymer, the softener component composition, and the temperature and pressure during compression. For example, when it is desired to increase the adhesion of the crumbs and decrease the specific surface area of ​​the bale, it is preferable to decrease the molecular weight of the conjugated diene polymer, increase the amount of the softener component, and increase the temperature and pressure during compression.

[0141] The specific surface area of ​​the molded body of this embodiment is preferably 0.005 to 0.05 m 2 / g, and more preferably, 0.01 to 0.04 m from the viewpoint of film packaging properties. 2 / g. The specific surface area of ​​the compact is 0.005 m 2 / g or more, the expansion of the bale is suppressed, and the specific surface area of ​​the compact is 0.05m 2 / g or less is preferable because it reduces the peeling of crumbs from the molded body. The specific surface area of ​​the molded body can be determined by the BET method. Generally, the specific surface area of ​​a large-sized molded body may vary depending on the location, so it is preferable to collect the sample from near the center of the molded body.

[0142] The molding compression pressure for the molded product is preferably 3 MPa to 30 MPa, more preferably 10 MPa to 20 MPa. When the molding compression pressure is 30 MPa or less, the device can be designed compactly and installation efficiency is good, while when the molding compression pressure is 3 MPa or more, moldability is good. When moldability is good, the surface of the molded product is smooth, there is no peeling of the polymer after the molding process, and expansion after molding tends to be suppressed.

[0143] The temperature of the conjugated diene polymer or the rubber composition containing the conjugated diene polymer during molding is preferably 30 to 120°C, more preferably 50 to 100°C from the viewpoint of reducing residual solvent and suppressing thermal degradation. A molding temperature of 30°C or higher provides good moldability, while a temperature of 120°C or lower is preferred because gel formation due to thermal degradation of the rubber composition can be suppressed. The higher the temperature and pressure during molding, the smaller the specific surface area of ​​the bale. The pressure retention time during molding is preferably 3 to 30 seconds, more preferably 5 to 20 seconds. When the pressure retention time during compression is 30 seconds or less, production efficiency is good, and when it is 5 seconds or more, moldability is good.

[0144] In order to prevent the molded articles from sticking together, it is preferable to wrap them in a resin film (wrapping sheet). The type of resin that can be used for the film includes, for example, polyethylene, ethylene copolymer resin, polystyrene, high impact polystyrene, and PET. From the viewpoint of ease of handling during transportation of the molded article and preventing condensation from forming in the gap between the packaging sheet and the bale, it is preferable that the packaging sheet has good adhesion. The molded article of this embodiment is used, for example, for storage in a container for transportation. If the expansion rate of the molded article one day after molding is less than 5%, the molded article will have good storage properties in the container, which is preferable.

[0145] A softener component, which will be described later, may be added to a sheet- or block-shaped molded product using the conjugated diene polymer of this embodiment. However, in the molded product of this embodiment, from the viewpoint of improving the degree of freedom in compounding during the production of a rubber composition, which will be described later, the amount of the softener component is preferably 2 parts by mass or less, more preferably 1.5 parts by mass or less, even more preferably 1 part by mass or less, even more preferably less than 1 part by mass, per 100 parts by mass of the conjugated diene polymer, and it is most preferable that no softener component is added. The softener component used in the production of the rubber composition described below may be referred to as a "rubber softener," but this is merely a literal distinction from the softener component used in the molded article of the conjugated diene polymer, and does not distinguish between the materials themselves.

[0146] [Rubber composition] The rubber composition of this embodiment contains a rubber component containing the conjugated diene polymer of this embodiment described above. When the conjugated diene polymer of the present embodiment is compounded in a tire, the oil contained in the bale molded article will inevitably be contained in the tire. However, if the amount of oil extension is reduced, the oil contained in the tire will also be reduced, which has the advantage of increasing the degree of freedom in the composition in tire design. The conjugated diene polymer and its sheet- or block-shaped molded product (also referred to as a bale) of this embodiment may contain a softener component, which will be described later. From the viewpoint of improving the degree of freedom in compounding design during the production of a rubber composition, the molded product (bale) preferably contains 2 parts by mass or less of the rubber softener per 100 parts by mass of the conjugated diene polymer, more preferably 1.5 parts by mass or less, even more preferably 1 part by mass or less, even more preferably less than 1 part by mass, and most preferably no softener is added.

[0147] The rubber softener is not particularly limited, but examples thereof include extender oil, liquid rubber, and resin.

[0148] It is preferable that the conjugated diene polymer and its sheet-like or block-like molded product are provided without adding a rubber softener, from the viewpoint of improving the degree of freedom in compounding design when producing a rubber composition using the molded product. Generally, there is an upper limit to the total amount of rubber softeners in the entire rubber composition, but when a rubber softener is added to a sheet- or block-shaped molded body of a conjugated diene polymer, the rubber composition produced by compounding the molded body also contains the rubber material softener, which puts a strain on the total amount of rubber softeners in the entire rubber composition and limits the degree of freedom in the type and amount of rubber softener that needs to be compounded when producing the rubber composition. From the perspective of improving the degree of freedom in selecting the type and amount of rubber softener to be compounded in accordance with the performance required of the rubber composition, it is preferable to reduce the amount of softener added to a sheet- or block-shaped molded body of a conjugated diene polymer.

[0149] Although not particularly limited, for example, by reducing the amount of extender oil added to the conjugated diene-based polymer of the present embodiment and its sheet- or block-shaped molded product, it becomes possible to compound a larger amount of resin such as extender oil when producing a rubber composition using them, which is preferable from the viewpoint of further improving the breaking strength of the rubber composition and its vulcanizate.

[0150] The rubber composition using the conjugated diene-based polymer of the present embodiment and its sheet- or block-shaped molded product may further contain a rubber stabilizer from the viewpoint of suppressing gel formation and improving stability during processing.

[0151] The rubber stabilizer is not limited to the following and known stabilizers can be used, but examples thereof include antioxidants such as 2,6-di-tert-butyl-4-hydroxytoluene (hereinafter also referred to as "BHT"), n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenol) propionate, and 2-methyl-4,6-bis[(octylthio)methyl]phenol.

[0152] The veil of this embodiment contains 100 parts by mass of the modified conjugated diene polymer of this embodiment and less than 1 part by mass of a softener component. The rubber composition of the present embodiment includes 100 parts by mass of a rubber component and 5.0 parts by mass or more and 150 parts by mass or less of a filler, and the rubber component includes 10 parts by mass or more of the modified conjugated diene-based polymer of the present embodiment or the veil of the present embodiment relative to a total of 100 parts by mass of the rubber component.

