Silane coupling agent composition and rubber composition containing same

Abstract

[Problem] To provide a silane coupling agent composition from which a rubber composition having excellent uncrosslinked compound viscosity and scorch resistance, a crosslinked product of a rubber composition having excellent viscoelastic properties, and a tire using the silane coupling agent composition and the crosslinked product and having a superior balance in terms of wet-gripping ability and low fuel consumption. [Solution] A silane coupling agent composition according to the present invention contains silane compounds including a first silane compound represented by formula (1) and a second silane compound represented by formula (11).

Description

[Technical Field]

[0001] The present invention relates to a silane coupling agent composition and a rubber composition containing the same. The present invention also relates to a crosslinked product of the rubber composition and a tire using the rubber composition. [Background technology]

[0002] Conventionally, silane compounds having a reactive functional group and a hydrolyzable group have been used as components of silane coupling agents to improve the dispersibility of organic polymer materials such as rubber and inorganic materials such as silica in rubber compositions.

[0003] Typically, such silane compounds have a reactive functional group, such as a mercapto group, a polysulfide group, an amino group, or an epoxy group, which is highly reactive with organic polymer materials such as rubber, and a hydrolyzable group, such as an alkoxysilyl group, which is highly reactive with inorganic materials such as silica. For example, Patent Document 1 discloses a rubber composition containing a polysulfide-based silane coupling agent. Patent Document 2 proposes a silane compound having an amino group as a reactive functional group and a methoxy group as a hydrolyzable group.

[0004] Furthermore, Patent Document 3 proposes a rubber composition containing an organic silane compound having a monosulfide bond in order to improve the scorch resistance of the rubber composition and the heat generation characteristics (viscoelasticity characteristics) of a cross-linked product of the rubber composition. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 8-259736 [Patent Document 2] Japanese Patent Application Publication No. 11-335381 [Patent Document 3] Japanese Patent Application Laid-Open No. 2014-177432 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the reactive functional groups of the silane compounds proposed in Patent Documents 1 and 2 have high polarity, and when the organic polymer material to be mixed is low-polar, the silane compound and the organic polymer material have low affinity, tending to result in poor dispersion or poor mixing. Therefore, when a silane coupling agent composition containing such a silane compound is added to a rubber composition, the viscosity of the uncrosslinked (unvulcanized) rubber tends to deteriorate. On the other hand, when a conventional silane compound having a low-polarity reactive functional group is added to increase affinity with low-polarity organic polymer materials, the reactivity with the organic polymer material is low, resulting in insufficient performance as a silane coupling agent.

[0007] Furthermore, the silane compound described in Patent Document 3 does not have an appropriate reactivity with organic polymer materials.

[0008] Therefore, an object of the present invention is to provide a silane coupling agent composition that can give a rubber composition that has moderate reactivity with organic polymer materials such as rubber and that is excellent in scorch resistance and viscosity characteristics (uncrosslinked compound viscosity) when compounded.Another object of the present invention is to provide a rubber composition that is excellent in scorch resistance and uncrosslinked compound viscosity, as well as a crosslinked product of the rubber composition that is excellent in viscoelastic properties, and a tire that uses the crosslinked product and has an excellent balance of wet grip performance and fuel economy. [Means for solving the problem]

[0009] As a result of extensive research, the present inventors have found that by using two types of silane compounds as silane coupling agents, one having an alicyclic hydrocarbon moiety with an olefin structure and the other having an alicyclic silyl group, which have affinity with organic polymer materials and moderate reactivity, the coupling reaction is promoted, and as a result, when the compounded product is a rubber composition, the dispersibility of inorganic materials such as silica is improved, resulting in a rubber composition with excellent scorch resistance and uncrosslinked compound viscosity, as well as a crosslinked product of the rubber composition with excellent viscoelastic properties, and a tire using the same that has an excellent balance of wet grip properties and fuel economy. The present invention is based on this finding.

[0010] The present invention includes the following inventions. [1] A silane coupling agent composition containing a silane compound, The silane compound is represented by the following formula (1): [ka] [In the formula, R 1 , R 2 and R 3 each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom; L is a hydrocarbon group which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur; a is an integer between 0 and 1, b is an integer between 0 and 1, c's are each independently an integer of 0 or 1; each d is independently an integer of 0 or 1; e is an integer from 0 to 5, R 4 , R 5 , R 6 and R 7 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 One of them is -(CH2)f - may form a crosslinked structure represented by f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 One of them is -(CH2) g - may form a crosslinked structure represented by g is an integer from 1 to 5, R 16 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 8 carbon atoms, and R 17 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, where R 12 and R 13 are bonded to each other to form a double bond, and R 14 , R 15 and R 18 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 14 and R 15 are bonded to each other to form a double bond, and R 12 , R 13 and R 18 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 16 and R 17 may be bonded to each other to form a 4- to 9-membered alicyclic hydrocarbon, where R 14 and R 15 are bonded to each other to form a double bond, and R 12 , R 13 and R 18 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms.] a first silane compound represented by the formula: The following formula (11): [ka] [In the formula, Each R 1 , R 2 and R 3 each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom; each L is independently a hydrocarbon group which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur; a is an integer between 0 and 1, b is an integer between 0 and 1, c's are each independently an integer of 0 or 1; each d is independently an integer of 0 or 1; e is an integer from 0 to 5, R 4 , R 5 , R 6 and R 7 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 One of them is -(CH2) f - may form a crosslinked structure represented by f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 One of them is -(CH2) g - may form a crosslinked structure represented by g is an integer from 1 to 5, R 26 , R 27 and R 28 each independently represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms.] A silane coupling agent composition comprising a second silane compound represented by the formula: [2] The first silane compound is represented by the following formula (2): [ka] [In the formula, R 1 , R 2 and R 3 each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom; h is an integer from 1 to 10; a is an integer between 0 and 1, b is an integer between 0 and 1, c's are each independently an integer of 0 or 1; each d is independently an integer of 0 or 1; e is an integer from 0 to 5, R 4 , R 5 , R 6 and R 7 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 One of them is -(CH2) f - may form a crosslinked structure represented by f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 One of them is -(CH2) g - may form a crosslinked structure represented by g is an integer from 1 to 5, R 16 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 8 carbon atoms, and R 17 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, where R 12 and R13 are bonded to each other to form a double bond, and R 14 , R 15 and R 18 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 14 and R 15 are bonded to each other to form a double bond, and R 12 , R 13 and R 18 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 16 and R 17 may be bonded to each other to form a 4- to 9-membered alicyclic hydrocarbon, where R 14 and R 15 are bonded to each other to form a double bond, and R 12 , R 13 and R 18 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms.] The silane coupling agent composition according to [1], wherein the compound is represented by the formula: [3] The second silane compound is represented by the following formula (12): [ka] [In the formula, Each R 1 , R 2 and R 3 each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom; h is an integer from 1 to 10; m is an integer from 1 to 10, a is an integer between 0 and 1, b is an integer between 0 and 1, c's are each independently an integer of 0 or 1; each d is independently an integer of 0 or 1; e is an integer from 0 to 5, R 4 , R 5 , R 6 and R7 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 One of them is -(CH2) f - may form a crosslinked structure represented by f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 One of them is -(CH2) g - may form a crosslinked structure represented by g is an integer from 1 to 5, R 26 , R 27 and R 28 each independently represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms.] The silane coupling agent composition according to [1] or [2], wherein the compound is represented by the formula: [4] The silane coupling agent composition according to any one of [1] to [3], wherein the content of the second silane compound is 1 to 50 mass% based on the total content of the first silane compound and the second silane compound. [5] The silane coupling agent composition according to any one of [1] to [4], wherein the silane compound further comprises a silane compound other than the first silane compound and the second silane compound. [6] The other silane compound is represented by the formula (13): [ka] [In the formula, t and v each independently represent an integer of 0 to 10; u is an integer from 2 to 10, q and r each independently represent an integer of 1 to 3; w and z are each independently an integer of 0 or 1; L 2 and L 3 are each independently a hydrocarbon group which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur, R 21 and R 23 are each independently an amino group substituted with an alkoxy group or one or more alkyl groups, R 22 and R 24 are each independently hydrogen or an alkyl group. The silane coupling agent composition according to [5], wherein the silane compound is represented by the formula: [7] The silane coupling agent composition according to any one of [1] to [6], which is used for a diene rubber. [8] A rubber composition comprising the silane coupling agent composition according to any one of [1] to [7], a diene rubber, and silica, A rubber composition, wherein the total content of the first silane compound and the second silane compound is 0.5 to 30 parts by mass per 100 parts by mass of the silica. [9] The rubber composition according to [8], wherein the content of the silica is 0.5 to 300 parts by mass per 100 parts by mass of the diene rubber.

[10] The rubber composition according to [8] or [9], which is used for a tire.

[11] A crosslinked product of the rubber composition according to any one of [8] to

[10] .

