Silane coupling agent composition and rubber composition containing the same

Abstract

The present invention provides a silane coupling agent composition, etc., which can produce a rubber composition having excellent scorch resistance and a cross-linked product of a rubber composition having excellent viscoelastic properties. The silane coupling agent composition of the present invention comprises a silane compound, a protein modifier, and / or a silylation reaction accelerator, wherein the silane compound comprises a first silane compound represented by the following formula (1) and a second silane compound represented by the following formula (11).

Description

Technical Field

[0001] The present invention relates to a silane coupling agent composition and a rubber composition containing the silane coupling agent composition. The present invention also relates to a cross-linked product of the rubber composition and a tire obtained using the rubber composition. Background Art

[0002] Conventionally, silane compounds having reactive functional groups and hydrolyzable groups 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 substituents such as mercapto, polysulfide, amino, and epoxy groups as reactive functional groups highly reactive with organic polymer materials such as rubber, and substituents such as alkoxysilyl groups as hydrolyzable groups highly reactive with inorganic materials such as silica. For example, Patent Document 1 discloses a rubber composition containing a polysulfide silane coupling agent. Furthermore, 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 organosilane compound having a monosulfide bond in order to improve the scorch resistance of the rubber composition and the heat generation properties (viscoelastic properties) of a cross-linked product of the rubber composition.

[0005] Furthermore, to address the issue of impurities in natural rubber hindering the reaction of silane coupling agents, Patent Document 4 discloses a rubber composition comprising silica having a specific specific surface area and a specific monoglyceride in specific amounts. Furthermore, Patent Document 5 discloses a tire rubber composition obtained by treating modified natural rubber with a protease and then further treating it with a lipase and / or phospholipidase. Furthermore, Patent Document 6 discloses a method for producing deproteinized natural rubber latex, characterized in that a protein modifier selected from urea compounds and NaClO is added to the natural rubber latex, and the protein in the latex is removed after the modification treatment. Furthermore, Patent Document 7 discloses a method for producing modified natural rubber, wherein a urea compound is added to the natural rubber latex to release protein from the rubber particles in the natural rubber latex, and the latex is dried in such a manner as to contain the released protein.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 8-259736

[0009] Patent Document 2: Japanese Patent Application Laid-Open No. 11-335381

[0010] Patent Document 3: Japanese Patent Application Laid-Open No. 2014-177432

[0011] Patent Document 4: Japanese Patent Application Laid-Open No. 2016-113515

[0012] Patent Document 5: Japanese Patent Application Laid-Open No. 2016-74844

[0013] Patent Document 6: Japanese Patent Application Laid-Open No. 2004-99696

[0014] Patent Document 7: Japanese Patent Application Laid-Open No. 2010-111722 Summary of the Invention

[0015] However, the reactive functional groups of the silane compounds proposed in Patent Documents 1 and 2 have high polarity. When the organic polymer material being mixed has low polarity, the silane compounds have low affinity for the organic polymer material, which can lead to poor dispersion and mixing. Therefore, when a rubber composition contains a silane coupling agent composition containing such a silane compound, the viscoelastic properties of the crosslinked rubber composition obtained by molding the rubber composition tend to be insufficient. On the other hand, when conventional silane compounds having low-polarity reactive functional groups are added to improve affinity with low-polarity organic polymer materials, their reactivity with the organic polymer material is low, resulting in insufficient performance as silane coupling agents.

[0016] Furthermore, the silane compound described in Patent Document 3 does not have appropriate reactivity with organic polymer materials.

[0017] Furthermore, the rubber composition described in Patent Document 4, which contains silica having a specific specific surface area and a specific monoglyceride in specific amounts, has room for further improvement in tensile properties such as modulus. Furthermore, the tire rubber composition described in Patent Document 5, which uses a modified natural rubber obtained by enzymatic treatment with a protease and then with a lipolytic enzyme and / or a phospholipidase, has concerns that the process is complicated and may become a major factor in increasing costs.

[0018] Furthermore, while Patent Document 6 uses a protein modifier, it is a technology related to the production of liquid natural rubber latex and does not mention dry rubber-like natural rubber. Furthermore, there is no description of a specific silane coupling agent. Patent Document 7 involves adding a protein modifier to natural rubber latex and then using a special device to produce solid natural rubber, but does not describe a specific silane coupling agent.

[0019] The present inventors have discovered that impurities (proteins, phospholipids, etc.) in natural rubber hinder coupling reactions, which can lead to poor mixing and dispersion of organic polymer materials containing natural rubber and inorganic materials such as silica. The present inventors have conducted in-depth research on methods to solve such problems and have discovered that by adding a silane compound having a specific structure and functioning as a coupling agent and a protein modifier to a rubber composition containing a diene rubber (particularly natural rubber or synthetic isoprene rubber), the coupling reaction is promoted. As a result, the dispersibility of inorganic materials such as silica is improved, and the viscoelastic properties of rubber products obtained from the rubber composition are improved. In addition, the present inventors have discovered that by adding the above-mentioned silane compound and a silanization reaction accelerator to a rubber composition containing a diene rubber (particularly natural rubber or synthetic isoprene rubber), the coupling reaction is promoted. As a result, the dispersibility of inorganic materials such as silica is improved, and the viscoelastic properties of rubber products obtained from the rubber composition are improved. The present invention has been completed based on the above findings.

[0020] Therefore, an object of the present invention is to provide a silane coupling agent composition that has appropriate reactivity with organic polymer materials such as rubber and that can produce a rubber composition having excellent scorch resistance and a cross-linked product of the rubber composition having excellent viscoelastic properties. Another object of the present invention is to provide a rubber composition having excellent scorch resistance, a cross-linked product of the rubber composition having excellent viscoelastic properties, and a tire using these compositions that has an excellent balance between wet grip performance and fuel efficiency.

[0021] The present inventors have conducted intensive research and have discovered that by using two alicyclic silane compounds having affinity and appropriate reactivity with organic polymer materials, and having an alicyclic hydrocarbon moiety containing an olefin structure and a silyl group as silane coupling agents, the coupling reaction is promoted. As a result, when the compound is a rubber composition, the dispersibility of inorganic materials such as silica is improved, and the viscoelastic properties of cross-linked products (rubber products) obtained from the rubber composition are improved. The present invention has been completed based on the above findings.

[0022] The present invention includes the following inventions.

[0023] [1] A silane coupling agent composition comprising a silane compound, a protein modifier and / or a silanization reaction accelerator,

[0024] The silane compound includes a first silane compound represented by the following formula (1) and a second silane compound represented by the following formula (11).

[0025]

[0026] [Where,

[0027] 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,

[0028] L is a hydrocarbon group which may contain at least one heteroatom selected from nitrogen, oxygen and sulfur,

[0029] a is an integer of 0 or 1,

[0030] b is an integer of 0 or 1,

[0031] c are each independently an integer of 0 or 1,

[0032] d are each independently an integer of 0 or 1,

[0033] e is an integer from 0 to 5,

[0034] 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 can form -(CH2) f - indicates the cross-linked structure,

[0035] f is an integer from 1 to 5,

[0036] 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 can form -(CH2) g - indicates the cross-linked structure,

[0037] g is an integer from 1 to 5,

[0038] 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, wherein R 12 and R 13 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 R14 and R 15 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,

[0039] Or, R 16 and R 17 Can bond with each other to form four to nine-membered alicyclic hydrocarbons, where R 14 and R 15 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.]

[0040]

[0041] [Where,

[0042] 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,

[0043] Each L is independently a hydrocarbon group which may contain at least one heteroatom selected from nitrogen, oxygen and sulfur,

[0044] a is an integer of 0 or 1,

[0045] b is an integer of 0 or 1,

[0046] c are each independently an integer of 0 or 1,

[0047] d are each independently an integer of 0 or 1,

[0048] e is an integer from 0 to 5,

[0049] 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 can form -(CH2) f - indicates the cross-linked structure,

[0050] f is an integer from 1 to 5,

[0051] 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 can form -(CH2) g - indicates the cross-linked structure,

[0052] g is an integer from 1 to 5,

[0053] 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.]

[0054] [2] The silane coupling agent composition according to [1], wherein the first silane compound is a compound represented by the following formula (2).

[0055]

[0056] [Where,

[0057] 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,

[0058] h is an integer from 1 to 10,

[0059] a is an integer of 0 or 1,

[0060] b is an integer of 0 or 1,

[0061] c are each independently an integer of 0 or 1,

[0062] d are each independently an integer of 0 or 1,

[0063] e is an integer from 0 to 5,

[0064] 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 can form -(CH2) f - indicates the cross-linked structure,

[0065] f is an integer from 1 to 5,

[0066] R 8 、R9 、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 can form -(CH2) g - indicates the cross-linked structure,

[0067] g is an integer from 1 to 5,

[0068] 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, wherein R 12 and R 13 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 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,

[0069] Or, R 16 and R 17 Can bond with each other to form four to nine-membered alicyclic hydrocarbons, where R 14 and R 15 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.]

[0070] [3] The silane coupling agent composition according to [1] or [2], wherein the second silane compound is a compound represented by the following formula (12).

[0071]

[0072] [Where,

[0073] 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,

[0074] h is an integer from 1 to 10,

[0075] m is an integer from 1 to 10,

[0076] a is an integer of 0 or 1,

[0077] b is an integer of 0 or 1,

[0078] c are each independently an integer of 0 or 1,

[0079] d are each independently an integer of 0 or 1,

[0080] e is an integer from 0 to 5,

[0081] 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 can form -(CH2) f - indicates the cross-linked structure,

[0082] f is an integer from 1 to 5,

[0083] 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 can form -(CH2) g - indicates the cross-linked structure,

[0084] g is an integer from 1 to 5,

[0085] 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.]

[0086] [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% by mass relative to the total content of the first and second silane compounds.

[0087] [5] The silane coupling agent composition according to any one of [1] to [4], wherein the silane compound further contains another silane compound other than the first silane compound and the second silane compound.

[0088] [6] The silane coupling agent composition according to [5], wherein the other silane compound is a silane compound represented by formula (13).

[0089]

[0090] [Where,

[0091] t and v are each independently an integer from 0 to 10,

[0092] u is an integer from 2 to 10,

[0093] q and r are each independently an integer of 1 to 3,

[0094] w and z are each independently an integer of 0 or 1,

[0095] L 2 and L 3 are each independently a hydrocarbon group which may contain at least one heteroatom selected from nitrogen, oxygen and sulfur,

[0096] R 21 and R 23 are each independently an alkoxy group or an amino group substituted with one or more alkyl groups,

[0097] R 22 and R 24 are each independently hydrogen or alkyl.]

[0098] [7] The silane coupling agent composition according to any one of [1] to [6], wherein the protein modifier is at least one selected from the group consisting of urea compounds, guanidine compounds, and surfactants.

[0099] [8] The silane coupling agent composition according to any one of [1] to [6], wherein the silylation reaction accelerator is at least one selected from urea compounds and guanidine compounds.

[0100] [9] The silane coupling agent composition according to [7] or [8], wherein the urea compound is urea.

[0101]

[10] The silane coupling agent composition according to [7] or [8], wherein the guanidine compound is diphenylguanidine.

[0102]

[11] The silane coupling agent composition according to any one of [1] to

[10] , further comprising carbon black.

[0103]

[12] The silane coupling agent composition according to any one of [1] to

[11] , which is used in natural rubber and / or synthetic isoprene rubber.

[0104]

[13] A rubber composition comprising the silane coupling agent composition according to any one of [1] to

[12] , a diene rubber, and silica.

[0105] The diene rubber comprises at least natural rubber and / or synthetic isoprene rubber.