[0153] The rubber composition of the present embodiment contains 100 parts by mass of the rubber component and 5.0 parts by mass or more and 150 parts by mass or less of a filler. The rubber component preferably contains 10 parts by mass or more of the conjugated diene polymer of the present embodiment relative to 100 parts by mass of the total amount of the rubber component. By dispersing a filler in a rubber component containing the conjugated diene polymer of this embodiment, it is possible to obtain a rubber composition that has better processability during vulcanization and that has better low hysteresis loss, fracture properties, and abrasion resistance of the vulcanizate. Furthermore, by containing the conjugated diene polymer of this embodiment in a predetermined proportion in the rubber component, fuel economy performance, processability, and abrasion resistance are further improved.

[0154] Examples of fillers include, but are not limited to, silica-based inorganic fillers, carbon black, metal oxides, and metal hydroxides. Among these, silica-based inorganic fillers are preferred. In particular, when the rubber composition of this embodiment is used for vulcanized rubber applications such as tires, automobile parts such as anti-vibration rubber, and shoes, it is particularly preferred that the rubber composition contain a silica-based inorganic filler. Such fillers may be used alone or in combination of two or more.

[0155] The silica-based inorganic filler is not particularly limited and any known filler can be used, but solid particles containing SiO2 or Si3Al as a structural unit are preferred, and solid particles containing SiO2 or Si3Al as a main component of the structural unit are more preferred. Here, the main component refers to a component contained in the silica-based inorganic filler in an amount of more than 50 mass%, preferably 70 mass% or more, and more preferably 80 mass% or more.

[0156] Specific silica-based inorganic fillers include, but are not limited to, inorganic fibrous materials such as silica, clay, talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolite, and glass fiber. Surface-hydrophobized silica-based inorganic fillers and mixtures of silica-based inorganic fillers with non-silica-based inorganic fillers may also be used. Among these, silica or glass fiber is preferred, and silica is more preferred, from the viewpoint of further improving the strength and abrasion resistance of the rubber composition. Examples of silica include, but are not limited to, dry silica, wet silica, and synthetic silicate silica. Among these silicas, wet silica is preferred from the viewpoint of further improving the breaking strength of the rubber composition. The rubber composition may contain the modified conjugated diene polymer in an amount of 10% by weight or more, 10% to 100% by weight, or 20% to 90% by weight. When the amount is within this range, excellent mechanical properties such as tensile strength and abrasion resistance are achieved, and an excellent balance between the various physical properties is achieved.

[0157] From the viewpoint of more reliably obtaining a rubber composition having practically good abrasion resistance and breaking strength, the nitrogen adsorption specific surface area determined by the BET adsorption method of the silica-based inorganic filler is 100 m 2 / g or more 300m 2 / g or less, and 170m 2 / g or more 250m 2 / g or less. If necessary, a relatively small specific surface area (for example, a specific surface area of ​​200 m 2 / g) silica-based inorganic filler and a relatively large specific surface area (e.g., 200 m 2 / g or more) of silica-based inorganic filler. 2 When a silica-based inorganic filler (wt. / g or more) is used, the conjugated diene polymer further improves the dispersibility of the silica, and as a result, the resulting rubber composition tends to have even better abrasion resistance, fracture strength, and low hysteresis loss.

[0158] Examples of carbon black include, but are not limited to, carbon blacks of various classes such as SRF, FEF, HAF, ISAF, and SAF. Among these, carbon blacks having a nitrogen adsorption specific surface area of ​​50 m or more as determined by the BET adsorption method are preferred. 2 / g or more and a dibutyl phthalate (DBP) oil absorption of 80 mL / 100 g or less is preferred.

[0159] Metal oxides include those with the chemical formula M x O y (M represents a metal atom, and x and y each independently represent an integer of 1 to 6.) As long as the solid particles have as the main component of the structural unit, there are no particular limitations, but examples include alumina, titanium oxide, magnesium oxide, and zinc oxide.

[0160] Examples of metal hydroxides include, but are not limited to, aluminum hydroxide, magnesium hydroxide, and zirconium hydroxide.

[0161] The content of the filler in the rubber composition of this embodiment is 5.0 parts by mass to 150 parts by mass, preferably 20 parts by mass to 100 parts by mass, and more preferably 30 parts by mass to 90 parts by mass, per 100 parts by mass of the rubber component. When the filler content is within the above range, the rubber composition has better processability during vulcanization, and the vulcanizate tends to have better low hysteresis loss, fracture properties, and abrasion resistance.

[0162] From the viewpoint of reliably imparting the performance required for applications such as tires, such as dry grip performance and conductivity, the rubber composition of this embodiment preferably contains 0.5 parts by mass to 100 parts by mass of carbon black per 100 parts by mass of the rubber component containing the conjugated diene polymer. From the same viewpoint, the rubber composition preferably contains 3.0 parts by mass to 100 parts by mass, and even more preferably 5.0 parts by mass to 50 parts by mass of carbon black per 100 parts by mass of the rubber component containing the conjugated diene polymer.

[0163] The rubber composition of the present embodiment may further contain a silane coupling agent. When the rubber composition contains a silane coupling agent, the interaction between the rubber component and the filler can be further improved. The silane coupling agent is preferably, but not limited to, a compound having a sulfur bond and an alkoxysilyl group or a silanol group in one molecule. Examples of such compounds include, but are not limited to, bis-[3-(triethoxysilyl)-propyl]-tetrasulfide, bis-[3-(triethoxysilyl)-propyl]-disulfide, bis-[2-(triethoxysilyl)-ethyl]-tetrasulfide, etc.

[0164] In the rubber composition of this embodiment, the content of the silane coupling agent is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1.0 to 15 parts by mass, relative to 100 parts by mass of the filler. When the content of the silane coupling agent is within the above range, the interaction between the rubber component and the filler tends to be further improved.

[0165] The rubber composition of the present embodiment may contain, as a rubber component, a rubbery polymer other than the conjugated diene polymer of the present embodiment (hereinafter simply referred to as a "rubbery polymer"). The conjugated diene polymer of the present embodiment and the rubbery polymer are collectively referred to as the "rubber component."

[0166] Examples of rubbery polymers include, but are not limited to, conjugated diene polymers and hydrogenated products thereof, random copolymers of conjugated diene compounds and vinyl aromatic compounds and hydrogenated products thereof, block copolymers of conjugated diene compounds and vinyl aromatic compounds and hydrogenated products thereof, non-diene polymers, and natural rubber.