[12] A pneumatic tire using the crosslinked product according to

[11] in the tire tread. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a silane coupling agent composition that can give a rubber composition that has moderate reactivity with organic polymer materials such as rubber and that is excellent in scorch resistance and uncrosslinked compound viscosity.In addition, according to the present invention, it is possible to provide a rubber composition that is excellent in scorch resistance and uncrosslinked compound viscosity, a crosslinked product of the rubber composition that is excellent in viscoelastic properties, and a tire that uses the same and that has an excellent balance of wet grip properties and fuel economy. [Brief explanation of the drawings]

[0012] [Figure 1] 1 shows a 1H-NMR chart of silane compound 1 synthesized in Preparation Example 1. [Figure 2] 1 is a chromatogram showing that silane compound 1 synthesized in Preparation Example 1 was fractionated into fractions (1A) and (1B) by gas chromatography and each fraction was collected. [Figure 3] This shows the H-NMR chart of fraction (1A) of silane compound 1 synthesized in Preparation Example 1. The peaks indicated by a to g and integers 1 to 7 in circles represent the peaks of protons bonded to each carbon atom (shown in FIG. 3) of the compound represented by formula (1A). [Figure 4] This shows the C-NMR chart of fraction (1A) of silane compound 1 synthesized in Preparation Example 1. Peaks indicated by a to g and integers 1 to 7 in circles represent the peaks of each carbon atom (shown in FIG. 4) of the compound represented by formula (1A). [Figure 5] This shows the H-NMR chart of the (1B) fraction of silane compound 1 synthesized in Preparation Example 1. The peaks A to G and the circled peaks 1 to 7 indicate the peaks of protons bonded to each carbon atom (shown in FIG. 5) of the compound represented by formula (1B). [Figure 6] This shows the C-NMR chart of the (1B) fraction of silane compound 1 synthesized in Preparation Example 1. The peaks A to G and the circled peaks 1 to 7 indicate the peaks of protons bonded to each carbon atom (shown in FIG. 6) of the compound represented by formula (1B). [Figure 7]1 shows a 1H-NMR chart of silane compound 2 synthesized in Preparation Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0013] [Definition] In this specification, "parts", "%" and the like indicating the composition are based on mass unless otherwise specified.

[0014] [Silane Coupling Agent Composition] The silane coupling agent composition of the present invention contains a silane compound, which contains a first silane compound and a second silane compound. The silane coupling agent composition of the present invention can provide a rubber composition that has appropriate reactivity with organic polymer materials such as rubber and is excellent in scorch resistance and uncrosslinked compound viscosity.

[0015] The total content of the first silane compound and the second silane compound in the silane coupling agent composition is preferably 20 to 100 mass%, more preferably 50 to 100 mass%, and may be 60 to 99 mass%, based on the total mass of the silane coupling agent composition.

[0016] The content of the second silane compound in the silane coupling agent composition is preferably 1 to 50 mass %, more preferably 2 to 40 mass %, and even more preferably 5 to 30 mass %, based on the total content of the first silane compound and the second silane compound. When the content ratio of the second silane compound in the silane coupling agent composition is within the above range, it is possible to provide a rubber composition that has moderate reactivity with organic polymer materials such as rubber, while exhibiting excellent scorch resistance and uncrosslinked compound viscosity. It is also possible to provide a crosslinked product of the rubber composition that has excellent viscoelastic properties, and a tire using the same that exhibits an excellent balance between wet grip properties and fuel economy. A rubber composition with excellent scorch resistance and compound viscosity can be easily obtained.

[0017] The silane coupling agent composition may further contain carbon black. As the carbon black, the carbon black described below in the inorganic material section can be used. Each component of the silane coupling agent composition will be described in detail below.

[0018] (First silane compound) The first silane compound contained in the silane coupling agent composition of the present invention is represented by the following formula (1): [ka] [In the formula, R 1 , R 2 and R 3 each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom; L is a hydrocarbon group which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur; a is an integer between 0 and 1, b is an integer between 0 and 1, c's are each independently an integer of 0 or 1; each d is independently an integer of 0 or 1; e is an integer from 0 to 5, R 4 , R 5 , R 6 and R 7 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 One of them is -(CH2) f - may form a crosslinked structure represented by f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R10 or R 11 One of them is -(CH2) g - may form a crosslinked structure represented by g is an integer from 1 to 5, R 16 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 8 carbon atoms, and R 17 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, where R 12 and R 13 are bonded to each other to form a double bond, and R 14 , R 15 and R 18 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 14 and R 15 are bonded to each other to form a double bond, and R 12 , R 13 and R 18 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 16 and R 17 may be bonded to each other to form a 4- to 9-membered alicyclic hydrocarbon, where R 14 and R 15 are bonded to each other to form a double bond, and R 12 , R 13 and R 18 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms.] It is a compound represented by the formula:

[0019] In the above formula (1), a is an integer of 0 or 1, and is preferably 1. Furthermore, b is an integer of 0 or 1, and is preferably 1. Furthermore, each c is independently an integer of 0 or 1, and is preferably 1. Each d is independently an integer of 0 or 1, preferably 1. Furthermore, e is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably an integer of 0 or 1. Also, R 4 , R 5 , R 6 and R 7 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 One of them is -(CH2) f A crosslinked structure represented by - may be formed. Furthermore, f is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably 1. Also, R 8 , R 9 , R 10 and R 11 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 One of them is -(CH2) g A crosslinked structure represented by - may be formed. Furthermore, g is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably 1. Also, R 16 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 8 carbon atoms, preferably a hydrogen atom, a methyl group, or an alkyl group having 2 or 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom, and R 17 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, preferably a hydrogen atom, a methyl group, or an alkyl group having 2 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom; 12 and R 13 are bonded to each other to form a double bond, and R 14 , R 15 and R 18 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 14 and R 15are bonded to each other to form a double bond, and R 12 , R 13 and R 18 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 16 and R 17 may be bonded to each other to form a 4- to 9-membered alicyclic hydrocarbon, preferably a 4- to 7-membered alicyclic hydrocarbon, more preferably a 5- or 6-membered alicyclic hydrocarbon, and even more preferably a 5-membered alicyclic hydrocarbon, wherein R 14 and R 15 are bonded to each other to form a double bond, and R 12 , R 13 and R 18 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms.

[0020] In addition, in the above formula (1), R 1 , R 2 and R 3 each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom. Examples of the hydrocarbon group include an alkyl group, an aralkyl group, and an aryl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2-ethylhexyl group, a cyclopentyl group, and a cyclohexyl group. The alkyl group preferably has 1 to 60 carbon atoms, more preferably 1 to 30 carbon atoms, and is preferably a methyl group or an ethyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. The aralkyl group preferably has 7 to 60 carbon atoms, more preferably 7 to 20 carbon atoms, and even more preferably 7 to 14 carbon atoms. Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, etc. The aryl group preferably has 6 to 60 carbon atoms, more preferably 6 to 24 carbon atoms, and even more preferably 6 to 12 carbon atoms. A hydrocarbon group containing an oxygen atom or a nitrogen atom is a group having a structure in which a carbon atom in a hydrocarbon group is replaced with an oxygen atom or a nitrogen atom.

[0021] In a further preferred embodiment of the present invention, the R 1 , R 2 and R 3 The hydrocarbon group, which may contain an oxygen atom or a nitrogen atom, is an alkoxy group, an amino group substituted with one or more alkyl groups, or an alkyl group. More preferably, it is an alkoxy group having 1 to 30 carbon atoms, even more preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an amino group substituted with one or more alkyl groups having 1 to 30 carbon atoms, even more preferably an amino group substituted with one or more alkyl groups having 1 to 20 carbon atoms, or even more preferably an alkyl group having 1 to 30 carbon atoms, even more preferably an alkyl group having 1 to 20 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group. Of these, a methoxy group or an ethoxy group is preferred. Examples of the amino group substituted with one or more alkyl groups include an N-methylamino group, an N,N-dimethylamino group, an N-ethylamino group, an N,N-diethylamino group, and an N-isopropylamino group. Of these, an N-methylamino group or an N-ethylamino group is preferred. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a cyclopentyl group, a hexyl group, and a cyclohexyl group. Of these, a methyl group and an ethyl group are preferred.

[0022] In the formula (1), L is a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur. Preferably, it is a hydrocarbon group having 1 to 30 carbon atoms optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur. More preferably, it is a hydrocarbon group having 1 to 20 carbon atoms optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur. Even more preferably, it is a hydrocarbon group having 1 to 10 carbon atoms optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur. Among these, it is particularly preferable that L is a hydrocarbon group containing sulfur. The length of the linear portion connecting the silyl group and the alicyclic hydrocarbon moiety in such a hydrocarbon group is preferably 3 to 8, more preferably 4 to 7, and even more preferably 4 to 6, in terms of the total number of carbon, nitrogen, oxygen, or sulfur atoms.

[0023] The first silane compound in the silane coupling agent composition of the present invention is preferably a sulfur-containing silane compound.

[0024] The first silane compound contained in the silane coupling agent composition of the present invention is preferably a compound represented by the formula (2): [ka] [In the formula, R 1 , R 2 and R 3 each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom; h is an integer from 1 to 10; a is an integer between 0 and 1, b is an integer between 0 and 1, c's are each independently an integer of 0 or 1; each d is independently an integer of 0 or 1; e is an integer from 0 to 5, R 4 , R 5 , R 6 and R7 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 One of them is -(CH2) f - may form a crosslinked structure represented by f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 One of them is -(CH2) g - may form a crosslinked structure represented by g is an integer from 1 to 5, R 16 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 8 carbon atoms, and R 17 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, where R 12 and R 13 are bonded to each other to form a double bond, and R 14 , R 15 and R 18 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 14 and R 15 are bonded to each other to form a double bond, and R 12 , R 13 and R 18 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 16 and R 17 may be bonded to each other to form a 4- to 9-membered alicyclic hydrocarbon, where R 14 and R 15 are bonded to each other to form a double bond, and R 12 , R 13 and R 18is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms.] It is a compound represented by the formula:

[0025] In the compound represented by the formula (2), h is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 2 to 7, even more preferably an integer of 3 to 6, still more preferably an integer of 3 to 5, and particularly preferably 3. In addition, a to g and R 1 ~R 18 is as explained in the above formula (1).