[0106] The total content of the first silane compound and the second silane compound is 0.5 to 30 parts by mass relative to 100 parts by mass of the silica.

[0107]

[14] The rubber composition according to

[13] , wherein the content of the silica is 0.5 to 300 parts by mass per 100 parts by mass of the diene rubber.

[0108]

[15] The rubber composition according to

[13] or

[14] , which is used in a tire.

[0109]

[16] A cross-linked product of the rubber composition according to any one of

[13] to

[15] .

[0110]

[17] A pneumatic tire obtained by using the cross-linked product described in

[16] as a tread.

[0111] According to the present invention, a silane coupling agent composition can be provided that has appropriate reactivity with organic polymer materials such as rubber and that can produce a rubber composition having excellent scorch resistance and a cross-linked product of the rubber composition having excellent viscoelastic properties. Furthermore, according to the present invention, a rubber composition having excellent scorch resistance, a cross-linked product of the rubber composition having excellent viscoelastic properties, and a tire obtained using these and having an excellent balance between wet grip performance and fuel efficiency can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0112] Figure 1 The silane compound 1 synthesized in Preparation Example 1 is shown. 1 H-NMR spectrum.

[0113] Figure 2 This is a chromatogram showing the silane compound 1 synthesized in Preparation Example 1 separated into fraction (1A) and fraction (1B) by gas chromatography and the fractions respectively taken out.

[0114] Figure 3 The (1A) fraction of the silane compound 1 synthesized in Preparation Example 1 is shown. 1 H-NMR spectrum. a to g and the peaks represented by integers 1 to 7 enclosed by circles represent the carbon atoms ( Figure 3 The peak of the proton is shown in FIG.

[0115] Figure 4The (1A) fraction of the silane compound 1 synthesized in Preparation Example 1 is shown. 13 C-NMR spectrum. a to g and the peaks represented by integers 1 to 7 enclosed by circles represent the carbon atoms ( Figure 4 The peaks are shown in FIG.

[0116] Figure 5 The (1B) fraction of the silane compound 1 synthesized in Preparation Example 1 is shown. 1 H-NMR spectrum. Peaks A to G and 1 to 7 surrounded by circles represent the carbon atoms ( Figure 5 The peak of the proton is shown in FIG.

[0117] Figure 6 The (1B) fraction of the silane compound 1 synthesized in Preparation Example 1 is shown. 13 C-NMR spectrum. Peaks A to G and 1 to 7 surrounded by circles represent the carbon atoms ( Figure 6 The peak of the proton is shown in FIG.

[0118] Figure 7 The silane compound 2 synthesized in Preparation Example 2 is shown. 1 H-NMR spectrum. DETAILED DESCRIPTION

[0119] [definition]

[0120] In this specification, "parts", "%" and the like indicating the amount of mixture are by mass unless otherwise specified.

[0121] [Silane coupling agent composition]

[0122] The silane coupling agent composition of the present invention is characterized by comprising a first silane compound, a second silane compound, and a protein modifier and / or a silylation reaction accelerator. The silane coupling agent composition of the present invention has appropriate reactivity with organic polymer materials such as rubber and can produce a rubber composition having excellent scorch resistance and a cross-linked product of the rubber composition having excellent viscoelastic properties.

[0123] The total content of the first silane compound and the second silane compound in the silane coupling agent composition is preferably 20 to 99% by mass, more preferably 50 to 95% by mass, and even more preferably 60 to 90% by mass, relative to the total mass of the silane coupling agent composition. Furthermore, the total content of the protein modifier and the silylation reaction accelerator in the silane coupling agent composition is preferably 0.1 to 50% by mass, more preferably 1 to 45% by mass, and even more preferably 5 to 40% by mass, relative to the total mass of the silane coupling agent composition.

[0124] The content of the second silane compound in the silane coupling agent composition is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, and even more preferably 5 to 30% by mass relative to the total content of the first and second silane compounds. When the content ratio of the second silane compound in the silane coupling agent composition is within the above numerical range, the composition exhibits appropriate reactivity with organic polymer materials such as rubber, and a rubber composition having excellent scorch resistance and a cross-linked product of the rubber composition having excellent viscoelastic properties can be readily obtained.

[0125] The silane coupling agent composition may further contain carbon black. As carbon black, the carbon black described in the inorganic material described below can be used. The following describes each component of the silane coupling agent composition in detail.

[0126] (First Silane Compound)

[0127] The first silane compound contained in the silane coupling agent composition of the present invention is a compound represented by the following formula (1).

[0128]

[0129] [Where,

[0130] 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,

[0131] L is a hydrocarbon group which may contain at least one heteroatom selected from nitrogen, oxygen and sulfur,

[0132] a is an integer of 0 or 1,

[0133] b is an integer of 0 or 1,

[0134] c are each independently an integer of 0 or 1,

[0135] d are each independently an integer of 0 or 1,

[0136] e is an integer from 0 to 5,

[0137] 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 can form -(CH2) f - indicates the cross-linked structure,

[0138] f is an integer from 1 to 5,

[0139] 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 can form -(CH2) g - indicates the cross-linked structure,

[0140] g is an integer from 1 to 5,

[0141] 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, wherein R 12 and R 13 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 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,

[0142] Or, R 16 and R 17 Can bond with each other to form four to nine-membered alicyclic hydrocarbons, where R 14 and R 15 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.]

[0143] In the above formula (1), a is an integer of 0 or 1, and preferably 1.

[0144] In addition, b is an integer of 0 or 1, and is preferably 1.

[0145] In addition, c is each independently an integer of 0 or 1, and is preferably 1.

[0146] In addition, d is each independently an integer of 0 or 1, and is preferably 1.

[0147] 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.

[0148] In addition, 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 can form -(CH2) f - represents the cross-linked structure.

[0149] Moreover, f is an integer of 1-5, Preferably it is an integer of 1-4, More preferably, it is an integer of 1-3, More preferably, it is 1.

[0150] In addition, 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 can form -(CH2) g - represents the cross-linked structure.

[0151] 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.

[0152] In addition, 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, further 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, further preferably a hydrogen atom, wherein R 12 and R 13 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 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,

[0153] Or, R 16 and R 17can be bonded to each other to form a four- to nine-membered alicyclic hydrocarbon, preferably a four- to seven-membered alicyclic hydrocarbon, more preferably a five- or six-membered alicyclic hydrocarbon, and further preferably a five-membered alicyclic hydrocarbon, wherein R 14 and R 15 bonded to each other to form a double bond, and R 12 、R 13 and R 18 It is a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms.

[0154] 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.

[0155] Examples of the alkyl group include methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2-ethylhexyl, cyclopentyl, and cyclohexyl. The alkyl group preferably has 1 to 60 carbon atoms, more preferably 1 to 30 carbon atoms. Among them, a methyl group or an ethyl group is preferred.

[0156] Examples of the aralkyl group include benzyl, phenethyl, naphthylmethyl, and biphenylmethyl. 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.

[0157] Examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, and xylyl groups. 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.

[0158] The hydrocarbon group containing an oxygen atom or a nitrogen atom means a group having a structure in which a carbon atom in the hydrocarbon group is substituted with an oxygen atom or a nitrogen atom.

[0159] In a further preferred embodiment of the present invention, the above R 1 、R 2 and R 3The hydrocarbon group in the group optionally containing 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, even 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 methoxy, ethoxy, propoxy, isopropoxy, butoxy, and isobutoxy, with methoxy and ethoxy being preferred. Examples of the amino group substituted with one or more alkyl groups include N-methylamino, N,N-dimethylamino, N-ethylamino, N,N-diethylamino, and N-isopropylamino, with N-methylamino and N-ethylamino being preferred. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, hexyl, and cyclohexyl. Among them, methyl and ethyl are preferred.

[0160] In the above formula (1), L is a hydrocarbon group that may contain at least one heteroatom selected from nitrogen, oxygen, and sulfur. It is preferably a hydrocarbon group having 1 to 30 carbon atoms that may contain at least one heteroatom selected from nitrogen, oxygen, and sulfur. It is more preferably a hydrocarbon group having 1 to 20 carbon atoms that may contain at least one heteroatom selected from nitrogen, oxygen, and sulfur. It is even more preferably a hydrocarbon group having 1 to 10 carbon atoms that may contain at least one heteroatom selected from nitrogen, oxygen, and sulfur. Among them, L is particularly preferably a hydrocarbon group containing sulfur. The length of the linear portion connecting the silyl group to the alicyclic hydrocarbon portion in the above hydrocarbon group is preferably 3 to 8, more preferably 4 to 7, and even more preferably 4 to 6, based on the total number of carbon, nitrogen, oxygen, or sulfur atoms.

[0161] The first silane compound in the silane coupling agent composition of the present invention is preferably a sulfur-containing silane compound.

[0162] The first silane compound contained in the silane coupling agent composition of the present invention is preferably a compound represented by formula (2).

[0163]

[0164] [Where,

[0165] 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,

[0166] h is an integer from 1 to 10,

[0167] a is an integer of 0 or 1,

[0168] b is an integer of 0 or 1,

[0169] c are each independently an integer of 0 or 1,

[0170] d are each independently an integer of 0 or 1,

[0171] e is an integer from 0 to 5,

[0172] 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 can form -(CH2) f - indicates the cross-linked structure,

[0173] f is an integer from 1 to 5,

[0174] 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 can form -(CH2) g - indicates the cross-linked structure,

[0175] g is an integer from 1 to 5,

[0176] 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, wherein R 12 and R 13 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 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,

[0177] Or, R 16 and R 17 Can bond with each other to form four to nine-membered alicyclic hydrocarbons, where R14 and R 15 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.]

[0178] In the compound represented by the above formula (2), h is an integer of 1 to 10, preferably 1 to 8, more preferably 2 to 7, further preferably 3 to 6, further preferably 3 to 5, and particularly preferably 3. 1 ~R 18 As described in the above formula (1).

[0179] The first silane compound contained in the silane coupling agent composition of the present invention is more preferably a compound represented by formula (3).

[0180]

[0181] [Where,

[0182] 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,

[0183] h is an integer from 1 to 10,

[0184] a is an integer of 0 or 1,

[0185] b is an integer of 0 or 1,

[0186] c are each independently an integer of 0 or 1,

[0187] d are each independently an integer of 0 or 1,

[0188] e is an integer from 0 to 5,

[0189] 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 can form -(CH2) f - indicates the cross-linked structure,

[0190] f is an integer from 1 to 5,

[0191] R 8 、R 9 、R10 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 can form -(CH2) g - indicates the cross-linked structure,

[0192] g is an integer from 1 to 5,

[0193] R 31 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 8 carbon atoms.]

[0194] In the compound represented by the above formula (3), a to g and R 1 ~R 11 As described in the above formula (1), h is as described in the above formula (2).

[0195] R in formula (3) 31 It 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 further preferably a hydrogen atom.

[0196] The first silane compound contained in the silane coupling agent composition of the present invention is more preferably a compound represented by formula (4).

[0197]

[0198] [Where,

[0199] 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,

[0200] h is an integer from 1 to 10,

[0201] a is an integer of 0 or 1,

[0202] b is an integer of 0 or 1,

[0203] c are each independently an integer of 0 or 1,

[0204] d are each independently an integer of 0 or 1,

[0205] e is an integer from 0 to 5,

[0206] R 4 、R 5 、R 6 and R 7represents 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 can form -(CH2) f - indicates the cross-linked structure,

[0207] f is an integer from 1 to 5,

[0208] 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 can form -(CH2) g - indicates the cross-linked structure,

[0209] g is an integer from 1 to 5,

[0210] R 32 is a hydrogen atom, a methyl group, or an alkyl group having 2 to 9 carbon atoms.]