[0167] Examples of rubber-like polymers include, but are not limited to, styrene-based elastomers such as butadiene rubber and hydrogenated products thereof, isoprene rubber and hydrogenated products thereof, styrene-butadiene rubber and hydrogenated products thereof, styrene-butadiene block copolymers and hydrogenated products thereof, and styrene-isoprene block copolymers and hydrogenated products thereof; and acrylonitrile-butadiene rubber and hydrogenated products thereof.

[0168] Examples of non-diene polymers include, but are not limited to, olefin elastomers such as ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber, and ethylene-octene rubber; butyl rubber, brominated butyl rubber, acrylic rubber, fluororubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, α,β-unsaturated nitrile-acrylate-conjugated diene copolymer rubber, urethane rubber, and polysulfide rubber.

[0169] Examples of natural rubber include, but are not limited to, smoked sheets such as RSS3 to 5, SMR, and epoxidized natural rubber.

[0170] The rubbery polymer may be a modified rubber to which a polar functional group such as a hydroxyl group or an amino group has been added. When the rubber composition of the present embodiment is used for a tire, the rubbery polymer is preferably at least one selected from the group consisting of butadiene rubber, isoprene rubber, styrene-butadiene rubber, natural rubber, and butyl rubber.

[0171] From the viewpoint of the balance between the abrasion resistance, breaking strength, low hysteresis loss, and processability of the rubber composition, the weight average molecular weight of the rubber polymer is preferably 2,000 to 2,000,000, and more preferably 5,000 to 1,500,000. Furthermore, a low molecular weight rubber polymer, so-called liquid rubber, can also be used as the rubber polymer. These rubber polymers may be used alone or in combination of two or more.

[0172] When the rubber composition of the present embodiment contains a conjugated diene polymer and a rubbery polymer, the content ratio (mass ratio) of the conjugated diene polymer to the rubbery polymer (conjugated diene polymer / rubbery polymer) is preferably 10 / 90 or more and 100 / 0 or less, more preferably 20 / 80 or more and 90 / 10 or less, and even more preferably 30 / 70 or more and 80 / 20 or less. That is, the rubber component preferably contains 10 parts by mass or more and 100 parts by mass or less of the conjugated diene polymer of the present embodiment, more preferably 20 parts by mass or more and 90 parts by mass or less, and even more preferably 30 parts by mass or more and 80 parts by mass or less, per 100 parts by mass of the total amount of the rubber component. When the proportion of the conjugated diene polymer in the rubber component is within the above range, the vulcanizate of the rubber composition tends to have even better abrasion resistance and low hysteresis loss.

[0173] The rubber composition of the present embodiment contains a softener component (for example, a rubber softener) in addition to the rubber component, from the viewpoint of further improving its processability. The softener component is not particularly limited, but examples thereof include liquid rubber, resin, and extender oil. The liquid rubber is not particularly limited, but examples thereof include liquid polybutadiene and liquid styrene-butadiene rubber. When a liquid rubber is used as the softener component, in addition to the above-mentioned effects, the glass transition temperature of the conjugated diene polymer composition can be lowered, and therefore the abrasion resistance, low hysteresis loss, and low-temperature properties of the vulcanizate tend to be further improved. Examples of resins include, but are not limited to, aromatic petroleum resins, coumarone-indene resins, terpene resins, rosin derivatives (including tung oil resins), tall oil, tall oil derivatives, rosin ester resins, natural and synthetic terpene resins, aliphatic hydrocarbon resins, aromatic hydrocarbon resins, mixed aliphatic-aromatic hydrocarbon resins, coumarin-indene resins, phenolic resins, p-tert-butylphenol-acetylene resins, phenol-formaldehyde resins, xylene-formaldehyde resins, monoolefin oligomers, diolefin oligomers, hydrogenated aromatic hydrocarbon resins, cycloaliphatic hydrocarbon resins, hydrogenated hydrocarbon resins, hydrocarbon resins, hydrogenated tung oil resins, hydrogenated oil resins, and esters of hydrogenated oil resins with monofunctional or polyfunctional alcohols. These resins may be used alone or in combination. Furthermore, when these resins are hydrogenated, all unsaturated groups may be hydrogenated, or some may remain.

[0174] When a resin is used as the softener component, in addition to the above-mentioned effects, the breaking strength of the vulcanizate of the conjugated diene polymer composition tends to be further improved. In order to further improve the breaking strength of the vulcanizate, it is preferable to add a resin as a softener component to the rubber composition of the present embodiment in addition to the rubber component.

[0175] In order to further improve the processability of the rubber composition of this embodiment, a softener component may be added in addition to the rubber component, and mineral oil or a liquid or low-molecular-weight synthetic softener is preferred.

[0176] Examples of extender oils include aromatic oils, naphthenic oils, and paraffin oils. Among these, aromatic substitute oils having a polycyclic aromatic (PCA) content of 3% by mass or less according to the IP346 method are preferred from the viewpoint of environmental safety, preventing oil bleeding, and improving wet grip performance. Examples of aromatic substitute oils include, but are not limited to, TDAE (Treated Distillate Aromatic Extracts), MES (Mild Extraction Solvate), and RAE (Residual Aromatic Extracts), as shown in KautschukGummiKunststoffe 52(12)799(1999).

[0177] Mineral oil-based rubber softeners, also known as process oils or extender oils, are used to soften rubber, increase its volume, and improve its processability. They are mixtures of aromatic rings, naphthenic rings, and paraffin chains. Among these, those in which the carbon atoms belonging to paraffin chains account for 50% or more of the total carbon atoms are called paraffinic, those in which the carbon atoms belonging to naphthenic rings account for 30% to 45% of the total carbon atoms are called naphthenic, and those in which the carbon atoms belonging to aromatic carbons account for more than 30% of the total carbon atoms are called aromatic. The rubber composition of this embodiment preferably contains a rubber softener with an appropriate aromatic content. The inclusion of such a rubber softener further improves compatibility with conjugated diene polymers.

[0178] The content of the softener component in the rubber composition of this embodiment is represented by the total amount of the softener component added in advance to the conjugated diene-based polymer of this embodiment and the above-mentioned rubber-like polymer, and the softener component added when preparing the rubber composition.

[0179] In the rubber composition of this embodiment, the content of the softener component is preferably 0 to 100 parts by mass, more preferably 10 to 90 parts by mass, and even more preferably 30 to 90 parts by mass, per 100 parts by mass of the rubber component. By having the content of the rubber softener be 100 parts by mass or less per 100 parts by mass of the rubber component, bleeding out can be suppressed, and stickiness on the surface of the rubber composition can be further suppressed.