[0026] The first silane compound contained in the silane coupling agent composition of the present invention is more preferably a compound represented by formula (3): [ka] [In the formula, R 1 , R 2 and R 3 each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom; h is an integer from 1 to 10; a is an integer between 0 and 1, b is an integer between 0 and 1, c's are each independently an integer of 0 or 1; each d is independently an integer of 0 or 1; e is an integer from 0 to 5, R 4 , R 5 , R 6 and R 7 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 One of them is -(CH2) f - may form a crosslinked structure represented by f is an integer from 1 to 5, R 8 , R 9 , R 10 and R11 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 One of them is -(CH2) g - may form a crosslinked structure represented by g is an integer from 1 to 5, R 31 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 8 carbon atoms.] It is a compound represented by the formula:

[0027] Among the compounds represented by the above formula (3), a to g and R 1 ~R 11 is as explained in the above formula (1), and h is as explained in the above formula (2).

[0028] R in Equation (3) 31 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 8 carbon atoms, preferably a hydrogen atom, a methyl group, or an alkyl group having 2 to 5 carbon atoms, more preferably a hydrogen atom, a methyl group, or an alkyl group having 1 or 2 carbon atoms, and even more preferably a hydrogen atom.

[0029] The first silane compound contained in the silane coupling agent composition of the present invention is more preferably a compound represented by formula (4): [ka] [In the formula, R 1 , R 2 and R 3 each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom; h is an integer from 1 to 10; a is an integer between 0 and 1, b is an integer between 0 and 1, c's are each independently an integer of 0 or 1; each d is independently an integer of 0 or 1; e is an integer from 0 to 5, R 4 , R 5 , R 6 and R 7 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 One of them is -(CH2) f - may form a crosslinked structure represented by f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 One of them is -(CH2) g - may form a crosslinked structure represented by g is an integer from 1 to 5, R 32 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 9 carbon atoms. It is a compound represented by the formula:

[0030] Among the compounds represented by the above formula (4), a to g and R 1 ~R 11 is as explained in the above formula (1), and h is as explained in the above formula (2).

[0031] R in Equation (4) 32 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 9 carbon atoms, preferably a methyl group or an alkyl group having 2 to 5 carbon atoms, more preferably a methyl group or an alkyl group having 1 or 2 carbon atoms, and even more preferably a methyl group.

[0032] The first silane compound contained in the silane coupling agent composition of the present invention is more preferably a compound represented by formula (5): [ka] [In the formula, R 1 , R 2 and R 3 each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom; h is an integer from 1 to 10; a is an integer between 0 and 1, b is an integer between 0 and 1, c's are each independently an integer of 0 or 1; each d is independently an integer of 0 or 1; e is an integer from 0 to 5, R 4 , R 5 , R 6 and R 7 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 One of them is -(CH2) f - may form a crosslinked structure represented by f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 One of them is -(CH2) g - may form a crosslinked structure represented by g is an integer from 1 to 5, and x is an integer from 0 to 5. It is a compound represented by the formula:

[0033] Among the compounds represented by the above formula (5), a to g and R 1 ~R 11is as explained in the above formula (1), and h is as explained in the above formula (2).

[0034] In formula (5), x is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 1 or 2, and even more preferably 1.

[0035] The first silane compound contained in the silane coupling agent composition of the present invention is more preferably a compound represented by formula (6): [ka] [In the formula, R 1 , R 2 and R 3 each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom; or Formula (7): [ka] [In the formula, R 1 , R 2 and R 3 each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom; or Formula (8): [ka] [In the formula, R 1 , R 2 and R 3 each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom; or Formula (9): [ka] [In the formula, R 1 , R 2 and R 3 each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom. It is a compound represented by the formula:

[0036] In the compounds represented by the above formulas (6) to (9), R 1 ~R 3 is as explained in the above formula (1).

[0037] Another more preferred embodiment of the first silane compound in the silane coupling agent composition of the present invention is a compound represented by the following formula: In the compound represented by the following formula, R 1 ~R 3 is as explained in the above formula (1). [ka] [In each formula, R 1 , R 2 and R 3 each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom.

[0038] An even more preferred embodiment of the first silane compound contained in the silane coupling agent composition of the present invention is a compound represented by the formulas (1) to (9) above, wherein R 1 R 2 R 3 The Si group is represented by the formula (10): [ka] [In the formula, R 19 are each independently an amino group substituted with an alkoxy group or one or more alkyl groups, R 20 are each independently a hydrogen atom or an alkyl group, L 1 are each independently a hydrocarbon group which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur, each j is independently an integer of 0 or 1; k is an integer from 1 to 3, The asterisk (*) indicates a bonded portion to a portion other than the silyl group of the silane compound. Examples of suitable silane compounds include those having the following chemical structure:

[0039] In the above formula (10), R 19 are each independently an alkoxy group or an amino group substituted with one or more alkyl groups. In one preferred embodiment, R 19 are each independently a hydrolyzable group, and are an alkoxy group, more preferably an alkoxy group having 1 to 30 carbon atoms, even more preferably an alkoxy group having 1 to 20 carbon atoms, or an amino group substituted with one or more alkyl groups, more preferably an amino group substituted with one or more alkyl groups having 1 to 30 carbon atoms, even more preferably an amino group substituted with one or more alkyl groups having 1 to 20 carbon atoms. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group. Of these, a methoxy group or an ethoxy group is preferred. Furthermore, examples of the amino group substituted with one or more alkyl groups include an N-methylamino group, an N,N-dimethylamino group, an N-ethylamino group, an N,N-diethylamino group, and an N-isopropylamino group. Of these, an N-methylamino group or an N-ethylamino group is preferred. The alkoxy group and the amino group may be bonded to silicon (Si) via a linking group consisting of a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur. Also, R 20 are each independently a hydrogen atom or an alkyl group, more preferably an alkyl group having 1 to 30 carbon atoms, and even more preferably an alkyl group having 1 to 20 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a cyclopentyl group, a hexyl group, and a cyclohexyl group. Of these, a methyl group and an ethyl group are preferred.

[0040] In the above formula (10), L 1are each independently a hydrocarbon group which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur, and are preferably a hydrocarbon group having 1 to 30 carbon atoms which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur, more preferably a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur, and even more preferably a hydrocarbon group having 1 to 10 carbon atoms which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur.

[0041] In the above formula (10), k is an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3. Each j is independently an integer of 0 or 1, preferably 0.

[0042] The first silane compound contained in the silane coupling agent composition of the present invention is represented by the formulas (1) to (9) above, wherein R 1 R 2 R 3 Silane compounds in which the Si group is a triethoxysilyl group or a trimethoxysilyl group are more preferred, and R 1 R 2 R 3 Even more preferred are silane compounds in which the Si group is a triethoxysilyl group.

[0043] A particularly preferred embodiment of the first silane compound contained in the silane coupling agent composition of the present invention is a compound represented by the following formula: [ka]

[0044] The first silane compound of the present invention is preferably a stereoisomer thereof or any mixture of stereoisomers thereof.

[0045] (First method for producing silane compound) One embodiment of a method for producing the first silane compound represented by formula (1) contained in the silane coupling agent composition of the present invention will be described below, but the method is not limited to the following. For example, the first silane compound may be a compound represented by formula (14): [ka] [In the formula, a is an integer between 0 and 1, b is an integer between 0 and 1, c's are each independently an integer of 0 or 1; each d is independently an integer of 0 or 1; e is an integer from 0 to 5, R 4 , R 5 , R 6 and R 7 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 One of them is -(CH2) f - may form a crosslinked structure represented by f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 One of them is -(CH2) g - may form a crosslinked structure represented by g is an integer from 1 to 5, R 16 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 8 carbon atoms, and R 17 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, where R 12 and R 13 are bonded to each other to form a double bond, and R 14 , R 15and R 18 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 14 and R 15 are bonded to each other to form a double bond, and R 12 , R 13 and R 18 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 16 and R 17 may be bonded to each other to form a 4- to 9-membered alicyclic hydrocarbon, where R 14 and R 15 are bonded to each other to form a double bond, and R 12 , R 13 and R 18 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms.] and a compound represented by formula (15): [ka] [In the formula, R 1 , R 2 and R 3 each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom; Y is a hydrocarbon group that may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur. The compound can be produced by reacting a compound represented by the following formula:

[0046] In the above formulas (14) and (15), R 1 ~R 18 and a to g are as described in the first silane compound represented by formula (1).

[0047] In the formula (15), Y is a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur, preferably a hydrocarbon group having 1 to 30 carbon atoms optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur, more preferably a hydrocarbon group having 1 to 20 carbon atoms optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur, and even more preferably a hydrocarbon group having 1 to 10 carbon atoms optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur. Among these, Y is particularly preferably a hydrocarbon group containing sulfur. The length of the linear portion connecting the bonding points of the silyl group and the alicyclic hydrocarbon moiety in such a hydrocarbon group is preferably 3 to 8, more preferably 4 to 7, and even more preferably 4 to 6, in terms of the total number of carbon, nitrogen, oxygen, or sulfur atoms.