[0211] In the compound represented by the above formula (4), a to g and R 1 ~R 11 As described in the above formula (1), h is as described in the above formula (2).

[0212] R in formula (4) 32 It 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 further preferably a methyl group.

[0213] The first silane compound contained in the silane coupling agent composition of the present invention is more preferably a compound represented by formula (5).

[0214]

[0215] [Where,

[0216] 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,

[0217] h is an integer from 1 to 10,

[0218] a is an integer of 0 or 1,

[0219] b is an integer of 0 or 1,

[0220] c are each independently an integer of 0 or 1,

[0221] d are each independently an integer of 0 or 1,

[0222] e is an integer from 0 to 5,

[0223] 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 can form -(CH2) f - indicates the cross-linked structure,

[0224] f is an integer from 1 to 5,

[0225] 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 can form -(CH2) g - indicates the cross-linked structure,

[0226] g is an integer from 1 to 5,

[0227] x is an integer from 0 to 5.]

[0228] In the compound represented by the above formula (5), a to g and R 1 ~R 11 As described in the above formula (1), h is as described in the above formula (2).

[0229] 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.

[0230] The first silane compound contained in the silane coupling agent composition of the present invention is more preferably a compound represented by formula (6), formula (7), formula (8) or formula (9).

[0231]

[0232] [Where R 1 、R 2 and R 3Each independently represents a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom.]

[0233]

[0234] [Where 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.]

[0235]

[0236] [Where 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.]

[0237]

[0238] [Where 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.]

[0239] In the compounds represented by the above formulae (6) to (9), R 1 ~R 3 As described in the above formula (1).

[0240] As another further preferred embodiment of the first silane compound in the silane coupling agent composition of the present invention, there can be mentioned a compound represented by the following formula. In the compound represented by the following formula, R 1 ~R 3 As described in the above formula (1).

[0241]

[0242] [In various forms, 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.]

[0243] As a further preferred embodiment of the first silane compound contained in the silane coupling agent composition of the present invention, R in the above formulas (1) to (9) can be mentioned. 1 R 2 R 3 The Si group is a silane compound having a chemical structure of formula (10).

[0244]

[0245] [Where,

[0246] R 19 are each independently an alkoxy group or an amino group substituted with one or more alkyl groups,

[0247] R 20 are each independently a hydrogen atom or an alkyl group,

[0248] L 1 are each independently a hydrocarbon group which may contain at least one heteroatom selected from nitrogen, oxygen and sulfur,

[0249] j are each independently an integer of 0 or 1,

[0250] k is an integer from 1 to 3,

[0251] The asterisk (*) indicates a site bonded to a portion other than the silyl group of the above-mentioned silane compound.]

[0252] In the above formula (10), R 19 Each independently represents an alkoxy group or an amino group substituted with one or more alkyl groups. 19 Each is independently a hydrolyzable group, and is 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. Specifically, examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, and isobutoxy, with methoxy and ethoxy being preferred. Examples of the amino group substituted with one or more alkyl groups include N-methylamino, N,N-dimethylamino, N-ethylamino, N,N-diethylamino, and N-isopropylamino, with N-methylamino and N-ethylamino being preferred. The alkoxy and amino groups may be bonded to silicon (Si) via a linking group composed of a hydrocarbon group that may contain at least one heteroatom selected from nitrogen, oxygen, and sulfur.

[0253] In addition, R 20 Each is 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. Specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, hexyl and cyclohexyl groups are mentioned, among which methyl and ethyl groups are preferred.

[0254] In the above formula (10), L 1Each is independently a hydrocarbon group which may contain at least one heteroatom selected from nitrogen, oxygen and sulfur, preferably a hydrocarbon group having 1 to 30 carbon atoms which may contain at least one heteroatom selected from nitrogen, oxygen and sulfur, more preferably a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom selected from nitrogen, oxygen and sulfur, and still more preferably a hydrocarbon group having 1 to 10 carbon atoms which may contain at least one heteroatom selected from nitrogen, oxygen and sulfur.

[0255] In the above formula (10), k is an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3.

[0256] In addition, j is each independently an integer of 0 or 1, and is preferably 0.

[0257] The first silane compound contained in the silane coupling agent composition of the present invention is more preferably 1 R 2 R 3 The silane compound wherein the Si group is a triethoxysilyl group or a trimethoxysilyl group, and further preferably R 1 R 2 R 3 A silane compound in which the Si group is a triethoxysilyl group.

[0258] As a particularly preferred embodiment of the first silane compound contained in the silane coupling agent composition of the present invention, a compound represented by the following formula can be mentioned.

[0259]

[0260] The first silane compound of the present invention is preferably a stereoisomer thereof or an arbitrary mixture of these stereoisomers.

[0261] (Method for producing the first silane compound)

[0262] 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 is described below, but the method is not limited to the following. For example, the first silane compound can be produced by reacting a compound represented by formula (14) with a compound represented by formula (15).

[0263]

[0264] [Where,

[0265] a is an integer of 0 or 1,

[0266] b is an integer of 0 or 1,

[0267] c are each independently an integer of 0 or 1,

[0268] d are each independently an integer of 0 or 1,

[0269] e is an integer from 0 to 5,

[0270] 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 can form -(CH2) f - represents a cross-linked structure,

[0271] f is an integer from 1 to 5,

[0272] 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 can form -(CH2) g - represents a cross-linked structure,

[0273] g is an integer from 1 to 5,

[0274] 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, wherein R 12 and R 13 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 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,

[0275] Or, R 16 and R 17 Can bond with each other to form four to nine-membered alicyclic hydrocarbons, where R 14 and R 15 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.]

[0276] R 1 R 2 R 3 Si-Y (15)

[0277] [Where,

[0278] 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,

[0279] Y is a hydrocarbon group which may contain at least one heteroatom selected from nitrogen, oxygen and sulfur.]

[0280] In the above formula (14) and formula (15), R 1 ~R 18 and a to g are as described for the first silane compound represented by formula (1).

[0281] In the above formula (15), Y is a hydrocarbon group that may contain at least one heteroatom selected from nitrogen, oxygen, and sulfur. It is preferably a hydrocarbon group having 1 to 30 carbon atoms that may contain at least one heteroatom selected from nitrogen, oxygen, and sulfur, more preferably a hydrocarbon group having 1 to 20 carbon atoms that may contain at least one heteroatom selected from nitrogen, oxygen, and sulfur, and even more preferably a hydrocarbon group having 1 to 10 carbon atoms that may contain at least one heteroatom selected from nitrogen, oxygen, and sulfur. Among them, Y is particularly preferably a hydrocarbon group containing sulfur. The length of the linear portion connecting the silyl group to the position bonded to the alicyclic hydrocarbon portion in the above hydrocarbon group is preferably 3 to 8, more preferably 4 to 7, and even more preferably 4 to 6, based on the total number of carbon, nitrogen, oxygen, or sulfur atoms.

[0282] Here, in the manufacture of the first silane compound represented by the above-mentioned formula (1), the compound represented by the formula (14) and the compound represented by the formula (15) can be synthesized by subjecting them to an addition reaction or a condensation reaction. As the addition reaction, free radical addition reaction, conjugate addition reaction, nucleophilic addition reaction, electrophilic addition reaction, etc. can be used, for example, a reaction similar to a pericyclic reaction, hydrosilylation reaction, hydroamination reaction, etc. can be used. As the condensation reaction, for example, esterification reaction, amidation reaction, thioesterification reaction, thioamidation reaction, Friedel-Crafts reaction, etc. can be used.

[0283] It should be noted that the compound represented by the above formula (14) can be synthesized based on the knowledge known to those skilled in the art by using the Diels-Alder reaction of the same or different conjugated diene compounds, or the Diels-Alder reaction of a conjugated diene compound and an olefin compound. In addition, the compound represented by the formula (14) can be prepared by thermally modifying the compound synthesized by the Diels-Alder reaction and / or purifying it as needed.

[0284] The first silane compound represented by formula (2) contained in the silane coupling agent composition of the present invention can be produced by reacting the compound represented by formula (14) with the compound represented by formula (16).

[0285]

[0286] [Where,

[0287] 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,

[0288] h is an integer from 1 to 10.]

[0289] In the above formula (14) and formula (16), R 1 ~R 18 and a to g are as described for the first silane compound represented by formula (1). Moreover, h is as described for the compound represented by formula (2).

[0290] Here, it is considered that the compound represented by the above formula (2) is synthesized by mixing the compound represented by the above formula (14) and the compound represented by the above formula (16) and heating them so that the mercapto group in the compound represented by the above formula (16) reacts with the carbon-carbon unsaturated bond portion 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 mol, more preferably 0.2 to 3 mol, relative to 1 mol of the compound represented by the above formula (14). In addition, the heating temperature is preferably 40 to 300°C, more preferably 50 to 200°C.

[0291] Examples of the compound represented by the formula (16) include alkoxysilane compounds having a mercapto group. Examples of the alkoxysilane compound having a mercapto group include mercaptotrimethoxysilane, mercaptotriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyltripropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 4-mercaptobutyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 4-mercaptobutyltriethoxysilane, 2-mercaptoethyltripropoxysilane, 3-mercaptopropyltripropoxysilane, 4-mercaptobutyltripropoxysilane, 2-mercaptoethylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 4-mercaptobutylmethyldimethoxysilane, 2-mercaptoethylmethyldiethoxysilane, 3-mercaptopropylmethyldiethoxysilane, and 4-mercaptobutylmethyldiethoxysilane.

[0292] In addition, the compound represented by the above formula (2) can also be synthesized by mixing the compound represented by the above formula (14) with the compound represented by the formula (13) described later and heating them. It is believed that the polysulfide bond in the compound represented by the formula (13) described later is cleaved and reacts with the carbon-carbon unsaturated bond portion in the compound represented by the formula (14) described above to synthesize it. The compound represented by the formula (13) described later is preferably mixed in an amount of 0.1 to 4 moles, more preferably 0.3 to 3 moles, relative to 1 mole of the compound represented by the formula (14). In addition, the heating temperature is preferably 40 to 300°C, more preferably 50 to 200°C.

[0293] If necessary, a free radical initiator may be used in combination. Examples of free 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), dihalogenated compounds such as chlorine molecules, and redox initiators combining oxidizing and reducing agents such as hydrogen peroxide and iron (II) salts, persulfates, and sodium bisulfite, which generate free radicals at low temperatures; triethylboron (Et3B), and diethylzinc (Et2Zn).

[0294] It should be noted that among the compounds represented by formula (13) described later, commercially available bis[3-(triethoxysilyl)propyl]tetrasulfide can be used, for example, Si-69 manufactured by Evonik. Furthermore, commercially available bis[3-(triethoxysilyl)propyl]disulfide can be used, for example, Si-75 manufactured by Evonik.

[0295] (Second Silane Compound)

[0296] The second silane compound contained in the silane coupling agent composition of the present invention is a compound represented by the following formula (11).

[0297]

[0298] [Where,

[0299] 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,

[0300] Each L is independently a hydrocarbon group which may contain at least one heteroatom selected from nitrogen, oxygen and sulfur,

[0301] a is an integer of 0 or 1,

[0302] b is an integer of 0 or 1,

[0303] c are each independently an integer of 0 or 1,

[0304] d are each independently an integer of 0 or 1,

[0305] e is an integer from 0 to 5,

[0306] 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 can form -(CH2) f - indicates the cross-linked structure,

[0307] f is an integer from 1 to 5,

[0308] 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 can form -(CH2) g - indicates the cross-linked structure,

[0309] g is an integer from 1 to 5,

[0310] R26 、R 27 and R 28 Each independently represents a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms.]