[0180] Regarding the method for producing the rubber composition of this embodiment, the method for mixing the conjugated diene polymer of this embodiment, a rubbery polymer other than the conjugated diene polymer of this embodiment, a filler, and optionally, a silane coupling agent and a rubber softener, etc., is not particularly limited. Examples include melt-kneading methods using a general mixer such as an open roll, a Banbury mixer, a kneader, a single-screw extruder, a twin-screw extruder, or a multi-screw extruder, and methods in which the components are dissolved and mixed and then the solvent is removed by heating. Of these, melt-kneading methods using a roll, a Banbury mixer, a kneader, or an extruder are preferred from the viewpoints of productivity and good kneading ability. Furthermore, the rubber component, the filler, the silane coupling agent, and the additives may be kneaded all at once, or may be mixed in multiple batches.

[0181] The rubber composition of the present embodiment may be vulcanized with a vulcanizing agent to form a vulcanizate. Examples of vulcanizing agents include, but are not limited to, radical generators such as organic peroxides and azo compounds, oxime compounds, nitroso compounds, polyamine compounds, sulfur, and sulfur compounds. Examples of sulfur compounds include sulfur monochloride, sulfur dichloride, disulfide compounds, and polymeric polysulfur compounds.

[0182] In the rubber composition of this embodiment, the content of the vulcanizing agent is preferably 0.01 to 20 parts by mass, and more preferably 0.1 to 15 parts by mass, per 100 parts by mass of the rubber component. A conventionally known method can be used as the vulcanization method. The vulcanization temperature is preferably 120°C to 200°C, and more preferably 140°C to 180°C.

[0183] When vulcanizing the rubber composition, a vulcanization accelerator and / or a vulcanization aid may be used as necessary. As the vulcanization accelerator, a conventionally known material can be used, and examples thereof include, but are not limited to, sulfenamide-based, guanidine-based, thiuram-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole-based, thiourea-based, and dithiocarbamate-based vulcanization accelerators. Furthermore, examples of the vulcanization aid include, but are not limited to, zinc oxide and stearic acid. The content of each of the vulcanization accelerator and the vulcanization aid is preferably 0.01 parts by mass or more and 20 parts by mass or less, and more preferably 0.1 parts by mass or more and 15 parts by mass or less, per 100 parts by mass of the rubber component.

[0184] The rubber composition of this embodiment may contain various additives other than those described above, such as softeners and fillers, heat stabilizers, antistatic agents, weather stabilizers, antioxidants, colorants, and lubricants, as long as the effects of this embodiment are not impaired. Known softeners can be used as softeners. Specific examples of fillers include, but are not limited to, calcium carbonate, magnesium carbonate, aluminum sulfate, and barium sulfate. Known materials can be used as heat stabilizers, antistatic agents, weather stabilizers, antioxidants, colorants, and lubricants.

[0185] 〔tire〕 The tire of the present embodiment contains the rubber composition of the present embodiment described above. The tire of the present embodiment is not limited to the following, but examples thereof include various types of tires such as fuel-efficient tires, all-season tires, high-performance tires, and studless tires, and the rubber composition of the present embodiment can be suitably used in each part of the tire such as the tread, carcass, sidewall, and bead portion.

[0186] In addition, the numerical ranges described above as preferred ranges, etc., may be replaced with numerical ranges that arbitrarily combine the values ​​described as upper limits and the values ​​described as lower limits, unless otherwise specified. [Example]

[0187] The present invention will be described in detail below with reference to examples. However, the examples according to the present invention can be modified in various ways, and the scope of the present invention should not be construed as being limited to the examples described below. The examples of the present invention are provided to more completely explain the present invention to those skilled in the art.

[0188] [Manufacturing Example 1] Two vacuum-dried 4-liter stainless steel pressure vessels were prepared. 985 g of cyclohexane, 120 g of the compound represented by Formula 10-1 below, and 86 g of tetramethylethylenediamine were added to the first pressure vessel to produce a first reaction solution. Simultaneously, 237 g of 20 wt% liquid n-butyllithium and 874 g of cyclohexane were added to the second pressure vessel to produce a second reaction solution. The molar ratio of the compound represented by Formula 10-1, n-butyllithium, and tetramethylethylenediamine was 1:1:1. The pressure in each pressure vessel was maintained at 7 bar. Using a mass flow meter, the first reaction solution was injected into the first continuous channel at a rate of 1.0 g / min, and the second reaction solution was injected into the second continuous channel at a rate of 1.0 g / min. The temperature of the continuous reactor was maintained at -10°C, the internal pressure was maintained at 3 bar using a back pressure regulator, and the residence time in the reactor was adjusted to within 10 minutes. The reaction was terminated to obtain a modified initiator ("initiator F"). [ka]

[0189] [Example 1] Into the first reactor of the series reactor in which three reactors were connected in series, styrene solution in n-hexane at 60 wt% was dissolved at 18 g / min, 1,3-butadiene solution in n-hexane at 60 wt% was dissolved at 135 g / min, n-hexane at 818 g / min, 1,2-butadiene solution in n-hexane at 2.0 wt% was dissolved at 0.67 g / min, 2,2-di-2 (tetrahydrofuryl) propane in n-hexane as a polar additive at 10 wt% was dissolved at 0.70 mol / min, and n-butyllithium solution in n-hexane at 10 wt% was dissolved at 1.5 mmol / min as a polymerization initiator. During the supply, n-butyllithium was continuously added at a rate of 0.25 mmol / min with a static mixer to inactivate remaining impurities immediately before the mixed solution entered the first reactor. During this supply, the temperature of the first reactor was maintained at 50°C, and when the polymerization conversion rate reached 30%, the polymer was transferred from the first reactor to the second reactor via a transfer pipe.

[0190] Next, a 1,3-butadiene solution in which 1,3-butadiene was dissolved in n-hexane at a concentration of 60 wt% was continuously fed to the second reactor at a rate of 7.1 g / min. During this, the temperature of the second reactor was maintained at 65°C, and when the polymerization conversion rate reached 95% or more, the polymer was transferred from the second reactor to the third reactor via a transfer pipe.

[0191] The polymer was transferred from the second reactor to a third reactor, and N,N-diethyl-3-(trimethoxysilyl)propan-1-amine ("modifier A") and 3,3'-(piperazine-1,4-diyl)bis(N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine" ("modifier B") were added as modifiers to the third reactor at a rate of 0.64 mmol / min and 0.06 mmol / min, respectively. The temperature of the third reactor was maintained at 65°C.

[0192] Then, to the polymerization solution discharged from the third reactor, an n-hexane solution of antioxidant (BHT) was continuously fed at a rate of 0.32 g / min so that the antioxidant (BHT) was 0.2 g per 100 g of polymer, and stirred. The resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and formed into a bale, thereby producing modified conjugated diene polymer A1. The results are shown in Table 1.