[0048] Here, in producing the first silane compound represented by the above formula (1), the compound represented by formula (14) and the compound represented by formula (15) can be synthesized by subjecting them to an addition reaction or a condensation reaction. The addition reaction may be a radical addition reaction, a conjugate addition reaction, a nucleophilic addition reaction, an electrophilic addition reaction, or the like, such as a pericyclic reaction, a hydrosilylation reaction, or a hydroamination reaction. The condensation reaction may be an esterification reaction, an amidation reaction, a thioesterification reaction, a thioamidation reaction, or a Friedel-Crafts reaction, for example.

[0049] The compound represented by formula (14) can be synthesized by the Diels-Alder reaction of the same or different conjugated diene compounds, or the Diels-Alder reaction of a conjugated diene compound with an alkene compound, based on knowledge already known to those skilled in the art. The compound represented by formula (14) can also be prepared by optionally heat-denaturing and / or purifying the compound synthesized by the Diels-Alder reaction.

[0050] The first silane compound represented by formula (2) contained in the silane coupling agent composition of the present invention is a compound represented by formula (14) above and a compound represented by formula (16): [ka] [In the formula, R 1 , R 2 and R 3 each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom; and h is an integer from 1 to 10. The compound can be produced by reacting a compound represented by the following formula:

[0051] In the above formula (14) and formula (16), R 1 ~R 18 and a to g are as described in the first silane compound represented by formula (1), and h is as described in the compound represented by formula (2).

[0052] Here, the compound represented by formula (2) is thought to be synthesized by mixing a compound represented by formula (14) and a compound represented by formula (16) and heating the mixture, resulting in a reaction between the mercapto group in the compound represented by formula (16) and the carbon-carbon unsaturated bond in the compound represented by formula (14). The compound represented by formula (16) is preferably mixed in an amount of 0.1 to 4 moles, more preferably 0.2 to 3 moles, per mole of the compound represented by formula (14). The heating temperature is preferably 40 to 300°C, more preferably 50 to 200°C.

[0053] Examples of the compound represented by the formula (16) include alkoxysilane compounds having a mercapto group. Examples of the alkoxysilane compounds having a mercapto group include mercaptotrimethoxysilane, mercaptotriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyltripropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 4-mercaptobutyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 4 ... butyltriethoxysilane, 2-mercaptoethyltrippropoxysilane, 3-mercaptopropyltrippropoxysilane, 4-mercaptobutyltrippropoxysilane, 2-mercaptoethylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 4-mercaptobutylmethyldimethoxysilane, 2-mercaptoethylmethyldiethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 4-mercaptobutylmethyldiethoxysilane, and the like.

[0054] The compound represented by the formula (2) can also be synthesized by mixing the compound represented by the formula (14) with the compound represented by the formula (13) described below and heating the mixture. It is believed that the compound is synthesized by cleaving the polysulfide bond in the compound represented by the formula (13) described below and reacting this with the carbon-carbon unsaturated bond moiety in the compound represented by the formula (14) above. The compound represented by the formula (13) described below is preferably mixed in an amount of 0.1 to 4 moles, more preferably 0.3 to 3 moles, per mole of the compound represented by the formula (14) above. The heating temperature is preferably 40 to 300°C, more preferably 50 to 200°C.

[0055] If necessary, a radical initiator can be used in combination. Examples of radical initiators include azo compounds such as azobisisobutyronitrile (AIBN) and 1,1'-azobis(cyclohexanecarbonitrile) (ABCN), peroxides such as di-tert-butyl peroxide (t-BuOOBu-t), tert-butyl hydroperoxide (t-BuOOH), benzoyl peroxide (BPO, PhC(=O)OOC(=O)pH), methyl ethyl ketone peroxide, and dicumyl peroxide (DCP), dihalogen compounds such as chlorine molecules, and redox initiators that combine an oxidizing agent and a reducing agent, such as hydrogen peroxide and iron(II) salts or persulfates and sodium bisulfite, which can generate radicals at low temperatures. Examples of initiators that can also be used include triethylborane (Et3B) and diethylzinc (Et2Zn).

[0056] Among the compounds represented by formula (13) described below, commercially available bis[3-(triethoxysilyl)propyl]tetrasulfide may be used, for example, Si-69 manufactured by Evonik. Also, commercially available bis[3-(triethoxysilyl)propyl]disulfide may be used, for example, Si-75 manufactured by Evonik.

[0057] (Second silane compound) The second silane compound contained in the silane coupling agent composition of the present invention is represented by the following formula (11): [ka] [In the formula, Each R 1 , R 2 and R 3 each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom; each L is independently a hydrocarbon group which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur; a is an integer between 0 and 1, b is an integer between 0 and 1, c's are each independently an integer of 0 or 1; each d is independently an integer of 0 or 1; e is an integer from 0 to 5, R 4 , R 5 , R 6 and R 7 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 One of them is -(CH2) f - may form a crosslinked structure represented by f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 One of them is -(CH2) g - may form a crosslinked structure represented by g is an integer from 1 to 5, R 26 , R 27 and R 28 each independently represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms.] It is a compound represented by the formula:

[0058] In the above formula (11), each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 A preferred embodiment of is as explained above in formula (1). In addition, preferred embodiments of each L are as explained in the above formula (1). In addition, preferred embodiments of a, b, c, d, and e are as explained in the above formula (1). R 26 , R 27 and R 28 are each independently a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, and are preferably a hydrogen atom.

[0059] The second silane compound in the silane coupling agent composition of the present invention is preferably a sulfur-containing silane compound.

[0060] The first silane compound represented by formula (11) contained in the silane coupling agent composition of the present invention is preferably a compound represented by formula (12): [ka] [In the formula, Each R 1 , R 2 and R 3 each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom; h is an integer from 1 to 10; m is an integer from 1 to 10, a is an integer between 0 and 1, b is an integer between 0 and 1, c's are each independently an integer of 0 or 1; each d is independently an integer of 0 or 1; e is an integer from 0 to 5, R 4 , R 5 , R 6 and R 7 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 One of them is -(CH2) f - may form a crosslinked structure represented by f is an integer from 1 to 5, R 8 , R 9, R 10 and R 11 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 One of them is -(CH2) g - may form a crosslinked structure represented by g is an integer from 1 to 5, R 26 , R 27 and R 28 each independently represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms.] It is a compound represented by the formula:

[0061] In the above formula (12), each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 26 , R 27 and R 28 A preferred embodiment of is as explained above in formula (11). In addition, preferred embodiments of each L are as explained in the above formula (11). Moreover, the preferred embodiments of a, b, c, d, and e are as explained in the above formula (11). Moreover, the preferred embodiment of h is as explained in the above formula (2). In the above formula (12), m is an integer of 1 to 10, preferably 1 to 8, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3.

[0062] The second silane compound contained in the silane coupling agent composition of the present invention is more preferably a compound represented by formula (17): [ka] [In the formula, each R 1 , R 2 and R 3 each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom; or Formula (18): [ka] [In the formula, each R 1 , R 2 and R 3 each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom. It is a compound represented by the formula:

[0063] In the compounds represented by the above formulas (17) and (18), each R 1 , R 2 and R 3 is as explained in the above formula (11).

[0064] Another more preferred embodiment of the first silane compound in the silane coupling agent composition of the present invention is a compound represented by the following formula: In the compound represented by the following formula, R 1 ~R 3 is as explained in the above formula (1). [ka] TIFF0007731881000026.tif134155

[0065] An even more preferred embodiment of the second silane compound represented by the formula (11) contained in the silane coupling agent composition of the present invention is R 1 R 2 R 3 The second silane compound may be a silane compound in which the Si group has the chemical structure of the above formula (10). 1 R 2 R 3Silane compounds in which the Si group is a triethoxysilyl group or a trimethoxysilyl group are more preferred, and R 1 R 2 R 3 Even more preferred are silane compounds in which the Si group is a triethoxysilyl group.

[0066] A particularly preferred embodiment of the second silane compound contained in the silane coupling agent composition of the present invention is a compound represented by the following formula: [ka] TIFF0007731881000028.tif162155

[0067] The second silane compound of the present invention is preferably a stereoisomer thereof, or any mixture of stereoisomers thereof.

[0068] (Second method for producing silane compound) One embodiment of a method for producing the second silane compound represented by formula (11) contained in the silane coupling agent composition of the present invention will be described below, but the method is not limited to the following method. For example, the second silane compound may be a compound represented by the following formula (14): [ka] [In the formula, a is an integer between 0 and 1, b is an integer between 0 and 1, c's are each independently an integer of 0 or 1; each d is independently an integer of 0 or 1; e is an integer from 0 to 5, R 4 , R 5 , R 6 and R 7 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 One of them is -(CH2)f - may form a crosslinked structure represented by f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 One of them is -(CH2) g - may form a crosslinked structure represented by g is an integer from 1 to 5, R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, provided that R 12 and R 13 are bonded to each other to form a double bond, or R 14 and R 15 are bonded to each other to form a double bond, and R 16 and R 17 may be bonded to each other to form a 4- to 9-membered alicyclic hydrocarbon.] The compound represented by the formula (14) can be produced by reacting a compound represented by the formula (14) with a compound represented by the formula (15). Preferred embodiments of the formulas (14) and (15) are as explained in the first silane compound.

[0069] Here, the second silane compound can be synthesized by subjecting the compound represented by the above formula (14) and the compound represented by the above formula (15) to an addition reaction or a condensation reaction. The addition reaction may be a radical addition reaction, a conjugate addition reaction, a nucleophilic addition reaction, an electrophilic addition reaction, or the like, such as a pericyclic reaction, a hydrosilylation reaction, or a hydroamination reaction. The condensation reaction may be an esterification reaction, an amidation reaction, a thioesterification reaction, a thioamidation reaction, or a Friedel-Crafts reaction, for example.