[0311] 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 described in the above formula (1).

[0312] In addition, preferred embodiments of each L are as described in the above formula (1).

[0313] In addition, preferred embodiments of a, b, c, d, and e are as described in the above formula (1).

[0314] 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, and is preferably a hydrogen atom.

[0315] The second silane compound in the silane coupling agent composition of the present invention is preferably a sulfur-containing silane compound.

[0316] The second 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).

[0317]

[0318] [Where,

[0319] 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,

[0320] h is an integer from 1 to 10,

[0321] m is an integer from 1 to 10,

[0322] a is an integer of 0 or 1,

[0323] b is an integer of 0 or 1,

[0324] c are each independently an integer of 0 or 1,

[0325] d are each independently an integer of 0 or 1,

[0326] e is an integer from 0 to 5,

[0327] 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 can form -(CH2) f - indicates the cross-linked structure,

[0328] f is an integer from 1 to 5,

[0329] 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 can form -(CH2) g - indicates the cross-linked structure,

[0330] g is an integer from 1 to 5,

[0331] 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.]

[0332] 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 described in the above formula (11).

[0333] In addition, preferred embodiments of each L are as described in the above formula (11).

[0334] In addition, preferred embodiments of a, b, c, d, and e are as described in the above formula (11).

[0335] In addition, a preferred embodiment of h is as described in the above formula (2).

[0336] In the above formula (12), m is an integer of 1 to 10, preferably 1 to 8, more preferably 1 to 6, further preferably 1 to 4, and even more preferably 1 to 3.

[0337] The second silane compound contained in the silane coupling agent composition of the present invention is more preferably a compound represented by formula (17) or formula (18).

[0338]

[0339] [Wherein, 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.]

[0340]

[0341] [Wherein, 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.]

[0342] In the compounds represented by the above formula (17) and formula (18), each R 1 、R 2 and R 3 As described in the above formula (11).

[0343] As another further preferred embodiment of the second silane compound in the silane coupling agent composition of the present invention, there can be mentioned a compound represented by the following formula. In the compound represented by the following formula, R 1 ~R 3 As described in the above formula (1).

[0344]

[0345]

[0346] As a further preferred embodiment of the second silane compound represented by the above formula (11) contained in the silane coupling agent composition of the present invention, R 1 R 2 R 3The Si group is a silane compound having the chemical structure of the above formula (10). In particular, the second silane compound is more preferably R 1 R 2 R 3 The silane compound wherein the Si group is a triethoxysilyl group or a trimethoxysilyl group, and further preferably R 1 R 2 R 3 A silane compound in which the Si group is a triethoxysilyl group.

[0347] As a particularly preferred embodiment of the second silane compound contained in the silane coupling agent composition of the present invention, a compound represented by the following formula can be mentioned.

[0348]

[0349]

[0350] The second silane compound of the present invention is preferably a stereoisomer thereof or an arbitrary mixture of these stereoisomers.

[0351] (Method for producing the second silane compound)

[0352] 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 is described below, but the method is not limited to the following. For example, the second silane compound can be produced by reacting a compound represented by the following formula (14) with a compound represented by the above formula (15).

[0353]

[0354] [Where,

[0355] a is an integer of 0 or 1,

[0356] b is an integer of 0 or 1,

[0357] c are each independently an integer of 0 or 1,

[0358] d are each independently an integer of 0 or 1,

[0359] e is an integer from 0 to 5,

[0360] 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 can form -(CH2)f - indicates the cross-linked structure,

[0361] f is an integer from 1 to 5,

[0362] 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 can form -(CH2) g - indicates the cross-linked structure,

[0363] g is an integer from 1 to 5,

[0364] 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, wherein R 12 and R 13 can bond to each other to form a double bond, or, R 14 and R 15 can bond to each other to form double bonds. In addition, R 16 and R 17 They can bond with each other to form four- to nine-membered alicyclic hydrocarbons.]

[0365] In addition, preferred embodiments of the above formulae (14) and (15) are as described with respect to the first silane compound.

[0366] Here, in the manufacture of the second silane compound, the compound represented by the above formula (14) and the compound represented by the above formula (15) 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. As the addition reaction, a free radical addition reaction, a conjugated addition reaction, a nucleophilic addition reaction, an electrophilic addition reaction, etc. can be used, for example, a reaction similar to a pericyclic reaction, a hydrosilylation reaction, a hydroamination reaction, etc. can be used. As the condensation reaction, for example, an esterification reaction, an amidation reaction, a thioesterification reaction, a thioamidation reaction, a Friedel-Crafts reaction, etc. can be used.

[0367] It should be noted that the compound represented by the above formula (14) can be synthesized by using the Diels-Alder reaction of the same or different conjugated diene compounds, or the Diels-Alder reaction of a conjugated diene compound and an olefin compound, based on the knowledge known to those skilled in the art. In addition, the compound represented by the above formula (14) can be prepared by thermally modifying the compound synthesized by the Diels-Alder reaction as needed and / or purifying it as needed.

[0368] The second silane compound can be produced by reacting the compound represented by the above formula (14) with the compound represented by the above formula (16). Preferred embodiments of the above formula (16) are as described for the first silane compound.

[0369] Here, it is considered that the second silane compound is synthesized by mixing the compound represented by the above formula (14) and the compound represented by the above formula (16) and heating them to react the mercapto group in the compound represented by the above formula (16) with 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 mol, more preferably 0.3 to 3 mol, per 1 mol of the compound represented by the above formula (14). In addition, the heating temperature is preferably 40 to 300°C, more preferably 50 to 200°C.

[0370] In addition, the second silane compound can also be synthesized by mixing the compound represented by the above formula (14) with the compound represented by the formula (13) described later and heating them. It is believed that the polysulfide bond in the compound represented by the formula (13) described later is cleaved and reacts with the two carbon-carbon unsaturated bond parts in the compound represented by the formula (14) described above to synthesize it. The compound represented by the formula (13) described later is preferably mixed in an amount of 0.1 to 4 moles, more preferably 0.3 to 3 moles, relative to 1 mole of the compound represented by the formula (14). In addition, the heating temperature is preferably 40 to 300°C, more preferably 50 to 200°C.

[0371] If necessary, a free radical initiator may be used in combination. Examples of free 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), dihalogenated compounds such as chlorine molecules, and redox initiators combining oxidizing and reducing agents such as hydrogen peroxide and iron (II) salts, persulfates, and sodium bisulfite, which generate free radicals at low temperatures; triethylboron (Et3B), and diethylzinc (Et2Zn).

[0372] It should be noted that among the compounds represented by formula (13) described later, commercially available bis[3-(triethoxysilyl)propyl]tetrasulfide can be used, for example, Si-69 manufactured by Evonik. Furthermore, commercially available bis[3-(triethoxysilyl)propyl]disulfide can be used, for example, Si-75 manufactured by Evonik.

[0373] (Other silane compounds)

[0374] The silane coupling agent composition of the present invention may further contain other silane compounds (sometimes referred to as "other silane compounds" in this specification) other than the first and second silane compounds. If the rubber composition containing the silane coupling agent composition of the present invention is subjected to a vulcanization reaction, the other silane compounds will also participate in the vulcanization reaction. Therefore, the first and second silane compounds that function as silane coupling agents react with the other silane compounds. It is believed that this reaction produces a synergistic effect that improves coupling efficiency. In the rubber composition of the present invention, the other silane compound is preferably a sulfur-containing silane compound other than the first and second silane compounds.

[0375] As other silane compounds, for example, compounds represented by formula (13) can be used.

[0376]

[0377] [Where,

[0378] t and v are each independently an integer from 0 to 10,

[0379] u is an integer from 2 to 10,

[0380] q and r are each independently an integer of 1 to 3,

[0381] w and z are each independently an integer of 0 or 1,

[0382] L 2 and L 3 are each independently a hydrocarbon group which may contain at least one heteroatom selected from nitrogen, oxygen and sulfur,

[0383] R 21 and R 23 are each independently an alkoxy group or an amino group substituted with one or more alkyl groups,

[0384] R 22 and R 24 are each independently a hydrogen atom or an alkyl group.]

[0385] In the above formula (13), t and v are each independently 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.

[0386] In addition, u is an integer of 2-10, and more preferably an integer of 2-8.

[0387] Furthermore, q and r are each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3.

[0388] In addition, w and z are each independently an integer of 0 or 1, and preferably 0.

[0389] In addition, L 2 and L 3 Each is independently a hydrocarbon group which may contain at least one heteroatom selected from nitrogen, oxygen and sulfur, preferably a hydrocarbon group having 1 to 30 carbon atoms which may contain at least one heteroatom selected from nitrogen, oxygen and sulfur, more preferably a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom selected from nitrogen, oxygen and sulfur, and still more preferably a hydrocarbon group having 1 to 10 carbon atoms which may contain at least one heteroatom selected from nitrogen, oxygen and sulfur.

[0390] In addition, R 21 and R 23 Each is independently a hydrolyzable group, and is 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. Specifically, examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, and isobutoxy, with methoxy and ethoxy being preferred. Examples of the amino group substituted with one or more alkyl groups include N-methylamino, N,N-dimethylamino, N-ethylamino, N,N-diethylamino, and N-isopropylamino, with N-methylamino and N-ethylamino being preferred. The alkoxy and amino groups may be bonded to silicon (Si) via a linking group composed of a hydrocarbon group that may contain at least one heteroatom selected from nitrogen, oxygen, and sulfur.

[0391] In addition, R 22 and R 24 Each is 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. Specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, hexyl and cyclohexyl groups are mentioned, among which methyl and ethyl groups are preferred.

[0392] As other silane compounds, in addition to the compound represented by the above formula (13), a compound represented by the above formula (16), particularly a silane compound having the following structure, can be used.

[0393]

[0394] 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 terms of mass ratio relative to the total content of the first silane compound, the second silane compound, and the other silane compounds.

[0395] (Protein Modifier)

[0396] Protein modifiers known to those skilled in the art can be used as protein modifiers in the silane coupling agent composition of the present invention. Any protein modifier can be used as long as it can reduce the stability of the higher-order structure of the protein in the diene rubber, especially natural rubber. Representative protein modifiers include urea compounds such as urea derivatives and thiourea; guanidine compounds such as guanidine hydrochloride, guanidine thiocyanate, guanidine, and diphenylguanidine; surfactants such as sodium lauryl sulfate; glutaraldehyde, dimethyl suberimidate dihydrochloride, β-mercaptoethanol, dithiothreitol, etc. Any one of these protein modifiers can be used, or two or more can be used in combination. Among them, urea compounds, guanidine compounds, surfactants, glutaraldehyde, and dimethyl suberimidate dihydrochloride are preferably used, and urea derivatives, guanidine hydrochloride, diphenylguanidine, sodium lauryl sulfate, glutaraldehyde, and dimethyl suberimidate dihydrochloride are more preferably used. Examples of urea derivatives include urea, methylurea, ethylurea, propylurea, butylurea, pentylurea, hexylurea, cyclohexylurea, N,N'-dimethylurea, N,N'-diethylurea, N,N,N',N'-tetramethylurea, N,N-dimethyl-N',N'-diphenylurea, diethylurea, dipropylurea, dibutylurea, dipentylurea, dihexylurea, and salts thereof. Among these, urea is preferred. The use of a protein modifier can improve the scorch resistance of the rubber composition. Furthermore, the silane coupling agent composition of the present invention preferably contains both a urea compound and a guanidine compound.