[0193] [Example 2] Modified conjugated diene polymer A2 was produced in the same manner as modified conjugated diene polymer A1, except that N,N-diethyl-3-(trimethoxysilyl)propan-1-amine ("modifier A") was continuously fed at a rate of 0.74 mmol / min and 3,3'-(piperazine-1,4-diyl)bis(N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine ("modifier B") was continuously fed at a rate of 0.22 mmol / min.

[0194] [Example 3] Into the first reactor of the series reactor in which three reactors were connected in series, styrene solution in n-hexane was dissolved at 60 wt% styrene, 18 g / min, 1,3-butadiene solution in n-hexane was dissolved at 60 wt% styrene, 135 g / min, n-hexane 818 g / min, 1,2-butadiene solution in n-hexane was dissolved at 2.0 wt% styrene, 0.67 g / min, 2,2-di-2 (tetrahydrofuryl) propane in n-hexane as a polar additive was dissolved at 10 wt% styrene in n-hexane as a polymerization initiator. 1.6 mmol / min of n-butyllithium solution was injected at a rate of 1.6 mmol / min. During the supply, n-butyllithium was continuously added at a rate of 0.25 mmol / min with a static mixer to inactivate remaining impurities immediately before the mixed solution entered the first reactor. During this supply, the temperature of the first reactor was maintained at 55°C, and when the polymerization conversion rate reached 30%, the polymer was transferred from the first reactor to the second reactor via a transfer pipe.

[0195] Next, a 1,3-butadiene solution in which 1,3-butadiene was dissolved in n-hexane at a concentration of 60 wt% was continuously fed to the second reactor at a rate of 7.1 g / min. During this, the temperature of the second reactor was maintained at 65°C, and when the polymerization conversion rate reached 95% or more, the polymer was transferred from the second reactor to the third reactor via a transfer pipe.

[0196] The polymer was transferred from the second reactor to a third reactor, and N,N-diethyl-3-(trimethoxysilyl)propan-1-amine ("modifier A") and 3,3'-(piperazine-1,4-diyl)bis(N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine" ("modifier B") were added as modifiers to the third reactor at a rate of 0.22 mmol / min and 0.17 mmol / min, respectively. The temperature of the third reactor was maintained at 65°C.

[0197] Thereafter, an n-hexane solution of antioxidant (BHT) was continuously fed to the polymerization solution discharged from the third reactor at a rate of 0.32 g / min and stirred so that the amount of antioxidant (BHT) per 100 g of polymer was 0.2 g. The resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and formed into a bale, thereby producing modified conjugated diene polymer A3.

[0198] [Example 4] Modified conjugated diene polymer A4 was produced in the same manner as modified conjugated diene polymer A3, except that N,N-diethyl-3-(trimethoxysilyl)propan-1-amine ("modifier A") was continuously fed at a rate of 0.74 mmol / min and 3,3'-(piperazine-1,4-diyl)bis(N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine ("modifier B") was continuously fed at a rate of 0.21 mmol / min.

[0199] [Example 5] Modified conjugated diene polymer A5 was produced in the same manner as modified conjugated diene polymer A4, except that N,N-diethyl-3-(trimethoxysilyl)propan-1-amine ("modifier A") was continuously fed at a rate of 0.45 mmol / min and 3,3'-(piperazine-1,4-diyl)bis(N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine ("modifier B") was continuously fed at a rate of 0.18 mmol / min.

[0200] [Example 6] Into the first reactor of a series of three reactors connected in series, a styrene solution in which styrene was dissolved in n-hexane at 60 wt%, a 1,3-butadiene solution in which 1,3-butadiene was dissolved in n-hexane at 60 wt%, 129 g / min, n-hexane at 794 g / min, a 1,2-butadiene solution in which 1,2-butadiene was dissolved in n-hexane at 2.0 wt%, a polar additive in which 2,2-(di-2(tetrahydrofuryl)propane was dissolved in n-hexane at 10 wt%, 0.46 mmol / min, and the modified initiator prepared in Preparation Example 1 ("initiator F") were injected at a rate of 292.50 g / h. During this time, the temperature of the first reactor was maintained at 50°C, and when the polymerization conversion rate reached 43%, the polymer was transferred from the first reactor to the second reactor via a transfer pipe.

[0201] Next, a 1,3-butadiene solution in which 1,3-butadiene was dissolved in n-hexane at a concentration of 60 wt % was injected into the second reactor at a rate of 6.8 g / h. At this time, the temperature of the second reactor was maintained at 65° C., and when the polymerization conversion rate reached 95% or more, the polymer was transferred from the second reactor to the third reactor via a transfer pipe.

[0202] The polymer was transferred from the second reactor to a third reactor, and N,N-diethyl-3-(trimethoxysilyl)propan-1-amine ("modifier A") and 3,3'-(piperazine-1,4-diyl)bis(N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine ("modifier B") were added as modifiers to the third reactor at a rate of 0.68 mmol / min and 0.06 mmol / min, respectively. The temperature of the third reactor was maintained at 65°C.

[0203] Thereafter, an n-hexane solution of antioxidant (BHT) was continuously fed at a rate of 0.32 g / min to the polymerization solution discharged from the third reactor and stirred so that the amount of antioxidant (BHT) per 100 g of polymer was 0.2 g. The resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and formed into a bale, thereby producing modified conjugated diene polymer A6.

[0204] [Example 7] Modified conjugated diene polymer A7 was produced in the same manner as modified conjugated diene polymer A1, except that the compound represented by chemical formula 9d ("modifier D") was continuously fed at a rate of 0.29 mmol / min and N,N-diethyl-3-(trimethoxysilyl)propan-1-amine ("modifier A") was continuously fed at a rate of 0.14 mmol / min.

[0205] [Comparative Example 1] Modified conjugated diene polymer B1 was produced in the same manner as modified conjugated diene polymer A1, except that only N,N-diethyl-3-(trimethoxysilyl)propan-1-amine ("modifier A") was continuously fed at a rate of 1.47 mmol / min as the modifier.

[0206] Comparative Example 2 Modified conjugated diene polymer B2 was produced in the same manner as modified conjugated diene polymer A1, except that N,N-diethyl-3-(trimethoxysilyl)propan-1-amine ("modifier A") was continuously fed at a rate of 1.29 mmol / min and 3,3'-(piperazine-1,4-diyl)bis(N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine ("modifier B") was continuously fed at a rate of 0.05 mmol / min.