[0070] The compound represented by formula (14) can be synthesized by the Diels-Alder reaction of the same or different conjugated diene compounds, or the Diels-Alder reaction of a conjugated diene compound with an alkene compound, based on knowledge already known to those skilled in the art. The compound represented by formula (14) can also be prepared by, if necessary, thermally denaturing and / or purifying the compound synthesized by the Diels-Alder reaction.

[0071] The second silane compound can be produced by reacting a compound represented by the above formula (14) with a compound represented by the above formula (16). A preferred embodiment of the above formula (16) is as described for the first silane compound.

[0072] Here, the second silane compound is thought to be synthesized by mixing a compound represented by the above formula (14) and a compound represented by the above formula (16) and heating the mixture, thereby causing a reaction between the mercapto group in the compound represented by the above formula (16) and the two carbon-carbon unsaturated bonds in the compound represented by the above formula (14). The compound represented by the above formula (16) is preferably mixed in an amount of 0.1 to 4 moles, more preferably 0.3 to 3 moles, per mole of the compound represented by the above formula (14). The heating temperature is preferably 40 to 300°C, more preferably 50 to 200°C.

[0073] The second silane compound can also be synthesized by mixing a compound represented by the formula (14) above with a compound represented by the formula (13) described below and heating the mixture. It is believed that the second silane compound is synthesized by cleaving the polysulfide bond in the compound represented by the formula (13) described below and reacting with two carbon-carbon unsaturated bonds in the compound represented by the formula (14) above. The compound represented by the formula (13) described below is preferably mixed in an amount of 0.1 to 4 moles, more preferably 0.3 to 3 moles, per mole of the compound represented by the formula (14) above. The heating temperature is preferably 40 to 300°C, more preferably 50 to 200°C.

[0074] If necessary, a radical initiator can be used in combination. Examples of radical initiators include azo compounds such as azobisisobutyronitrile (AIBN) and 1,1'-azobis(cyclohexanecarbonitrile) (ABCN), peroxides such as di-tert-butyl peroxide (t-BuOOBu-t), tert-butyl hydroperoxide (t-BuOOH), benzoyl peroxide (BPO, PhC(=O)OOC(=O)pH), methyl ethyl ketone peroxide, and dicumyl peroxide (DCP), dihalogen compounds such as chlorine molecules, and redox initiators that combine an oxidizing agent and a reducing agent, such as hydrogen peroxide and iron(II) salts or persulfates and sodium bisulfite, which can generate radicals at low temperatures. Examples of initiators that can also be used include triethylborane (Et3B) and diethylzinc (Et2Zn).

[0075] Among the compounds represented by formula (13) described below, commercially available bis[3-(triethoxysilyl)propyl]tetrasulfide may be used, for example, Si-69 manufactured by Evonik. Also, commercially available bis[3-(triethoxysilyl)propyl]disulfide may be used, for example, Si-75 manufactured by Evonik.

[0076] (Other silane compounds) The silane coupling agent composition of the present invention may further contain other silane compounds (sometimes referred to herein as "other silane compounds") other than the first silane compound and the second silane compound. When a rubber composition containing the silane coupling agent composition of the present invention is vulcanized, the other silane compounds are also incorporated into the vulcanization reaction, causing the first silane compound and the second silane compound, which function as silane coupling agents, to react with the other silane compounds. This reaction is thought to produce a synergistic effect of increasing coupling efficiency. In the rubber composition of the present invention, the other silane compounds are preferably sulfur-containing silane compounds other than the first silane compound and the second silane compound.

[0077] Other silane compounds include, for example, compounds of the formula (13): [ka] [In the formula, t and v each independently represent an integer of 0 to 10; u is an integer from 2 to 10, q and r each independently represent an integer of 1 to 3; w and z are each independently an integer of 0 or 1; L 2 and L 3 are each independently a hydrocarbon group which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur, R 21 and R 23 are each independently an amino group substituted with an alkoxy group or one or more alkyl groups, R 22 and R 24 are each independently a hydrogen atom or an alkyl group. A compound represented by the following formula can be used.

[0078] In the above formula (13), t and v each independently represent an integer of 0 to 10, preferably an integer of 0 to 5, more preferably an integer of 1 to 3, and even more preferably 2. Furthermore, u is an integer of 2 to 10, and more preferably an integer of 2 to 8. Furthermore, q and r each independently represent an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3. Furthermore, w and z are each independently an integer of 0 or 1, preferably 0. Also, L 2 and L 3 are each independently a hydrocarbon group which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur, and are preferably a hydrocarbon group having 1 to 30 carbon atoms which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur, more preferably a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur, and even more preferably a hydrocarbon group having 1 to 10 carbon atoms which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur. Also, R 21 and R 23are each independently a hydrolyzable group, and are an alkoxy group, more preferably an alkoxy group having 1 to 30 carbon atoms, even more preferably an alkoxy group having 1 to 20 carbon atoms, or an amino group substituted with one or more alkyl groups, more preferably an amino group substituted with one or more alkyl groups having 1 to 30 carbon atoms, and even more preferably an amino group substituted with one or more alkyl groups having 1 to 20 carbon atoms. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group. Of these, a methoxy group or an ethoxy group is preferred. Furthermore, examples of the amino group substituted with one or more alkyl groups include an N-methylamino group, an N,N-dimethylamino group, an N-ethylamino group, an N,N-diethylamino group, and an N-isopropylamino group. Of these, an N-methylamino group or an N-ethylamino group is preferred. The alkoxy group and the amino group may be bonded to silicon (Si) via a linking group consisting of a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur. Also, R 22 and R 24 are each independently a hydrogen atom or an alkyl group, more preferably an alkyl group having 1 to 30 carbon atoms, and even more preferably an alkyl group having 1 to 20 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a cyclopentyl group, a hexyl group, and a cyclohexyl group. Of these, a methyl group and an ethyl group are preferred.

[0079] As other silane compounds, in addition to the compound represented by the above formula (13), compounds represented by the above formula (16), particularly silane compounds having the following structure, can be used. [ka]

[0080] The content of the other silane compound in the silane coupling agent composition of the present invention is preferably 0.1 to 0.9, more preferably 0.2 to 0.8, in mass ratio relative to the total content of the first silane compound, the second silane compound, and the other silane compound.

[0081] [Rubber composition] The rubber composition of the present invention is characterized by comprising the silane coupling agent composition of the present invention, a diene rubber, and silica. The rubber composition of the present invention is excellent in scorch resistance and uncrosslinked compound viscosity, and can provide a crosslinked product of the rubber composition having excellent viscoelastic properties, and a tire using the same having an excellent balance of wet grip properties and fuel economy. Such a rubber composition can be suitably used for tires. Each component of the rubber composition will be described in detail below. The silane coupling agent composition is as described in detail above.

[0082] The total content of the first silane compound and the second silane compound in the rubber composition is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 2 to 15 parts by mass, per 100 parts by mass of silica. When the total content of the first silane compound and the second silane compound is within the above range, the rubber composition has excellent scorch resistance and uncrosslinked compound viscosity, and a crosslinked product of the rubber composition having excellent viscoelastic properties can be provided, as well as a tire using the same that has an excellent balance of wet grip performance and fuel economy.

[0083] The content of the other silane compound in the rubber composition is preferably 0.01 to 20 parts by mass, and more preferably 0.05 to 10 parts by mass, based on 100 parts by mass of silica.

[0084] (Diene rubber) The diene rubber contained in the rubber composition of the present invention is not particularly limited, and conventionally known diene rubbers can be used. Examples of diene rubbers include isoprene rubber and other diene rubbers. Examples of isoprene rubber include natural rubber (NR), deproteinized natural rubber, and synthetic isoprene rubber. Examples of natural rubber include natural rubber latex, technically graded rubber (TSR), smoked sheet (RSS), gutta percha, Eucommia-derived natural rubber, guayule-derived natural rubber, Russian dandelion-derived natural rubber, and plant-fermented rubber. Modified natural rubbers, such as epoxidized natural rubber, methacrylic acid-modified natural rubber, styrene-modified natural rubber, sulfonic acid-modified natural rubber, and zinc sulfonate-modified natural rubber, are also included. The cis / trans / vinyl ratio of the double bonds in natural rubber is not particularly limited, and any ratio can be suitably used. Examples of synthetic isoprene rubber include a copolymer of cis-1,4 isoprene, trans-1,4 isoprene, and 3,4 isoprene (so-called isoprene rubber (IR)). Examples of rubbers partially containing the structure of synthetic isoprene rubber include isoprene-butadiene rubber and halogenated isoprene rubber. In the present invention, it is preferable to use isoprene rubber (IR) as the diene rubber, and it is more preferable to use synthetic isoprene rubber containing 75% or more of a cis-1,4 isoprene structure. The number average molecular weight and molecular weight distribution of the diene rubber are not particularly limited, but a number average molecular weight of 500 to 3,000,000 and a molecular weight distribution of 1.5 to 15 are preferred.

[0085] Other diene rubbers include butadiene rubber, styrene-butadiene rubber, styrene-isoprene-butadiene rubber, styrene-isoprene rubber, partially hydrogenated styrene-butadiene rubber, styrene-α-methylstyrene-butadiene rubber, ethylene-propylene-diene rubber, etc. Among these, it is preferable to use butadiene rubber and styrene-butadiene rubber.