[0397] (Silanization reaction accelerator)

[0398] A silanization reaction accelerator can be used in the silane coupling agent composition of the present invention. The silanization reaction accelerator can be any silanization reaction accelerator as long as it accelerates the silanization reaction between silica and the silane coupling agent. Examples of silanization reaction accelerators include urea derivatives, urea compounds such as thiourea; and guanidine compounds such as guanidine hydrochloride, guanidine thiocyanate, guanidine, and diphenylguanidine. Any one of these silanization reaction accelerators can be used, or two or more can be used in combination. Examples of urea derivatives include urea, methylurea, ethylurea, propylurea, butylurea, pentylurea, hexylurea, cyclohexylurea, N,N'-dimethylurea, N,N'-diethylurea, N,N,N',N'-tetramethylurea, N,N-dimethyl-N',N'-diphenylurea, diethylurea, dipropylurea, dibutylurea, dipentylurea, dihexylurea, and salts thereof. Among these, urea is preferred.

[0399] In the first stage of the silanization reaction between silica and a silane coupling agent, there are two reaction processes: a direct reaction (dealcoholization condensation) between the alkoxy groups of the silane coupling agent and the silanol groups on the silica surface, and a dehydration condensation between the alkoxy groups of the silane coupling agent and the silanol groups on the silica surface after hydrolysis. Then, in the second stage of the silanization reaction, a condensation reaction occurs between adjacent silane coupling agents chemically bonded to the silica surface. The hydrolysis of the silane coupling agent in the first stage reaction is considered to be the rate-limiting reaction, but if a silanization reaction accelerator such as a urea derivative is present, the rate of the hydrolysis reaction increases, promoting the silanization reaction.

[0400] In the present invention, urea compounds, guanidine compounds, and the like can function as both protein modifiers and silylation reaction accelerators. For example, when a silane coupling agent composition containing urea is added to a rubber composition, the urea can both modify the protein in natural rubber and promote the silylation reaction between silica and the silane coupling agent. In this case, if the urea content is X mass % relative to the total mass of the silane coupling agent composition, the "total content of the protein modifier and silylation reaction accelerator" described above is X mass % relative to the total mass of the silane coupling agent composition (i.e., the urea content is not double-counted for both the protein modifier and the silylation reaction accelerator).

[0401] [Rubber composition]

[0402] The rubber composition of the present invention is characterized in that it comprises a silane coupling agent composition of the present invention, a diene rubber, and silica. The rubber composition of the present invention has excellent scorch resistance and therefore good processability. In addition, by using the rubber composition of the present invention, a cross-linked product with excellent viscoelastic properties can be obtained. Such a rubber composition can be suitable for use as a tire. Below, each component of the rubber composition is described in detail. It should be noted that the silane coupling agent composition is as described in detail above.

[0403] The combined content of the first and second silane compounds 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, relative to 100 parts by mass of silica. When the combined content of the first and second silane compounds is within this numerical range, the viscoelastic properties of the cross-linked rubber composition can be enhanced, resulting in a tire with an excellent balance between wet grip performance and fuel efficiency.

[0404] The content of other silane compounds in the rubber composition is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, relative to 100 parts by mass of silica.

[0405] The content of the protein modifier in the rubber composition varies depending on the type of protein modifier and can be any amount as long as it can reduce the stability of the higher-order structure of the protein. The content of the protein modifier in the rubber composition is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.2 to 3.0 parts by mass relative to 100 parts by mass of the diene rubber. It should be noted that when two or more protein modifiers are included, their total content may be within the above numerical range. If the content of the protein modifier is within the above numerical range, the scorch resistance of the rubber composition can be improved. In addition, for example, when a urea compound such as urea is used as the protein modifier, it is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass relative to 100 parts by mass of the diene rubber. Furthermore, when using a guanidine compound such as guanidine hydrochloride as a protein modifier, the content is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass per 100 parts by mass of the diene rubber. In particular, when the guanidine compound is used in combination with a urea compound, the viscosity of the uncrosslinked rubber composition can be reduced, thereby improving processability. In this case, the ratio of the guanidine compound content to the urea compound content (guanidine compound / urea compound) is preferably 0.01 to 3, more preferably 0.05 to 2, and even more preferably 0.1 to 1.

[0406] The content of the silanization reaction accelerator in the rubber composition varies depending on the type of silanization reaction accelerator and can be any amount as long as it promotes the silanization reaction. The content of the silanization reaction accelerator in the rubber composition is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and further preferably 0.2 to 3.0 parts by mass relative to 100 parts by mass of the diene rubber. It should be noted that when two or more silanization reaction accelerators are included, the total content thereof may be within the above numerical range. If the content of the silanization reaction accelerator is within the above numerical range, the scorch resistance of the rubber composition can be improved. In addition, for example, when a urea compound such as urea is used as the silanization reaction accelerator, it is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and further preferably 0.1 to 3 parts by mass relative to 100 parts by mass of the diene rubber. For example, when a guanidine compound such as guanidine hydrochloride is used as a silylation reaction accelerator, the amount thereof is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass per 100 parts by mass of the diene rubber. Guanidine compounds are particularly effective when used in combination with urea compounds. In such cases, the ratio of the guanidine compound content to the urea compound content (guanidine compound / urea compound) is preferably 0.01 to 3, more preferably 0.05 to 2, and even more preferably 0.1 to 1.

[0407] (Diene rubber)

[0408] The diene rubber contained in the rubber composition of the present invention can include isoprene rubber and other diene rubbers. As isoprene rubber, natural rubber (NR), deproteinized natural rubber and synthetic isoprene rubber can be mentioned. Here, deproteinized natural rubber is a natural rubber that has been deproteinized. Although the protein content is less than that of ordinary natural rubber, it is not completely removed. Natural rubber or deproteinized natural rubber contains impurities (protein, phospholipids, etc.) derived from natural rubber, which inhibit the coupling reaction of the silane coupling agent and produce the problem that the inorganic materials such as silica cannot be fully dispersed in the rubber composition. In the present invention, in order to solve such problems, when using natural rubber and / or synthetic isoprene rubber as the diene rubber, a protein modifier and / or a silanization reaction accelerator are added to the silane coupling agent composition. Examples of natural rubber include natural rubber latex, technically graded rubber (TSR), smoked rubber sheet (RSS), Eucommia ulmoides sheet, Eucommia ulmoides-derived natural rubber, guayule-derived natural rubber, Russian dandelion-derived natural rubber, and plant-derived 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 obtained by modifying these natural rubbers are also included in natural rubber. The ratio of cis / trans / vinyl groups in the double bond portion of natural rubber is not particularly limited, and any ratio can be used appropriately. Examples of synthetic isoprene rubber include copolymers of cis-1,4-isoprene, trans-1,4-isoprene, and 3,4-isoprene (so-called isoprene rubber (IR)). Examples of rubbers having a partial synthetic isoprene rubber structure include isoprene-butadiene rubber and halogenated isoprene rubber. In the present invention, the diene rubber used is preferably isoprene rubber (IR), and more preferably, 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 preferably have a number average molecular weight of 500 to 3,000,000 and a molecular weight distribution of 1.5 to 15.

[0409] Examples of 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, and ethylene-propylene-diene rubber.

[0410] 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.

[0411] The content of the diene rubber is preferably 20 to 80% by mass, more preferably 25 to 75% by mass, and even more preferably 30 to 70% by mass, based on the total mass of the solid content of the rubber composition.

[0412] (Inorganic materials)

[0413] Examples of the inorganic material included in the rubber composition of the present invention include silica, carbon black, calcium carbonate, titanium oxide, clay, and talc, which can be used alone or in combination. In particular, in the present invention, at least silica is used to further improve mechanical properties and heat resistance. The amount of the inorganic material added is preferably 0.1 to 500 parts by mass, and more preferably 1 to 300 parts by mass, per 100 parts by mass of the diene rubber.

[0414] There are no particular limitations on the silica, and examples thereof include dry silica, wet silica, colloidal silica, and precipitated silica. Among these, wet silica with hydrous silicic acid as the main component 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, and is generally 10 to 400 m2 in terms of nitrogen adsorption specific surface area (BET method). 2 / g, preferably 20 to 300 m 2 / g, more preferably 120 to 190m 2 / g range, sufficient improvements in reinforcement, wear resistance, and heat buildup are achieved, which is preferred. Here, the nitrogen adsorption specific surface area is a value measured using 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 the diene rubber.

[0415] Carbon black is appropriately selected and used depending on the intended use. In general, carbon black is classified into hard carbon and soft carbon according to 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 particularly preferred to use hard carbon with 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 relative to 100 parts by mass of diene rubber. It should be noted that carbon black can be added to the rubber composition or to the silane coupling agent composition.

[0416] (Other processing aids)

[0417] The rubber composition of the present invention may contain other processing aids such as sulfur vulcanizing agents, vulcanization accelerators, vulcanization accelerator aids, antioxidants, colorants, softeners, various oils, antioxidants, fillers, and plasticizers without departing from the scope of the present invention.

[0418] 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, lead oxide, p-quinone dioxime, dibenzoyl-p-quinone dioxime, tetrachloro-p-benzoquinone, poly-p-dinitrobenzene, methylenedianiline, phenolic resin, brominated alkylphenolic resin, and chlorinated alkylphenolic resin. The amount of the vulcanizing agent added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the diene rubber.

[0419] Examples of vulcanization accelerators include thiuram-based vulcanization accelerators such as tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), and tetramethylthiuram monosulfide (TMTM); aldehyde / ammonia-based vulcanization accelerators such as hexamethylenetetramine; guanidine-based vulcanization accelerators such as diphenylguanidine; thiazole-based vulcanization accelerators such as 2-mercaptobenzothiazole (MBT) and dibenzothiazyl disulfide (DM); sulfenamide-based vulcanization accelerators such as N-cyclohexyl-2-benzothiazolesulfenamide (CBS) and N-tert-butyl-2-benzothiazolesulfenamide (BBS); and dithiocarbamate-based vulcanization accelerators such as zinc dimethyldithiocarbamate (ZnPDC). The amount of the vulcanization accelerator added is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the diene rubber.

[0420] Examples of the vulcanization accelerator include fatty acids such as acetic acid, propionic acid, butyric acid, stearic acid, acrylic acid, and maleic acid; fatty acid zincs such as zinc acetate, zinc propionate, zinc butyrate, zinc stearate, zinc acrylate, and zinc maleate; and zinc oxide. The amount of the vulcanization accelerator added is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the diene rubber.

[0421] Examples of the antioxidant include hindered phenol compounds, aliphatic and aromatic hindered amine compounds, etc. The amount of the 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.

[0422] Examples of the antioxidant include butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), etc. The amount of the 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 the diene rubber.

[0423] Examples of colorants include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine blue, red iron, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochlorides, and sulfates, azo pigments, and copper phthalocyanine pigments. 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 the diene rubber.

[0424] In the present invention, other processing aids can be mixed using a known rubber mixer, such as a drum, a Banbury mixer, a kneader, etc., and vulcanized under any conditions to be used as a rubber composition. The amount of these other processing aids added can also be the conventional amount of addition within the scope of the present invention.

[0425] [Method for producing rubber composition]

[0426] The method for producing the rubber composition of the present invention includes the 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 includes the step of kneading the silane coupling agent, the diene rubber, the inorganic material, and the vulcanization accelerator.

[0427] 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 may include a step of kneading the vulcanizing agent and the vulcanization accelerator.

[0428] In each of the above steps, the rubber composition may be appropriately blended with the above-mentioned other processing aids within the scope not departing from the gist of the present invention.

[0429] A conventionally known kneading apparatus can be used for the production of the rubber composition, and the kneading temperature, time, mixing order, etc. can be appropriately selected.