[0207] Comparative Example 3 Modified conjugated diene polymer B3 was produced in the same manner as modified conjugated diene polymer A3, except that N,N-diethyl-3-(trimethoxysilyl)propan-1-amine ("modifier A") was continuously fed at a rate of 0.43 mmol / min and 3,3'-(piperazine-1,4-diyl)bis(N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine ("modifier B") was continuously fed at a rate of 0.03 mmol / min.

[0208] Comparative Example 4 Modified conjugated diene polymer B4 was produced in the same manner as modified conjugated diene polymer A3, except that the reaction temperatures were maintained at 70°C in the first reactor, 80°C in the second reactor, and 80°C in the third reactor; when the polymerization conversion rate in the first reactor reached 70%, the polymer was transferred from the first reactor to the second reactor via a transfer pipe; and N,N-diethyl-3-(trimethoxysilyl)propan-1-amine ("modifier A") and 3,3'-(piperazine-1,4-diyl)bis(N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine ("modifier B") were continuously fed as modifiers to the third reactor at rates of 0.73 mmol / min and 0.18 mmol / min, respectively.

[0209] Comparative Example 5 Modified conjugated diene polymer B5 was produced in the same manner as modified conjugated diene polymer A1, except that N,N-diethyl-3-(trimethoxysilyl)propan-1-amine ("modifier A") was continuously fed at a rate of 0.77 mmol / min and 1,4-bis(3-(triethoxysilyl)propyl)piperazine ("modifier C") was continuously fed at a rate of 0.13 mmol / min.

[0210] Comparative Example 6 Modified conjugated diene polymer B6 was produced in the same manner as modified conjugated diene polymer A6, except that N,N-diethyl-3-(trimethoxysilyl)propan-1-amine ("modifier A") was continuously fed at a rate of 0.94 mmol / min and 3,3'-(piperazine-1,4-diyl)bis(N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine ("modifier B") was continuously fed at a rate of 0.04 mmol / min.

[0211] Comparative Example 7 Modified conjugated diene polymer B7 was produced in the same manner as modified conjugated diene polymer A7, except that the compound represented by chemical formula 9d ("modifier D") was continuously fed at a rate of 0.12 mmol / min and N,N-diethyl-3-(trimethoxysilyl)propan-1-amine ("modifier A") was continuously fed at a rate of 1.03 mmol / min.

[0212] In Table 1 below, when two values ​​are listed for the polymerization temperature, the former indicates the polymerization temperature of the first reactor and the latter indicates the polymerization temperature of the second reactor. Initiators and modifiers are also shown. Modifier A: N,N-diethyl-3-(trimethoxysilyl)propan-1-amine Modifier B: 3,3'-(piperazine-1,4-diyl)bis(N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine) Modifier C: 1,4-bis(3-(triethoxysilyl)propyl)piperazine Modifier D: a compound represented by formula 9d Initiator E: n-butyllithium Initiator F: Modified initiator according to Production Method 1

[0213] [ka] [ka] [ka] [ka]

[0214] (Property 1) Molecular weight distribution curve, average molecular weight, and molecular weight distribution measured by gel permeation chromatography (GPC) Unmodified conjugated diene polymers and modified conjugated diene polymers were used as samples. GPC measurements were performed using a GPC measurement device (manufactured by Tosoh Corporation under the trade name "HLC-8320GPC") with two columns packed with polystyrene gel, and a refractive index (RI) detector (manufactured by Tosoh Corporation under the trade name "HLC8020"). The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) were determined based on a calibration curve obtained using standard polystyrene. The eluent used was a 2 wt% triethylamine-THF (tetrahydrofuran) solution. Two columns, "TSKgel GMHHR-H(S)" manufactured by Tosoh Corporation, were connected, and a "TSKguardcolumn SuperMP(HZ)-H" guard column, manufactured by Tosoh Corporation, was connected in front of them. 10 mg of the sample to be measured was dissolved in 10 mL of THF to prepare a measurement solution, and 100 μL of the measurement solution was injected into a GPC measurement device and measured under conditions of an oven temperature of 40° C. and a flow rate of 1.0 mL / min. The shape of the molecular weight distribution curve obtained as a result of the measurement and the presence or absence of a shoulder on the higher molecular weight side from the peak top were confirmed. The measurement results were recorded as the average molecular weight of each sample.

[0215] (Physical properties 2) Si content Measurement was performed using an inductively coupled plasma optical emission spectrometer (ICP-OES; Optima 7300DV) by ICP analysis. When using the inductively coupled plasma optical emission spectrometer, approximately 0.7 g of sample was placed in a platinum crucible, and approximately 1 mL of concentrated sulfuric acid (98 wt%, electronic grade) was added and heated at 300°C for 3 hours. The sample was then ashed in an electric furnace (Thermo Scientific, Lindberg Blue M) according to the following steps 1 to 3 of the program. 1) Step 1: Initial temperature 0℃, rate (temp / hr) 180℃ / hr, temp (hold time) 180℃ (1hr) 2) Step 2: Initial temperature 180℃, rate (temp / hr) 85℃ / hr, temp (hold time) 370℃ (2hr) 3) Step 3: Initial temperature 370℃, rate (temp / hr) 47℃ / hr, temp (hold time) 510℃ (3 hr) To the residue, 1 mL of concentrated nitric acid (48 wt%) and 20 μL of concentrated hydrofluoric acid (50 wt%) were added, and the platinum crucible was sealed and shaken for more than 30 minutes. After that, 1 mL of boric acid was added to the sample and stored at 0°C for more than 2 hours. Then, the sample was diluted with 30 mL of ultrapure water, incinerated, and measured.

[0216] (Physical Property 3) Polymer Mooney Viscosity Using an unmodified conjugated diene polymer and a modified conjugated diene polymer as samples, the Mooney viscosity was measured using a Mooney viscometer (trade name "VR1132" manufactured by Ueshima Seisakusho Co., Ltd.) with an L-shaped rotor in accordance with ISO289. The measurement temperature was 110°C when an unmodified conjugated diene polymer was used as the sample, and 100°C when a modified conjugated diene polymer was used as the sample. After preheating the sample at the test temperature for 1 minute, the rotor was rotated at 2 rpm, and the torque was measured after 4 minutes to measure the Mooney viscosity (ML(1+4)).

[0217] (Physical Property 4) Mooney Relaxation Rate (MSR) Using an unmodified conjugated diene polymer and a modified conjugated diene polymer as samples, a Mooney viscometer (trade name "VR1132" manufactured by Ueshima Seisakusho Co., Ltd.) was used to measure the Mooney viscosity using an L-shaped rotor in accordance with ISO289. After that, the rotation of the rotor was immediately stopped and the torque was recorded in Mooney units every 0.1 seconds for 1.6 to 5 seconds after the rotor had stopped. The slope of the straight line when the torque versus time (seconds) was plotted logarithmically was determined and the absolute value was taken as the Mooney relaxation rate (MSR). The measurement temperature was 110°C when an unmodified conjugated diene polymer was used as the sample, and 100°C when a modified conjugated diene polymer was used as the sample.