[0086] The method for producing the diene rubber is not particularly limited, and examples thereof include emulsion polymerization, solution polymerization, radical polymerization, anionic polymerization, cationic polymerization, etc. The glass transition temperature is also not particularly limited.

[0087] The content of the diene rubber is preferably 20 to 80 mass %, more preferably 25 to 75 mass %, and even more preferably 30 to 70 mass %, based on the total mass of the solid content of the rubber composition.

[0088] (Inorganic materials) Examples of inorganic materials contained in the rubber composition of the present invention include silica, carbon black, calcium carbonate, titanium oxide, clay, and talc, and these can be used alone or in combination. Among these, at least silica is used in the present invention because it can further improve mechanical properties and heat resistance. The amount of inorganic material added is preferably 0.1 to 500 parts by mass, more preferably 1 to 300 parts by mass, per 100 parts by mass of diene rubber.

[0089] The silica is not particularly limited, but examples thereof include dry process silica, wet process silica, colloidal silica, and precipitated silica. Among these, wet process silica, which is mainly composed of hydrous silicic acid, is preferred. These silicas can be used alone or in combination of two or more. The specific surface area of ​​these silicas is not particularly limited, but is usually 10 to 400 m as measured by nitrogen adsorption specific surface area (BET method). 2 / g, preferably 20 to 300m 2 / g, more preferably 120 to 190m 2 When the specific surface area is in the range of / g, sufficient improvements in reinforcement, abrasion resistance, heat buildup, etc. are achieved, and this is preferable. Here, the nitrogen adsorption specific surface area is a value measured by the BET method in accordance with ASTM D3037-81. The amount of silica added is preferably 1 to 300 parts by mass, more preferably 5 to 200 parts by mass, and even more preferably 10 to 150 parts by mass, per 100 parts by mass of diene rubber.

[0090] Carbon black is appropriately selected and used depending on the application. Generally, carbon black is classified into hard carbon and soft carbon based on particle size. Soft carbon has low reinforcing properties for rubber, while hard carbon has high reinforcing properties for rubber. In the rubber composition of the present invention, it is preferable to use hard carbon, which has particularly high reinforcing properties. The amount of carbon black added is preferably 1 to 300 parts by mass, more preferably 5 to 200 parts by mass, and even more preferably 10 to 150 parts by mass, per 100 parts by mass of diene rubber. Carbon black may be added to the rubber composition or to the silane coupling agent composition.

[0091] (Other processing aids) The rubber composition of the present invention may contain other processing aids such as a vulcanizing agent such as sulfur, a vulcanization accelerator, a vulcanization acceleration aid, an antioxidant, a colorant, a softener, various oils, an antioxidant, a filler, and a plasticizer, within the scope of the present invention.

[0092] Examples of the vulcanizing agent include sulfur-based vulcanizing agents such as powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, and alkylphenol disulfide, as well as zinc oxide, magnesium oxide, litharge, p-quinone dioxam, p-dibenzoylquinone dioxime, tetrachloro-p-benzoquinone, poly-p-dinitrobenzene, methylenedianiline, phenol resin, brominated alkylphenol resin, and chlorinated alkylphenol resin. The amount of the vulcanizing agent added is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the diene rubber.

[0093] Examples of vulcanization accelerators include thiuram-based accelerators such as tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), and tetramethylthiuram monosulfide (TMTM), aldehyde-ammonia-based accelerators such as hexamethylenetetramine, guanidine-based accelerators such as diphenylguanidine, thiazole-based accelerators such as 2-mercaptobenzothiazole (MBT) and dibenzothiazyl disulfide (DM), sulfenamide-based accelerators such as N-cyclohexyl-2-benzothiazyl sulfenamide (CBS) and Nt-butyl-2-benzothiazyl sulfenamide (BBS), and dithiocarbamate-based accelerators such as zinc dimethyldithiocarbamate (ZnPDC). The amount of vulcanization accelerator added is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of diene rubber.

[0094] Examples of the vulcanization accelerator aid include fatty acids such as acetyl acid, propionic acid, butanoic acid, stearic acid, acrylic acid, and maleic acid, zinc fatty acids such as zinc acetylate, zinc propionate, zinc butanoate, zinc stearate, zinc acrylate, and zinc maleate, and zinc oxide. The amount of the vulcanization accelerator aid added is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the diene rubber.

[0095] Examples of the antioxidant include hindered phenol compounds, aliphatic and aromatic hindered amine compounds, etc. The amount of antioxidant added is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the diene rubber.

[0096] Examples of antioxidants include butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), etc. The amount of antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of diene rubber.

[0097] Examples of colorants include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochlorides, sulfates, etc., azo pigments, copper phthalocyanine pigments, etc. The amount of colorant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of diene rubber.

[0098] In the present invention, the other processing aids can be used as a rubber composition by kneading them with a known rubber kneading machine, such as a roll, a Banbury mixer, a kneader, etc., and vulcanizing under any conditions. The amounts of these other processing aids added can be conventional amounts as long as they do not deviate from the spirit of the present invention.

[0099] [Method of manufacturing rubber composition] The method for producing the rubber composition of the present invention comprises a step of kneading the silane coupling agent, the diene rubber, and the inorganic material.The method for producing the rubber composition of the present invention preferably comprises a step of kneading the silane coupling agent, the diene rubber, the inorganic material, and the vulcanization accelerator aid.

[0100] The method for producing the rubber composition of the present invention may preferably further include a step of kneading the vulcanizing agent, and more preferably a step of kneading the vulcanizing agent and the vulcanization accelerator.

[0101] In each of the above steps, the rubber composition may be appropriately blended with the other processing aids described above within the scope of the present invention.

[0102] A conventionally known kneading device can be used to produce the rubber composition, and the kneading temperature, time, compounding order, etc. can be appropriately selected.

[0103] [Cross-linked rubber composition] Using the rubber composition of the present invention, a crosslinked product of the rubber composition can be produced according to a conventionally known method and common technical knowledge widely known to those skilled in the art. For example, the rubber composition can be extruded, molded using a molding machine, and then heated and pressurized using a vulcanizer to form crosslinks, thereby producing a crosslinked product.

[0104] [tire] The tire of the present invention comprises a crosslinked product of the rubber composition of the present invention. The tire of the present invention can be manufactured using the rubber composition by a conventionally known method and common technical knowledge widely known to those skilled in the art. For example, the rubber composition is extruded, then molded using a tire building machine, and then heated and pressurized using a vulcanizer to form crosslinks, thereby manufacturing a tire. By manufacturing a tire using the rubber composition of the present invention, it is possible to improve wet grip performance and fuel economy in tire performance in a well-balanced manner.

[0105] The use of the tire is not particularly limited, and examples thereof include tires for passenger cars, tires for heavy loads, tires for motorcycles (motorcycles), and studless tires.

[0106] The shape, structure, size, and material of the tire are not particularly limited and can be appropriately selected depending on the purpose. In addition, the rubber composition can be applied to various parts of the tire, and the part to which the rubber composition is applied is not particularly limited and can be appropriately selected depending on the purpose, such as the tread, carcass, sidewall, inner liner, undertread, or belt part of the tire. In the present invention, a pneumatic tire using the rubber composition in the tire tread is preferred. [Example]

[0107] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0108] [Preparation Example 1: Synthesis of Silane Compound 1 (VNB-SSi)] A 100 mL three-neck flask was fitted with a ball stopper, a three-way stopcock connected to a vacuum / dry nitrogen line, and a septum. A stir bar was then inserted. The system was heated with a hairdryer and degassed and replaced with nitrogen 10 times until a nitrogen atmosphere was achieved. 27.5 g (0.225 mol) of 2-vinylnorbornene (VNB) was injected into the flask using a syringe. 0.074 g (0.45 mmol) of azobisisobutyronitrile was added under a nitrogen atmosphere, followed by 20 minutes of nitrogen bubbling. Next, 10.7 g (0.045 mol) of mercaptopropyltriethoxysilane was aspirated using a gas-tight syringe and attached to a metering pump, which was set to drip the entire amount over 3 hours. Finally, the connection was sealed with silicone grease, and the needle tip of a gas-tight syringe was introduced into the flask through the septum. The flask was then immersed in an oil bath, and the bath temperature was gradually increased. When the internal temperature reached 50°C, the metering pump was activated and mercaptopropyltriethoxysilane was added dropwise to cause a reaction. Two hours after the entire amount had been added dropwise, the oil bath was removed from the flask and the flask was allowed to stand at room temperature. Next, the excess VNB was distilled off under reduced pressure, yielding 37.4 g of the desired colorless, clear liquid. 1 The results of H-NMR measurements are shown in Figure 1. 1 H-NMR measurement and 13 C-NMR measurements confirmed that the silane introduction rate was 100% and that the double bond in the norbornene ring had disappeared. [ka]