[0430] [Cross-linked rubber composition]

[0431] The rubber composition of the present invention can be used to produce a cross-linked rubber composition according to conventionally known methods and common technical knowledge known to those skilled in the art. For example, the cross-linked rubber composition can be produced by extruding the rubber composition, then forming the composition using a molding machine, and then heating and pressurizing the composition using a vulcanizer to form cross-links.

[0432] [tire]

[0433] The tire of the present invention comprises a cross-linked product of the rubber composition of the present invention. The tire of the present invention can be manufactured using the rubber composition according to conventionally known methods and common technical knowledge known to those skilled in the art. For example, the tire can be manufactured by extruding the rubber composition, then molding it using a tire molding machine, and then heating and pressurizing it using a vulcanizer to form cross-links. By using the rubber composition of the present invention to manufacture a tire, it is possible to achieve a well-balanced improvement in tire performance, including wet grip and fuel efficiency.

[0434] The use of the tire is not particularly limited, and examples thereof include passenger car tires, high-load tires, motorcycle (motorcycle) tires, and studless tires.

[0435] The shape, structure, size, and material of the tire are not particularly limited and may be appropriately selected depending on the intended purpose. Furthermore, the tire may be applied to various parts of the tire. The tire application area is not particularly limited and may be appropriately selected depending on the intended purpose, such as the tire tread, carcass, sidewall, inner liner, undertread, and belt. In the present invention, pneumatic tires using the rubber composition for the tread are preferred.

[0436] Example

[0437] Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not limited to these Examples.

[0438] [Preparation Example 1: Synthesis of Silane Compound 1 (VNB-SSi)]

[0439] A 100 mL three-necked flask was fitted with a ball stopper, a three-way stopcock connected to a vacuum / dry nitrogen line, and a septum. A stirring rod was placed in the flask, and while heating in a desiccator, degassing and nitrogen replacement were repeated 10 times to create a normal pressure nitrogen atmosphere. 27.5 g (0.225 mol) of 2-vinylnorbornene (VNB) was injected into the flask using a syringe. Under a nitrogen atmosphere, 0.074 g (0.45 mmol) of azobisisobutyronitrile was added, followed by nitrogen bubbling for 20 minutes. Next, 10.7 g (0.045 mol) of mercaptopropyltriethoxysilane was drawn into the flask using an airtight syringe and attached to a metering pump, set to add the entire amount dropwise over 3 hours. Finally, seal the connection with silicone lubricant, insert the needle of the airtight syringe through the septum into the flask, immerse the flask in an oil bath, slowly increase the bath temperature, start the metering pump when the internal temperature reaches 50°C, and add mercaptopropyltriethoxysilane dropwise to react. 2 hours after the addition of all the amounts, remove the flask from the oil bath and let it cool to room temperature. Then, after decompression and distilling off the excess VNB, 37.4 g of the target colorless clear liquid was obtained. 1 The results of H-NMR measurements are shown in Figure 1 .pass 1 H-NMR determination and 13 C-NMR measurement confirmed that the introduction rate of silane was 100% and the double bond of the norbornene ring had disappeared.

[0440]

[0441] [Detection of Stereoisomers of Silane Compound 1]

[0442] The obtained silane compound 1 was separated by gas chromatography into a fraction containing a large amount of the compound represented by the above formula (1A) ("(1A) fraction") and a fraction containing a large amount of the compound represented by the above formula (1B) ("(1B) fraction"), and the fractions were separated ( Figure 2 ). The fraction (1A) 1 The results of H-NMR measurements are shown in Figure 3 ,Will 13 The results of C-NMR measurements are shown in Figure 4 In addition, the fraction (1B) 1 The results of H-NMR measurements are shown in Figure 5 ,Will 13 The results of C-NMR measurements are shown in Figure 6 It was confirmed that the double bond of the vinyl group in the chemical structures represented by formula (1A) and (1B) is directly bonded to the carbon atom on one side of the norbornene ring ( Figure 3 or Figure 5 The peak splitting of the proton bonded to (where the carbon atom is represented by the integer 2 surrounded by a circle) is speculated. According to the data, it is speculated that there are two stereoisomers, one in which the vinyl group bonded to the norbornene ring and the cross-linked structure of the norbornene ring extend toward the front side of the paper (cis isomers), and the other in which the vinyl group bonded to the norbornene ring and the cross-linked structure of the norbornene ring extend toward the back side of the paper (trans isomers). Similarly, it is speculated that there are two stereoisomers, one in which the sulfur atom bonded to the norbornene ring and the cross-linked structure of the norbornene ring extend toward the front side of the paper (cis isomers), and the other in which the sulfur atom bonded to the norbornene ring and the cross-linked structure of the norbornene ring extend toward the back side of the paper (trans isomers). It is thus speculated that the obtained silane compound 1 is a mixture of 8 stereoisomers represented by the following structural formula.

[0443]

[0444] [Preparation Example 2: Synthesis of Silane Compound 2 (VNB-2SSi)]

[0445] After installing a spherical stopper, a three-way stopcock connected to a vacuum / dry nitrogen line, and a septum in a 50mL three-necked flask, a stirring rod was placed. While heating in a desiccator, the system was degassed and replaced with nitrogen 10 times to create a normal pressure nitrogen atmosphere. 5.2g (0.043mol) of 2-vinylnorbornene (VNB) and 20.3g (0.085mol) of mercaptopropyltriethoxysilane were injected into the flask using a syringe. After adding 0.14g (0.85mmol) of azobisisobutyronitrile under a nitrogen atmosphere, nitrogen was bubbled for 20 minutes. After sealing the connection with silicone lubricant, the flask was immersed in an oil bath and the bath temperature was slowly raised to 50°C. After reacting for 13 hours, the temperature was further raised to 70°C and reacted for 5 hours. Mercaptopropyltriethoxysilane was then added twice (first: 0.10 g (0.85 mmol), second: 0.26 g (2.13 mmol)), reacted at 70°C for 5 hours, and then cooled to room temperature to obtain 25.0 g of the target colorless to pale yellow clear liquid.

[0446] The obtained compound 1 The results of H-NMR measurements are shown in Figure 7 .according to 1 H-NMR measurement confirmed that the introduction rate of silane was 100% and both the double bonds of the norbornene ring and the vinyl group had disappeared.

[0447]

[0448] [Detection of Stereoisomers of Silane Compound 2]

[0449] The obtained silane compound 2 1 The results of H-NMR measurements are shown in Figure 7 .according to 1 The measurement results of H-NMR confirmed that the double bond of the vinyl group disappeared. Here, it is speculated that silane compound 2 is obtained by further reacting mercaptosilane with the vinyl groups of the 8 stereoisomers (monoadducts) of silane compound 1 synthesized in Preparation Example 1 to form a diadduct. At this time, it is speculated that the addition with the vinyl group only reacts with the 1-position (outside) of the vinyl group with less steric hindrance, and the stereoisomerism of silane compound 1 remains unchanged during the addition with the vinyl group. Based on the above, it is speculated that the obtained silane compound 2 is a mixture of 8 stereoisomers represented by the following structural formula.

[0450]

[0451] [Preparation Example 3: Preparation of Silane Coupling Agent Composition 1]

[0452] After installing a spherical stopcock, a three-way stopcock connected to a dry nitrogen tube, a stirring blade, and a Trinity motor in a 100 mL three-necked flask, nitrogen was introduced from the nitrogen tube to replace the system with a normal pressure nitrogen atmosphere. 6.0 g of carbon black (Seast KH manufactured by Tokai Carbon) and 3.0 g of urea were added to the flask and the stirring blade was rotated at 60 rpm to mix. 15 minutes after the start of stirring, 5.18 g of silane compound 1 (VNB-SSi) and 0.825 g of silane compound 2 (VNB-2SSi) were added dropwise using a dropper. After all the additions were made, the stirring blade speed was increased to 200 rpm and further mixing was carried out. After 1 hour, stirring was stopped to obtain 14.9 g of black granular solid (silane coupling agent composition 1) with a diameter of approximately 1 to 3 mm.

[0453] [Example 1-1]

[0454] (Preparation of Silane Coupling Agent Composition, Rubber Composition, and Rubber Sheet)

[0455] First, the total amount of silane compound 1 (VNB-SSi), the total amount of silane compound 2 (VNB-2SSi), and the total amount of protein modifier 1 (urea) were mixed to obtain a silane coupling agent composition. Next, the following components were kneaded using a 100 mL kneader (LaboPlastomill, manufactured by Toyo Seiki Co., Ltd.) to obtain a rubber composition. Details of the kneading operation are described in (i) to (iii) below.

[0456] (i) Mixing in a Mixer: Natural rubber was added to a sealed pressurized kneader heated to 150°C and kneaded at 30 rpm for 1 minute. Half of the measured mixture of silica, zinc oxide, stearic acid, and an antioxidant, along with the entire amount of the silane coupling agent composition prepared above, was then added. The speed was increased to 50 rpm and kneaded for 1 minute and 30 seconds. The remaining half of the mixture of silica, zinc oxide, stearic acid, and an antioxidant was further added. Kneading was continued for 1 minute and 30 seconds. The hammer (upper ram) was raised and any powder of the mixture of silica, zinc oxide, stearic acid, and an antioxidant adhering to the surface was brushed into the kneaded product. Kneading was continued for another 1 minute. The hammer was raised again and any powder of the mixture of silica, zinc oxide, stearic acid, and an antioxidant adhering to the surface was brushed into the kneaded product. Kneading was continued for another 3 minutes.

[0457] (ii) Re-kneading: In order to sufficiently disperse the silica, the kneaded product was released into a closed pressure kneader heated to 120° C. and the temperature was sufficiently lowered. The product was further kneaded at 50 rpm for 2 minutes and then released.

[0458] (iii) Roller kneading (addition of vulcanization system): After releasing and sufficiently lowering the temperature, sulfur, a vulcanization accelerator, etc. are added to the kneaded product using twin rolls and kneaded to obtain a rubber composition.

[0459] Then, the obtained unvulcanized rubber composition was placed in a mold (150 mm×150 mm×2 mm), and heated and pressed at 150° C. for 25 minutes to obtain a vulcanized rubber sheet having a thickness of 2 mm.

[0460]

[0461]

[0462] [Example 1-2]

[0463] 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 addition amount of silane compound 1 (VNB-SSi) was changed to 3.04 parts by mass and the addition amount of silane compound 2 (VNB-2SSi) was changed to 0.16 parts by mass.

[0464] [Examples 1-3]

[0465] 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 addition amount of the silane compound 1 (VNB-SSi) was changed to 2.88 parts by mass and the addition amount of the silane compound 2 (VNB-2SSi) was changed to 0.32 parts by mass.

[0466] [Examples 1-4]

[0467] 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 addition amount of the silane compound 1 (VNB-SSi) was changed to 2.72 parts by mass and the addition amount of the silane compound 2 (VNB-2SSi) was changed to 0.48 parts by mass.

[0468] [Examples 1-5]

[0469] 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 addition amount of the silane compound 1 (VNB-SSi) was changed to 2.40 parts by mass and the addition amount of the silane compound 2 (VNB-2SSi) was changed to 0.80 parts by mass.

[0470] [Examples 1-6]

[0471] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Example 1-4 except that the amount of urea added was changed to 0.5 parts by mass.

[0472] [Examples 1-7]

[0473] 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 1.36 parts by mass, the amount of silane compound 2 (VNB-2SSi) added was changed to 0.24 parts by mass, 1.60 parts by mass of another silane compound (Si69) was added, and the amount of sulfur added was changed to 2.38 parts by mass.

[0474] [Comparative Example 1-1]

[0475] 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, 3.20 parts by mass of another silane compound (Si69) was added, and the amount of sulfur added was changed to 2.00 parts by mass.