[0218] (Physical Property 5) Amount of bound vinyl aromatic monomer units (amount of bound styrene) The modified conjugated diene polymer was used as a sample, and 100 mg of the sample was dissolved in 100 mL of chloroform to prepare a sample for measurement. Each sample was measured using a spectrophotometer (Shimadzu Corporation, product name "UV-2450") to obtain an absorption spectrum. The amount of bound styrene (mass%) relative to 100 mass% of the modified conjugated diene polymer was calculated from the amount of absorbance of ultraviolet light (around 254 nm) derived from the phenyl group of styrene.

[0219] (Physical Property 6) Amount of vinyl bonds in bonded conjugated dienes (amount of 1,2-vinyl bonds in bonded butadiene) The modified conjugated diene polymer was used as a sample, and 50 mg of the sample was dissolved in 10 mL of carbon disulfide to prepare a sample for measurement. The infrared spectrum of each sample was measured in the range of 600 to 1000 cm −1 using a Fourier transform infrared spectrophotometer (trade name “FT-IR230” manufactured by JASCO Corporation). According to the Hampton method (method described in R.R. Hampton, Analytical Chemistry 21, 923 (1949)), the amount of 1,2-vinyl bonds (mol %) in the bound butadiene was determined from the absorbance at a predetermined wave number.

[0220] [Table 1]

[0221] [Preparation and Evaluation of Rubber Compositions] (Evaluation of Rubber Composition) Using the modified conjugated diene polymers A1 to A7 and B1 to B7 shown in Table 1 as raw materials, rubber compositions were obtained according to the formulations shown below. Modified conjugated diene polymer (A1 to A7, B1 to B7): 100 parts by mass (oil excluded) Silica (product name "Ultrasil 7000GR" manufactured by Evonik Degussa, nitrogen adsorption specific surface area 170 m 2 / g):75.0 parts by mass Carbon black (product name "Seat KH (N339)" manufactured by Tokai Carbon Co., Ltd.): 5.0 parts by mass Silane coupling agent (trade name "Si75" manufactured by Evonik Degussa, bis(triethoxysilylpropyl) disulfide): 6.0 parts by mass S-RAE oil (product name "Process NC140" manufactured by JX Nippon Oil & Energy Corporation): 32.0 parts by mass ·Zinc white: 2.5 parts by mass Stearic acid: 2.0 parts by weight Antioxidant (N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine): 2.0 parts by mass ·Sulfur: 1.7 parts by mass Vulcanization accelerator 1 (N-cyclohexyl-2-benzothiazylsulfinamide): 1.7 parts by mass Vulcanization accelerator 2 (diphenyl guanidine): 2.0 parts by mass

[0222] Specifically, the above materials were kneaded by the following method to obtain rubber compositions. In the first stage of kneading, a modified conjugated diene polymer (A1 to A7 or B1 to B7), a filler (silica, carbon black), a silane coupling agent, S-RAE oil, zinc oxide, and stearic acid were kneaded using an internal kneader (0.5 L capacity) equipped with a temperature control device at a filling rate of 65% and a rotor rotation speed of 30 to 50 rpm. The temperature of the internal kneader was controlled to obtain each rubber composition (compound) at a discharge temperature of 155 to 160°C.

[0223] Next, in the second stage of mixing, the compound obtained above was cooled to room temperature, and then an antioxidant was added. The compound was mixed again under the same conditions as in the first stage of mixing to improve the dispersion of the silica. Again, the temperature of the mixer was controlled so that the discharge temperature of the compound was 155-160°C. After cooling, in the third stage of mixing, sulfur and vulcanization accelerators 1 and 2 were added and mixed using an open roll set at 70°C. The mixture was then molded and vulcanized in a vulcanization press at 160°C for 20 minutes. The rubber composition before and after vulcanization was evaluated. Specifically, the evaluation was carried out by the following methods, and the evaluation results are shown in Table 2.

[0224] (Evaluation 1) Emissions coherence The unvulcanized modified conjugated diene polymers produced by the methods shown in the Examples and Comparative Examples were visually observed for cohesion (shape) immediately after being discharged from the pressure kneader (immediately after the completion of kneading in the pressure kneader in the first stage and the polymer was discharged), and evaluated by a panelist on the basis of the following criteria, with each panelist scoring 4 points as the maximum score. Cohesion is an index of the processability of the vulcanized product. IV: The edge of the sheet is 60% or less smooth, and the processability is very poor. III: The edge portion of the sheet is smooth by more than 60% but not more than 80%, and the processability is poor. II: The edge of the sheet is smooth by more than 80% but not more than 90%, and has excellent processability. I: 90% of the sheet edges are super smooth, providing excellent processability.

[0225] (Evaluation 2, 3, 4) Viscoelastic parameters (fuel economy, wet grip, handling stability) Viscoelastic parameters were measured in torsion mode using an ARES viscoelasticity tester manufactured by Rheometrics Scientific Inc. Each measurement value was indexed, with the result for the rubber composition of Comparative Example 1 being set at 100. Here, tan δ measured at 50°C, a frequency of 10 Hz, and a strain of 3% was used as an index of low hysteresis loss, i.e., fuel economy, and was standardized with the result of Comparative Example 1 set to 100. A larger index indicates better fuel economy. In addition, tan δ measured at 0° C., a frequency of 10 Hz, and a strain of 1% was used as an index of wet grip performance, and the result of Comparative Example 1 was standardized as 100. A larger index indicates better wet grip performance. Furthermore, the modulus of elasticity (G') measured at 50°C, a frequency of 10 Hz, and a strain of 3% was used as an index of handling stability. A larger index indicates better handling stability.

[0226] (Evaluation 5, 6) Tensile strength and tensile elongation The tensile strength and tensile elongation were measured in accordance with the tensile testing method of JIS K6251. Each measurement value was standardized with the result of Comparative Example 1 set to 100. The larger the value, the better the tensile strength and tensile elongation, and the more excellent the fracture properties.

[0227] (Rating 7) Abrasion resistance Using an Acron abrasion tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.), the amount of wear was measured after 1000 revolutions under a load of 44.4 N in accordance with JIS K6264-2. Each measurement value was standardized with the result of Comparative Example 1 set at 100. A larger value indicates better abrasion resistance. [Table 2]

[0228] As shown in Table 2, it was found that the conjugated diene polymer of the present invention has excellent processability of the vulcanizate and an excellent balance of performance such as low hysteresis loss, wet grip properties, handling stability, fracture properties, and abrasion resistance.