[0109] [Detection of stereoisomers of silane compound 1] The obtained silane compound 1 was fractionated by gas chromatography into a fraction containing a large amount of the compound represented by formula (1A) ("fraction (1A)") and a fraction containing a large amount of the compound represented by formula (1B) ("fraction (1B)"), and the fractions were collected (Figure 2). 1 The H-NMR measurement results are shown in Figure 3. 13 The results of C-NMR are shown in Figure 4. 1 The H-NMR measurement results are shown in Figure 5.13 The results of C-NMR are shown in Figure 6. In the chemical structures represented by formulas (1A) and (1B), the peak of the proton bonded to the carbon atom directly bonded to the norbornene ring of the double bond of the vinyl group (the carbon atom indicated by the circled integer 2 in Figure 3 or Figure 5) was observed to be split. From this data, it was inferred that two stereoisomers exist: an isomer in which the vinyl group bonded to the norbornene ring extends forward into the paper, similar to the crosslinked structure of the norbornene ring (syn isomer), and an isomer in which the vinyl group bonded to the norbornene ring extends backward into the paper, opposite the crosslinked structure of the norbornene ring (anti isomer). Similarly, it is presumed that there are two stereoisomers: an isomer in which the sulfur atom bonded to the norbornene ring extends forward into the paper, similar to the bridged structure of the norbornene ring (syn isomer), and an isomer in which the sulfur atom bonded to the norbornene ring extends backward into the paper, opposite the bridged structure of the norbornene ring (anti isomer). From the above, it is presumed that the obtained silane compound 1 is a mixture of eight stereoisomers represented by the following formulas. [ka]

[0110] [Preparation Example 2: Synthesis of silane compound 2 (VNB-2SSi)] A 50 mL three-neck flask was fitted with a ball stopper, a three-way stopcock connected to a vacuum / dry nitrogen line, and a septum. A stir bar was then inserted. The system was heated with a hair dryer and degassed and replaced with nitrogen 10 times until a nitrogen atmosphere was achieved. 5.2 g (0.043 mol) of 2-vinylnorbornene (VNB) and 20.3 g (0.085 mol) of mercaptopropyltriethoxysilane were injected into the flask using a syringe. 0.14 g (0.85 mmol) of azobisisobutyronitrile was added under a nitrogen atmosphere, followed by 20 minutes of nitrogen bubbling. After sealing the connections with silicone grease, the flask was immersed in an oil bath. The bath temperature was gradually increased to 50 °C and the reaction time was 13 hours, followed by an additional 5 hours at 70 °C. Next, mercaptopropyltriethoxysilane was added twice in total (first addition: 0.10 g (0.85 mmol), second addition: 0.26 g (2.13 mmol)), and the reaction was carried out at 70°C for 5 hours each time. After that, the mixture was allowed to cool to room temperature, and 25.0 g of the desired colorless to pale yellow, clear liquid was obtained. The obtained compound 1 The results of H-NMR measurements are shown in Figure 7. 1 H-NMR measurements confirmed that the silane introduction rate was 100%, and that the double bonds in both the norbornene ring and the vinyl group had disappeared. [ka]

[0111] [Detection of stereoisomers of silane compound 2] The obtained silane compound 2 1 The results of H-NMR measurements are shown in Figure 7. 1H-NMR analysis confirmed the disappearance of the double bond vinyl group of the vinyl group. It is presumed that silane compound 2 was obtained by further reacting mercaptosilane with the vinyl group of the eight stereoisomers (1-adducts) of silane compound 1 synthesized in Preparation Example 1 to produce the 2-adduct. It is presumed that the addition to the vinyl group only occurs at the 1-position (outside) of the vinyl group, which is less sterically hindered, and that the stereoisomerism of silane compound 1 is maintained during the addition to the vinyl group. Based on the above, it is presumed that the obtained silane compound 2 is a mixture of the eight stereoisomers represented by the following formula: [ka]

[0112] [Example 1-1] (Preparation of Silane Coupling Agent Composition, Rubber Composition, and Rubber Sheet) First, the entire amount of silane compound 1 (VNB-SSi) and the entire amount of silane compound 2 (VNB-2SSi) were mixed to obtain a silane coupling agent composition. Next, the following components were kneaded using a 100 mL kneader (Labo Plastomill, manufactured by Toyo Seiki Seisakusho) to obtain a rubber composition. Details of the kneading operation performed are as follows (i) to (iii). (i) Mixer kneading: Natural rubber was placed in an internal pressure kneader heated to 150°C and masticated at 30 rpm for 1 minute. Then, half of the silica, zinc oxide, stearic acid, and antioxidant mixture and the entire silane coupling agent composition prepared above were added, and the rotation speed was increased to 50 rpm. Mixing was continued for 1 minute 30 seconds. The remaining half of the silica, zinc oxide, stearic acid, and antioxidant mixture was added, and mixing was continued for 1 minute 30 seconds. After that, the ram (floating weight) was raised and the surrounding powder of the silica, zinc oxide, stearic acid, and antioxidant mixture was added to the kneaded mixture using a brush. Mixing was continued for another 1 minute. The ram was then raised again, and the surrounding powder of the silica, zinc oxide, stearic acid, and antioxidant mixture was added to the kneaded mixture using a brush. Mixing was continued for another 3 minutes, and the mixture was then discharged. (ii) Remilling: To improve the dispersion of the silica, the kneaded material was discharged into an internal pressure kneader heated to 120°C, and after the temperature had sufficiently decreased, it was further kneaded at 50 rpm for 2 minutes and then discharged. (iii) Roll kneading (addition of vulcanization system): After the temperature had dropped sufficiently after release, sulfur, vulcanization accelerator, etc. were added to the above kneaded material using two rolls and kneaded to obtain a rubber composition. Thereafter, the obtained unvulcanized rubber composition was placed in a mold (150 mm x 150 mm x 2 mm) and heated and pressed at 160°C for 30 minutes to obtain a vulcanized rubber sheet having a thickness of 2 mm. Styrene-butadiene rubber (manufactured by ZS Elastomers, product name: NS616) 70 parts by mass Butadiene rubber (manufactured by Ube Industries, product name: UBEPOL BR150) 30 parts by mass Silica AQ (manufactured by Tosoh Corporation, product name: Nipsil AQ) 60 parts by weight 3 parts by weight of zinc oxide No. 3 (manufactured by Toho Zinc Co., Ltd., product name: Ginrei R) 1 part by weight of stearic acid (manufactured by Shin-Nippon Rika, product name: Stearic Acid 300) Anti-aging agent (Ouchi Shinko Chemical Co., Ltd., product name: Nocrac 6C) 1 part by mass ·Silane compound 1 (VNB-SSi) (Preparation example 1) 4.56 parts by mass ·Silane compound 2 (VNB-2SSi) (Preparation example 2) 0.24 parts by mass Sulfur (Hosoi Chemical Co., Ltd., 5% oil-treated sulfur) 2.14 parts by mass 2.3 parts by mass of vulcanization accelerator (manufactured by Ouchi Shinko Chemical Co., Ltd., product name: Noccela CZ) Vulcanization accelerator (manufactured by Ouchi Shinko Chemical Co., Ltd., product name: Noccela D) 1.1 parts by mass

[0113] [Example 1-2] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Example 1-1, except that the amount of silane compound 1 (VNB-SSi) added was changed to 4.32 parts by mass and the amount of silane compound 2 (VNB-2SSi) added was changed to 0.48 parts by mass.

[0114] [Examples 1-3] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Example 1-1, except that the amount of silane compound 1 (VNB-SSi) added was changed to 4.08 parts by mass and the amount of silane compound 2 (VNB-2SSi) added was changed to 0.72 parts by mass.

[0115] [Examples 1-4] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Example 1-1, except that the amount of silane compound 1 (VNB-SSi) added was changed to 3.60 parts by mass and the amount of silane compound 2 (VNB-2SSi) added was changed to 1.20 parts by mass.

[0116] [Examples 1-5] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Example 1-1, except that the amount of silane compound 1 (VNB-SSi) added was changed to 3.06 parts by mass, the amount of silane compound 2 (VNB-2SSi) added was changed to 0.54 parts by mass, 1.20 parts by mass of another silane compound (Si69) was added, and the amount of sulfur added was changed to 1.86 parts by mass.

[0117] [Comparative Example 1-1] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Example 1-1, except that silane compound 1 (VNB-SSi) and silane compound 2 (VNB-2SSi) were not added, 4.80 parts by mass of another silane compound (Si69) was added, and the amount of sulfur added was changed to 1.00 parts by mass.

[0118] [Comparative Example 1-2] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Example 1-1, except that silane compound 1 (VNB-SSi) was not added and the amount of silane compound 2 (VNB-2SSi) added was changed to 4.80 parts by mass.

[0119] [Physical property evaluation] The physical properties of the rubber sheets obtained in Examples 1-1 to 1-5 and Comparative Examples 1-1 and 1-2 were evaluated by the following methods.

[0120] (viscoelasticity) Using a viscoelasticity measuring device (REOGEL E-4000 manufactured by UBM) in accordance with JIS K 6394, tan δ was determined at measurement temperatures of 0°C and 60°C for the rubber sheets obtained in Examples 1-1 to 1-5 and Comparative Examples 1-1 and 1-2 under conditions of a strain of approximately 0.1% and a frequency of 10 Hz, and the tan δ balance (= tan δ (0°C) / tan δ (60°C)) was calculated from these values. A larger tan δ balance means that the viscoelastic properties of the rubber sheet are better, and that the balance between wet grip properties and fuel economy as a tire is better.

[0121] (uncrosslinked compound viscosity) The Mooney viscosity of the rubber compositions obtained in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-2 was measured in accordance with JIS K6300 using a Mooney viscometer with an L-shaped rotor (38.1 mm diameter, 5.5 mm thickness) under conditions of 1 minute preheating time, 4 minutes rotor rotation time, 100°C, and 2 rpm. A smaller measurement result means a lower viscosity of the rubber composition and better processability.