[0476] [Comparative Example 1-2]

[0477] 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 silane compound 1 (VNB-SSi) was not added and the amount of the silane compound 2 (VNB-2SSi) added was changed to 3.20 parts by mass.

[0478] [Comparative Examples 1-3]

[0479] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Example 1-4 except that urea was not added.

[0480] [Physical property evaluation]

[0481] The physical properties of the rubber compositions and rubber sheets obtained in Examples 1-1 to 1-7 and Comparative Examples 1-1 to 1-3 were evaluated by the following methods.

[0482] (viscoelasticity)

[0483] Using a viscoelasticity measuring apparatus (REOGELE-4000 manufactured by UBM), in accordance with JIS K 6394, tan δ was measured at measurement temperatures of 0°C and 60°C for the rubber sheets obtained in Examples 1-1 to 1-7 and Comparative Examples 1-1 to 1-3 under the conditions of approximately 0.1% strain and 10 Hz frequency. Tan δ balance (= tan δ (0°C) / tan δ (60°C)) was calculated from these values. A higher tan δ balance indicates better viscoelastic properties of the rubber sheet and a better balance between wet grip performance and fuel efficiency as a tire.

[0484] (Scorch resistance)

[0485] The time t5 required for the unvulcanized rubber composition to increase by 5 Mooney units above the minimum viscosity Vm after preheating at 125°C for 1 minute was measured using a Rotorless Mooney tester manufactured by Toyo Seiki Co., Ltd. in accordance with JIS K6300. A larger scorch time indicates a longer scorch time and better processability of the rubber composition.

[0486] The above measurement results and calculation results (tan δ balance) are shown in Table 1. In addition, each measurement value and each calculation value are expressed as an index with each value in Comparative Example 1-1 being 100.

[0487] [Table 1]

[0488]

[0489] The results of Examples 1-1 to 1-7 and Comparative Examples 1-1 to 1-3 demonstrate that the use of a silane coupling agent composition containing Silane Compound 1, Silane Compound 2, and urea improves the scorch resistance of the rubber composition, and further enhances the viscoelastic properties of the rubber sheet. This demonstrates that the use of the silane coupling agent composition and rubber composition of the present invention improves the processability of the rubber, and enables the production of a tire that exhibits a practically excellent balance between wet grip performance and fuel efficiency.

[0490] [Example 2-1]

[0491] (Preparation of Silane Coupling Agent Composition, Rubber Composition, and Rubber Sheet)

[0492] The following components were kneaded using a 100 mL kneader (LaboPlastomill manufactured by Toyo Seiki Co., Ltd.) to obtain a rubber composition. The details of the kneading operation are described in (i) to (iii) below.

[0493] (i) Mixing in a mixer: natural rubber was added to a closed pressure kneader heated to 150°C and kneaded at 30 rpm for 1 minute. Then, 1 / 2 of the measured mixture of silica, carbon black, zinc oxide, stearic acid, and an antioxidant, as well as the entire amount of the silane coupling agent (silane compound 1 (VNB-SSi)), the entire amount of the silane compound 2 (VNB-2SSi), and the entire amount of the protein modifier 1 (urea) were added. The rotation speed was increased to 50 rpm and kneading was carried out for 1 minute and 30 seconds. Further add the remaining 1 / 2 amount of the above-mentioned mixture of silica, carbon black, zinc oxide, stearic acid and antioxidant, continue to mix for 1 minute and 30 seconds, lift the hammer (upper pin) and use a brush to put the powder of the above-mentioned mixture of silica, zinc oxide, stearic acid and antioxidant attached to the surrounding area into the mixture, continue to mix for 1 minute, lift the hammer again and use a brush to put the powder of the above-mentioned mixture of silica, carbon black, zinc oxide, stearic acid and antioxidant attached to the surrounding area into the mixture, and further mix for 3 minutes to release it.

[0494] (ii) Re-kneading: In order to sufficiently disperse the silica, the kneaded product was released into a closed pressure kneader heated to 120° C. and the temperature was sufficiently lowered. The product was further kneaded at 50 rpm for 2 minutes and then released.

[0495] (iii) Roller kneading (addition of vulcanization system): After the temperature is sufficiently lowered by release, sulfur, a vulcanization accelerator, etc. are added to the kneaded product using twin rolls and kneaded to obtain a rubber composition.

[0496] Then, the obtained rubber composition was placed in a mold (150 mm×150 mm×2 mm), and heated and pressed at 150° C. for 20 minutes to obtain a rubber sheet having a thickness of 2 mm.

[0497]

[0498]

[0499] [Example 2-2]

[0500] A rubber composition and a rubber sheet were obtained in the same manner as in Example 2-1 except that the operation of (i) mixer kneading in Example 2-1 was changed as follows.

[0501] (i) Mixing in a mixer: Natural rubber was added to a closed pressure kneader heated to 150°C and kneaded at 30 rpm for 1 minute. Then, 1 / 2 of the measured mixture of silica, zinc oxide, stearic acid, and an antioxidant and the entire amount of Silane Coupling Agent Composition 1 (7.4 parts by mass, Preparation Example 3) were added. The speed was increased to 50 rpm and kneading was continued for 1 minute 30 seconds. The speed was increased to 50 rpm and kneading was continued for 1 minute 30 seconds. Further add the remaining 1 / 2 amount of the above-mentioned mixture of silica, zinc oxide, stearic acid and antioxidant, continue to knead for 1 minute and 30 seconds, lift the hammer (upper pin) and use a brush to put the powder of the above-mentioned mixture of silica, zinc oxide, stearic acid and antioxidant attached to the surrounding area into the mixture, continue to knead for 1 minute, lift the hammer again and use a brush to put the powder of the above-mentioned mixture of silica, zinc oxide, stearic acid and antioxidant attached to the surrounding area into the mixture, and further knead for 3 minutes to release it.

[0502] [Comparative Example 2-1]

[0503] 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), silane compound 2 (VNB-2SSi) and urea were not added, 3.2 parts by mass of another silane compound (Si69) (manufactured by Degussa Corporation) was added, and the sulfur content was changed to 2.00 parts by mass.

[0504] [Comparative Example 2-2]

[0505] 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, 3.2 parts by mass of another silane compound (Si69) (manufactured by Degussa Corporation) was added, and the sulfur content was changed to 2.00 parts by mass.

[0506] [Physical property evaluation]

[0507] The physical properties of the rubber compositions and rubber sheets obtained in Examples 2-1 and 2-2 and Comparative Examples 2-1 and 2-2 were evaluated according to the methods described in the physical property evaluation of Example 1. The above measurement results and calculation results (tan δ balance) are shown in Table 2. The measured and calculated values ​​are expressed as indices with the values ​​in Comparative Example 2-1 set to 100.

[0508] [Table 2]

[0509]

[0510] The results of Examples 2-1 and 2-2 and Comparative Examples 2-1 and 2-2 show that the rubber compositions containing Silane Compound 1, Silane Compound 2, carbon black, urea, and natural rubber exhibit improved scorch resistance, and further, enhanced viscoelastic properties of the rubber sheet. This demonstrates that the use of the silane coupling agent composition and rubber composition of the present invention improves rubber processability, enabling the production of tires with a practically excellent balance between wet grip performance and fuel efficiency.

[0511] [Example 3-1]

[0512] (Preparation of Silane Coupling Agent Composition, Rubber Composition, and Rubber Sheet)

[0513] First, the total amount of silane compound 1 (VNB-SSi), the total amount of silane compound 2 (VNB-2SSi), and the total amount of protein modifier 2 (50% aqueous glutaraldehyde solution) were mixed to obtain a silane coupling agent composition. Next, the following components were kneaded using a 100 mL kneader (LaboPlastomill, manufactured by Toyo Seiki Co., Ltd.) to obtain a rubber composition. Details of the kneading operation are described in (i) to (iii) below.

[0514] (i) Mixing in a Mixer: Natural rubber was added to a sealed pressurized kneader heated to 150°C and kneaded at 30 rpm for 1 minute. Half of the measured mixture of silica, zinc oxide, stearic acid, and an antioxidant, along with the entire amount of the silane coupling agent composition prepared above, was then added. The speed was increased to 50 rpm and kneaded for 1 minute and 30 seconds. The remaining half of the mixture of silica, zinc oxide, stearic acid, and an antioxidant was further added. Kneading was continued for 1 minute and 30 seconds. The hammer (upper pin) was raised and any powder of the mixture of silica, zinc oxide, stearic acid, and an antioxidant adhering to the surface was brushed into the kneaded product. Kneading was continued for another 1 minute. The hammer was raised again and any powder of the mixture of silica, zinc oxide, stearic acid, and an antioxidant adhering to the surface was brushed into the kneaded product. Kneading was continued for another 3 minutes.

[0515] (ii) Re-kneading: In order to sufficiently disperse the silica, the kneaded product was released into a closed pressure kneader heated to 120° C. and the temperature was sufficiently lowered. The product was further kneaded at 50 rpm for 2 minutes and then released.

[0516] (iii) Roller kneading (addition of vulcanization system): After releasing and sufficiently lowering the temperature, sulfur, a vulcanization accelerator, etc. are added to the kneaded product using twin rolls and kneaded to obtain a rubber composition.

[0517] Then, the obtained unvulcanized rubber composition was placed in a mold (150 mm×150 mm×2 mm), and heated and pressed at 150° C. for 25 minutes to obtain a vulcanized rubber sheet having a thickness of 2 mm.

[0518]

[0519]

[0520] [Example 3-2]

[0521] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Example 3-1 except that Protein Modifier 2 was not added and 1 part by mass of Protein Modifier 3 (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: dimethyl suberimidate dihydrochloride) was added.

[0522] [Example 3-3]

[0523] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Example 3-1 except that Protein Modifier 2 was not added and 1 part by mass of Protein Modifier 4 (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: sodium lauryl sulfate) was added.

[0524] [Examples 3-4]

[0525] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Example 3-1 except that Protein Modifier 2 was not added and 1 part by mass of Protein Modifier 5 (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: guanidine hydrochloride) was added.

[0526] [Comparative Example 3-1]

[0527] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Example 3-1 except that silane compound 1 (VNB-SSi) and silane compound 2 (VNB-2SSi) were not added, 3.20 parts by mass of another silane compound (Si69) was added, and the amount of sulfur added was changed to 2.00 parts by mass.

[0528] [Comparative Example 3-2]

[0529] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Example 3-2 except that silane compound 1 (VNB-SSi) and silane compound 2 (VNB-2SSi) were not added, 3.20 parts by mass of another silane compound (Si69) was added, and the amount of sulfur added was changed to 2.00 parts by mass.

[0530] [Comparative Example 3-3]

[0531] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Example 3-3 except that silane compound 1 (VNB-SSi) and silane compound 2 (VNB-2SSi) were not added, 3.20 parts by mass of another silane compound (Si69) was added, and the amount of sulfur added was changed to 2.00 parts by mass.

[0532] [Comparative Examples 3-4]

[0533] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Example 3-4 except that silane compound 1 (VNB-SSi) and silane compound 2 (VNB-2SSi) were not added, 3.20 parts by mass of another silane compound (Si69) was added, and the amount of sulfur added was changed to 2.00 parts by mass.

[0534] [Comparative Examples 3-5]

[0535] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Comparative Example 3-1 except that the protein modifier 2 was not added.

[0536] [Physical property evaluation]

[0537] The viscoelasticity of the rubber sheets obtained in Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-5 and the scorch resistance of the rubber compositions were evaluated using the same methods as in Example 1-1. The above measurement results and calculation results (tan δ balance) are shown in Table 3. The measured and calculated values ​​are expressed as indices, with the values ​​in Comparative Example 3-5 set to 100.