[0229] The conjugated diene-based polymer and rubber composition of the present invention have excellent processability, and the vulcanizates thereof have an excellent balance of fuel economy, wet grip properties, handling stability, fracture properties, and abrasion resistance. Therefore, the conjugated diene-based polymer and rubber composition of the present invention have industrial applicability in applications such as tires, resin modification, automobile interior and exterior parts, vibration-proof rubber, and footwear.

Claims

1. Contains residues of two types of alkoxysilane-based modifiers, the difference in the number of alkoxy groups in the modifying agents is 4 or more, A modified conjugated diene polymer that satisfies the following <Condition (i)> to <Condition (iii)>. <Condition (i)> The molecular weight distribution curve measured by gel permeation chromatography (GPC) has a single peak, with a shoulder on the polymer side of the peak top. <Condition (ii)> The molecular weight distribution (PDI; MWD) is 1.45 or more and less than 1.

7. <Condition (iii)> The Si content is 100 ppm or more and less than 300 ppm by weight.

2. The modified conjugated diene polymer according to claim 1, wherein the alkoxysilane-based modifier is a compound represented by a chemical formula selected from the group consisting of the following chemical formulas 1 to 9: 【Chemical 1】 (In the above Chemical Formula 1, R 1 is a single bond or an alkylene group having 1 to 10 carbon atoms, R 2 and R 3 are each independently an alkyl group having 1 to 10 carbon atoms, R 4 is hydrogen, an alkyl group having 1 to 10 carbon atoms, a divalent, trivalent, or tetravalent alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a heterocyclic group having 2 to 10 carbon atoms; R 21 is a single bond, an alkylene group having 1 to 10 carbon atoms, or -[R 42 O] j - and R 42 is an alkylene group having 1 to 10 carbon atoms, a and m are each independently an integer selected from 1 to 3; n is 0, 1, or 2; j is an integer selected from 1 to 30. 【Chemistry 2】 (In the above chemical formula 2, R 5 , R 6 , and R 9 are each independently an alkylene group having 1 to 10 carbon atoms, R 7 , R 8 , R 10 , and R 11 are each independently an alkyl group having 1 to 10 carbon atoms, R 12 is hydrogen or an alkyl group having 1 to 10 carbon atoms, b and c are each independently 0, 1, 2, or 3, and b+c≧1; A is, 【Chemistry 3】 or 【Chemistry 4】 where the wavy line indicates the bond to the nitrogen adjacent to A, R 13 , R 14 , R 15 , and R 16 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms. 【Chemistry 5】 (In the above chemical formula 3, A 1 and A 2 are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, which may or may not contain an oxygen atom, R 17 ~R 20 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, L 1 ~L 4 are each independently a divalent, trivalent, or tetravalent alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or L 1 and L 2 And, L 3 and L 4 are linked together to form a ring having 1 to 5 carbon atoms, and L 1 and L 2 And, L 3 and L 4 When are linked to each other to form a ring, the formed ring may contain 1 to 3 heteroatoms of one or more types selected from the group consisting of N, O, and S. 【Chemistry 6】 (In the above chemical formula 4, R 22 and R 23 are each independently an alkylene group having 1 to 20 carbon atoms, or -R 28 [OR 29 ] f - and R 24 ~R 27 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 28 and R 29 are each independently an alkylene group having 1 to 20 carbon atoms, R 47 and R 48 are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms, d and e are each independently an integer selected from 0 to 3, and d+e is an integer of 1 or greater; f is an integer from 1 to 30. 【Chemistry 7】 (In the above chemical formula 5, R 30 is a monovalent hydrocarbon group having 1 to 30 carbon atoms, R 31 ~R 33 are each independently an alkylene group having 1 to 10 carbon atoms, R 34 ~R 37 are each independently an alkyl group having 1 to 10 carbon atoms, g and h are each independently an integer selected from 0 to 3, and g+h is an integer of 1 or greater. 【Chemistry 8】 (In the above chemical formula 6, A 3 and A 4 are each independently an alkylene group having 1 to 10 carbon atoms, R 38 ~R 41 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, i is an integer selected from 1 to 30. 【Chemistry 9】 (In the above chemical formula 7, R 43 , R 45 , and R 46 are each independently an alkyl group having 1 to 10 carbon atoms, R 44 is an alkylene group having 1 to 10 carbon atoms, k is an integer selected from 1 to 4; l is an integer selected from 1 to 3. 【Chemistry 10】 (In the above Chemical Formula 8, R b2 ~R b4 are each independently an alkylene group having 1 to 10 carbon atoms, R b5 ~R b8 are each independently an alkyl group having 1 to 10 carbon atoms, R b12 ~R b14 are each independently an alkylene group having 1 to 10 carbon atoms, R b15 ~R b18 are each independently an alkyl group having 1 to 10 carbon atoms, m1, m2, m3, and m4 are each independently an integer of 1 to 3. 【Chemistry 11】 (In the above Chemical Formula 9, R 1 ~R 8 are each independently an alkyl group having 1 to 20 carbon atoms; L 1 and L 2 are each independently an alkylene group having 1 to 20 carbon atoms; n is an integer from 2 to 4.

3. The modified conjugated diene polymer according to claim 2, wherein the compound represented by Chemical Formula 4 is a compound represented by a chemical formula selected from the group consisting of the following Chemical Formulas 4a to 4c: 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 (In the above Chemical Formula 4a, Chemical Formula 4b, and Chemical Formula 4c, R 22 ~R 27 , d and e are as defined above.)

4. A number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of 1,000 or more and 200 x 10 4 and the weight average molecular weight (Mw) is 1,000 or more and 300 × 10 4 Below is the The modified conjugated diene polymer according to claim 1 .

5. 2. The modified conjugated diene polymer according to claim 1, which has a Mooney viscosity measured at 100°C of 50 or more but less than 170, and a Mooney relaxation rate (MSR) measured at 100°C of 0.30 or more but 0.80 or less.

6. 100 parts by mass of the modified conjugated diene polymer according to claim 1; less than 1 part by weight of a softener component; A molded body containing the above.

7. 100 parts by mass of a rubber component, A filler is contained in an amount of 5.0 parts by mass or more and 150 parts by mass or less, The rubber component contains 10 parts by mass or more of the modified conjugated diene-based polymer according to any one of claims 1 to 5 relative to 100 parts by mass of the total amount of the rubber component. Rubber composition.

8. A tire comprising the rubber composition according to claim 7.

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