[0122] (Scorch resistance) In accordance with JIS K6300, an unvulcanized rubber composition was preheated at 125°C for 1 minute and then the time t5 required for the viscosity to increase by 5 Mooney units from the minimum viscosity Vm was measured using a rotorless Mooney measuring machine manufactured by Toyo Seiki Co., Ltd. A larger measurement result indicates a longer scorch time and better processability of the rubber composition.

[0123] The results of the above measurements are shown in Table 1. Each measurement value is expressed as an index, with the value in Comparative Example 1-1 being 100.

[0124] [Table 1]

[0125] The results of Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-2 show that the use of a silane coupling agent composition containing silane compound 1 and silane compound 2 improved the scorch resistance of the rubber composition, improved the viscosity of the uncrosslinked compound, and improved the viscoelastic properties of the rubber sheet. Therefore, it was found that the use of the silane coupling agent composition and rubber composition of the present invention improved the processability of the rubber and made it possible to manufacture a tire that had an excellent balance of wet grip performance and fuel economy in practical use.

[0126] [Example 2-1] (Preparation of Silane Coupling Agent Composition, Rubber Composition, and Rubber Sheet) First, the entire amount of silane compound 1 (VNB-SSi) and the entire amount of silane compound 2 (VNB-2SSi) were mixed to obtain a silane coupling agent composition. Next, the following components were kneaded using a 100 mL kneader (Labo Plastomill, manufactured by Toyo Seiki Seisakusho) to obtain a rubber composition. Details of the kneading operation performed are as follows (i) to (iii). (i) Mixer kneading: Natural rubber was placed in an internal pressure kneader heated to 150°C and masticated at 30 rpm for 1 minute. Then, half of the silica, zinc oxide, stearic acid, and antioxidant mixture and the entire silane coupling agent composition prepared above were added, and the rotation speed was increased to 50 rpm. Mixing was continued for 1 minute 30 seconds. The remaining half of the silica, zinc oxide, stearic acid, and antioxidant mixture was added, and mixing was continued for 1 minute 30 seconds. After that, the ram (floating weight) was raised and the surrounding powder of the silica, zinc oxide, stearic acid, and antioxidant mixture was added to the kneaded mixture using a brush. Mixing was continued for another 1 minute. The ram was then raised again, and the surrounding powder of the silica, zinc oxide, stearic acid, and antioxidant mixture was added to the kneaded mixture using a brush. Mixing was continued for another 3 minutes, and the mixture was then discharged. (ii) Remilling: To improve the dispersion of the silica, the kneaded material was discharged into an internal pressure kneader heated to 120°C, and after the temperature had sufficiently decreased, it was further kneaded at 50 rpm for 2 minutes and then discharged. (iii) Roll kneading (addition of vulcanization system): After the temperature had dropped sufficiently after release, sulfur, vulcanization accelerator, etc. were added to the above kneaded material using two rolls and kneaded to obtain a rubber composition. Thereafter, the obtained unvulcanized rubber composition was placed in a mold (150 mm x 150 mm x 2 mm) and heated and pressed at 160°C for 30 minutes to obtain a vulcanized rubber sheet having a thickness of 2 mm. Synthetic isoprene rubber (manufactured by Nippon Zeon Co., Ltd., product name: IR-2200) 100 parts by mass Silica AQ (manufactured by Tosoh Corporation, product name: Nipsil AQ) 60 parts by weight 3 parts by weight of zinc oxide No. 3 (manufactured by Toho Zinc Co., Ltd., product name: Ginrei R) 1 part by weight of stearic acid (manufactured by Shin-Nippon Rika, product name: Stearic Acid 300) Anti-aging agent (Ouchi Shinko Chemical Co., Ltd., product name: Nocrac 6C) 1 part by mass ·Silane compound 1 (VNB-SSi) (Preparation example 1) 4.27 parts by mass ·Silane compound 2 (VNB-2SSi) (Preparation example 2) 0.53 parts by mass Sulfur (Hosoi Chemical Co., Ltd., 5% oil-treated sulfur) 3.14 parts by mass Vulcanization accelerator (Ouchi Shinko Chemical Co., Ltd., product name: Noccela CZ) 1.00 parts by mass Vulcanization accelerator (manufactured by Ouchi Shinko Chemical Co., Ltd., product name: Noccela D) 0.5 parts by mass

[0127] [Comparative Example 2-1] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Example 2-1, except that silane compound 1 (VNB-SSi) and silane compound 2 (VNB-2SSi) were not added, 4.80 parts by mass of another silane compound (Si69) was added, and the amount of sulfur added was changed to 2.00 parts by mass.

[0128] [Physical property evaluation] The viscoelasticity of the rubber sheets obtained in Example 2-1 and Comparative Example 2-1 was evaluated, and the scorch resistance and uncrosslinked compound viscosity of the rubber compositions were evaluated by the same methods as in Example 1-1. The measurement results and calculation results (tan δ balance) are shown in Table 2. Each measured value and calculated value is expressed as an index, with the value in Comparative Example 2-1 set to 100.

[0129] [Table 2]

[0130] The results of Example 2-1 and Comparative Example 2-1 show that by using a silane coupling agent composition containing silane compound 1 (VNB-SSi) and silane compound 2 (VNB-SSi), the viscosity of a rubber composition containing synthetic isoprene rubber at the time of uncrosslinking compounding was reduced, and scorch resistance was improved, and further, the viscoelastic properties of the rubber sheet were improved. Therefore, it was found that the use of the silane coupling agent composition and rubber composition of the present invention improved the processability of the rubber, and furthermore, made it possible to manufacture a tire that, in practical terms, had an excellent balance between wet grip performance and fuel economy.

Claims

1. A silane coupling agent composition containing a silane compound, The silane compound is represented by the following formula (3): 【Chemical 1】 [In the formula, R １ , R ２ and R ３ each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom, provided that at least one of R 1 , R 2 and R 3 is an alkoxy group; h is an integer from 1 to 10; a is an integer of 0 or 1, b is an integer of 0 or 1, c's are each independently an integer of 0 or 1; Each d is independently an integer of 0 or 1; e is an integer from 0 to 5; R ４ , R ５ , R ６ and R ７ represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R ４ or R ５ and R ６ or R ７ One of them is -(CH ２ ) ｆ - may form a bridged structure represented by f is an integer from 1 to 5, R ８ , R ９ , R １０ and R １１ represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R ８ or R ９ and R １０ or R １１ One of them is -(CH ２ ) ｇ - may form a bridged structure represented by g is an integer from 1 to 5, R ３１ is a hydrogen atom, a methyl group, or an alkyl group having 2 to 8 carbon atoms. a first silane compound represented by the formula: The following formula (12): 【Chemistry 2】 [In the formula, Each R １ , R ２ and R ３ each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom, provided that at least one of R 1 , R 2 and R 3 is an alkoxy group; h is an integer from 1 to 10; m is an integer from 1 to 10, a is an integer of 0 or 1, b is an integer of 0 or 1; c's are each independently an integer of 0 or 1; Each d is independently an integer of 0 or 1; e is an integer from 0 to 5; R ４ , R ５ , R ６ and R ７ represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R ４ or R ５ and R ６ or R ７ One of them is -(CH ２ ) ｆ - may form a bridged structure represented by f is an integer from 1 to 5, R ８ , R ９ , R １０ and R １１ represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms, or R ８ or R ９ and R １０ or R １１ One of them is -(CH ２ ) ｇ - may form a bridged structure represented by g is an integer from 1 to 5, R ２６ , R ２７ and R ２８ each independently represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms. a second silane compound represented by A silane coupling agent composition, wherein the content of the second silane compound is 1 to 50 mass % based on the total content of the first silane compound and the second silane compound.

2. 2. The silane coupling agent composition according to claim 1, wherein the content of the second silane compound is 5 to 30 mass % based on the total content of the first silane compound and the second silane compound.

3. 3. The silane coupling agent composition according to claim 1, wherein the silane compound further comprises a silane compound other than the first silane compound and the second silane compound.

4. The other silane compound is represented by formula (13): 【Chemistry 3】 [In the formula, t and v are each independently an integer from 0 to 10; u is an integer from 2 to 10, q and r each independently represent an integer of 1 to 3; w and z are each independently an integer of 0 or 1; L ２ and L ３ are each independently a hydrocarbon group which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur, R ２１ and R ２３ are each independently an alkoxy group or an amino group substituted with one or more alkyl groups, provided that when R 21 is an alkoxy group, w is 0, when R 21 is an amino group substituted with one or more alkyl groups, w is 0 or 1, when R 23 is an alkoxy group, z is 0, and when R 23 is an amino group substituted with one or more alkyl groups, z is 0 or 1; R ２２ and R ２４ are each independently hydrogen or an alkyl group. The silane coupling agent composition according to claim 3, wherein the silane compound is represented by the formula:

5. The silane coupling agent composition according to any one of claims 1 to 4, which is used for a diene rubber.

6. A rubber composition comprising the silane coupling agent composition according to any one of claims 1 to 5, a diene rubber, and silica, The rubber composition has a total content of the first silane compound and the second silane compound of 0.5 to 30 parts by mass per 100 parts by mass of the silica.

7. The rubber composition according to claim 6, wherein the content of the silica is 0.5 to 300 parts by mass per 100 parts by mass of the diene rubber.

8. The rubber composition according to claim 6 or 7, which is used in a tire.

9. A crosslinked product of the rubber composition according to any one of claims 6 to 8.

10. A pneumatic tire using the crosslinked product according to claim 9 in the tire tread.

Images