[0538] [Table 3]

[0539]

[0540] The results of Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-5 demonstrate that the use of a silane coupling agent composition containing silane compound 1 (VNB-SSi), silane compound 2 (VNB-2SSi), and protein modifiers 2 to 5 improves the scorch resistance of a rubber composition containing natural rubber, thereby enhancing the viscoelastic properties of the rubber sheet. This demonstrates that the use of the silane coupling agent composition and rubber composition of the present invention improves the processability of the rubber, enabling the production of a practically excellent tire with an excellent balance between wet grip performance and fuel efficiency.

[0541] [Example 4-1]

[0542] (Preparation of Silane Coupling Agent Composition, Rubber Composition, and Rubber Sheet)

[0543] First, the total amount of silane compound 1 (VNB-SSi), the total amount of silane compound 2 (VNB-2SSi), the total amount of protein modifier 1 (urea), and the total amount of protein modifier 6 (diphenylguanidine) were mixed to obtain a silane coupling agent composition. Next, the following components were kneaded using a 100 mL kneader (LaboPlastomill, manufactured by Toyo Seiki Co., Ltd.) to obtain a rubber composition. Details of the kneading operation are described in (i) to (iii) below.

[0544] (i) Mixing in a Mixer: Natural rubber was placed in a sealed pressurized kneader heated to 150°C and kneaded at 30 rpm for 1 minute. Half of the measured mixture of silica, carbon black, zinc oxide, stearic acid, and an antioxidant, along with the entire amount of the silane coupling agent composition prepared above, was then added. The speed was increased to 50 rpm and kneaded for 1 minute and 30 seconds. The remaining half of the mixture of silica, zinc oxide, stearic acid, and an antioxidant was further added. Kneading was continued for 1 minute and 30 seconds. The hammer (upper pin) was raised and the powder of the mixture of silica, carbon black, zinc oxide, stearic acid, and an antioxidant adhering to the surrounding area was brushed into the kneaded material. Kneading was continued for another minute. The hammer was raised again and the powder of the mixture of silica, zinc oxide, stearic acid, and an antioxidant adhering to the surrounding area was brushed into the kneaded material. Kneading was continued for another 3 minutes.

[0545] (ii) Re-kneading: In order to sufficiently disperse the silica, the kneaded product was released into a closed pressure kneader heated to 120° C. and the temperature was sufficiently lowered. The product was further kneaded at 50 rpm for 2 minutes and then released.

[0546] (iii) Roller kneading (addition of vulcanization system): After releasing and sufficiently lowering the temperature, sulfur, a vulcanization accelerator, etc. are added to the kneaded product using twin rolls and kneaded to obtain a rubber composition.

[0547] Then, the obtained unvulcanized rubber composition was placed in a mold (150 mm×150 mm×2 mm), and heated and pressed at 160° C. for 30 minutes to obtain a vulcanized rubber sheet having a thickness of 2 mm.

[0548]

[0549]

[0550] [Example 4-2]

[0551] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Example 4-1 except that the amount of diphenylguanidine added was changed to 0.05 parts by mass.

[0552] [Comparative Example 4-1]

[0553] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Example 4-1 except that urea, diphenylguanidine, silane compound 1 (VNB-SSi), and silane compound 2 (VNB-2SSi) were not added, 3.20 parts by mass of another silane compound (Si69) was added, and the amount of sulfur added was changed to 2.00 parts by mass.

[0554] [Comparative Example 4-2]

[0555] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Comparative Example 4-1 except that 1 part by mass of urea was added.

[0556] [Comparative Example 4-3]

[0557] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Comparative Example 4-1 except that 1 part by mass of urea and 1 part by mass of diphenylguanidine were added.

[0558] [Example 4-3]

[0559] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Example 4-1 except that the following components were used.

[0560]

[0561]

[0562] [Comparative Example 4-4]

[0563] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Example 4-3 except that urea, diphenylguanidine, silane compound 1 (VNB-SSi), and silane compound 2 (VNB-2SSi) were not added, 4.00 parts by mass of another silane compound (Si69) was added, and the amount of sulfur added was changed to 2.00 parts by mass.

[0564] [Comparative Examples 4-5]

[0565] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Comparative Example 4-4 except that 1.25 parts by mass of urea was added.

[0566] [Physical property evaluation]

[0567] The viscoelasticity of the rubber sheets obtained in Examples 4-1 to 4-3 and Comparative Examples 4-1 to 4-5 and the scorch resistance of the rubber compositions were evaluated in the same manner as in Example 1-1 by the above-mentioned methods.

[0568] (Uncrosslinked compound viscosity)

[0569] The Mooney viscosities of the rubber compositions obtained in Examples 4-1 to 4-3 and Comparative Examples 4-1 to 4-5 were measured using a Mooney viscometer using an L-type rotor (38.1 mm diameter, 5.5 mm thickness) in accordance with JIS K6300, with a preheating time of 1 minute, a rotor rotation time of 4 minutes, a temperature of 100°C, and a rotation speed of 2 rpm. A lower measurement result indicates a lower viscosity of the rubber composition and better processability.

[0570] The above measurement results and calculation results (tan δ balance) are shown in Table 4. The measured values ​​and calculated values ​​for Example 4-1, Example 4-2, Comparative Example 4-2, and Comparative Example 4-3 are expressed as relative values, with the values ​​in Comparative Example 4-1 being 100. Furthermore, the measured values ​​and calculated values ​​for Example 4-3 and Comparative Example 4-5 are expressed as relative values, with the values ​​in Comparative Example 4-4 being 100.

[0571] [Table 4]

[0572]

[0573] The results of Examples 4-1 to 4-3 and Comparative Examples 4-1 to 4-5 demonstrate that the use of a silane coupling agent composition containing silane compound 1 (VNB-SSi), silane compound 2 (VNB-SSi), protein modifier 1 (urea), and protein modifier 6 (diphenylguanidine) reduces the viscosity of a rubber composition containing natural rubber in the form of an uncrosslinked composite, improves scorch resistance, and further enhances the viscoelastic properties of the rubber sheet. This demonstrates that the use of the silane coupling agent composition and rubber composition of the present invention improves rubber processability, enabling the production of a tire with a practically excellent balance between wet grip performance and fuel efficiency.

[0574] [Example 5-1]

[0575] (Preparation of Silane Coupling Agent Composition, Rubber Composition, and Rubber Sheet)

[0576] First, the total amount of silane compound 1 (VNB-SSi), the total amount of silane compound 2 (VNB-2SSi), and the total amount of silylation reaction accelerator (urea) were mixed to obtain a silane coupling agent composition. Next, the following components were kneaded using a 100 mL kneader (LaboPlastomill, manufactured by Toyo Seiki Co., Ltd.) to obtain a rubber composition. Details of the kneading operation are described in (i) to (iii) below.

[0577] (i) Mixing in a Mixer: Natural rubber was added to a sealed pressurized kneader heated to 150°C and kneaded at 30 rpm for 1 minute. Half of the measured mixture of silica, zinc oxide, stearic acid, and an antioxidant, along with the entire amount of the silane coupling agent composition prepared above, was then added. The speed was increased to 50 rpm and kneaded for 1 minute and 30 seconds. The remaining half of the mixture of silica, zinc oxide, stearic acid, and an antioxidant was further added. Kneading was continued for 1 minute and 30 seconds. The hammer (upper pin) was raised and the powder of the mixture of silica, zinc oxide, stearic acid, and an antioxidant adhering to the surrounding area was brushed into the kneaded material. Kneading was continued for another minute. The hammer was raised again and the powder of the mixture of silica, zinc oxide, stearic acid, and an antioxidant adhering to the surrounding area was brushed into the kneaded material. Kneading was continued for another 3 minutes.

[0578] (ii) Re-kneading: In order to sufficiently disperse the silica, the kneaded product was released into a closed pressure kneader heated to 120° C. and the temperature was sufficiently lowered. The product was further kneaded at 50 rpm for 2 minutes and then released.

[0579] (iii) Roller kneading (addition of vulcanization system): After releasing and sufficiently lowering the temperature, sulfur, a vulcanization accelerator, etc. are added to the kneaded product using twin rolls and kneaded to obtain a rubber composition.

[0580] Then, the obtained unvulcanized rubber composition was placed in a mold (150 mm×150 mm×2 mm), and heated and pressed at 160° C. for 30 minutes to obtain a vulcanized rubber sheet having a thickness of 2 mm.

[0581]

[0582]

[0583] [Comparative Example 5-1]

[0584] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Example 5-1, except that the silylation reaction accelerator, 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.

[0585] [Comparative Example 5-2]

[0586] A silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Comparative Example 5-1 except that 1.50 parts by mass of a silylation reaction accelerator was added.

[0587] [Physical property evaluation]

[0588] The viscoelasticity of the rubber sheets obtained in Example 5-1 and Comparative Examples 5-1 and 5-2, as well as the scorch resistance of the rubber compositions, were evaluated using the same methods as in Example 1-1. Furthermore, the viscosity of the uncrosslinked compound of the rubber composition was evaluated using the same method as in Example 4-1. The above measurement results and calculation results (tan δ balance) are shown in Table 5. The measured and calculated values ​​are expressed as indices, with the values ​​in Comparative Example 5-1 set to 100.

[0589] [Table 5]

[0590]

[0591] The results of Example 5-1 and Comparative Examples 5-1 and 5-2 demonstrate that the use of a silane coupling agent composition containing silane compound 1 (VNB-SSi), silane compound 2 (VNB-SSi), and a silylation reaction accelerator (urea) reduces the viscosity of the uncrosslinked rubber composition containing synthetic isoprene rubber, improves scorch resistance, and further enhances the viscoelastic properties of the rubber sheet. This demonstrates that the use of the silane coupling agent composition and rubber composition of the present invention improves rubber processability, enabling the production of a tire with a practically excellent balance between wet grip performance and fuel efficiency.

Claims

1. A silane coupling agent composition comprising a silane compound, a protein modifier and / or a silanization reaction accelerator, The silane compound includes a first silane compound represented by the following formula (1) and a second silane compound represented by the following formula (11), In 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, L is a hydrocarbon group which may contain at least one heteroatom selected from nitrogen, oxygen and sulfur, a is an integer of 0 or 1, b is an integer of 0 or 1, c are each independently an integer of 0 or 1, d are each 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 can form -(CH2) f - indicates the cross-linked structure, 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 can form -(CH2) g - indicates the cross-linked structure, 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, wherein R 12 and R 13 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 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 Can bond with each other to form four to nine-membered alicyclic hydrocarbons, where R 14 and R 15 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, In formula (11), 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 nitrogen, oxygen and sulfur, a is an integer of 0 or 1, b is an integer of 0 or 1, c are each independently an integer of 0 or 1, d are each 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 can form -(CH2) f - indicates the cross-linked structure, 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 can form -(CH2) g - indicates the cross-linked structure, 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 content of the second silane compound is 1 to 50% by mass relative to the total content of the first silane compound and the second silane compound. The protein modifier is at least one selected from urea compounds, guanidine compounds and surfactants, The silylation reaction accelerator is at least one selected from urea compounds and guanidine compounds.

2. The silane coupling agent composition according to claim 1, wherein The first silane compound is a compound represented by the following formula (2): In formula (2), 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 of 0 or 1, b is an integer of 0 or 1, c are each independently an integer of 0 or 1, d are each 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 can form -(CH2) f - indicates the cross-linked structure, 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 can form -(CH2) g - indicates the cross-linked structure, 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, wherein R 12 and R 13 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 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 Can bond with each other to form four to nine-membered alicyclic hydrocarbons, where R 14 and R 15 bonded to each other to form a double bond and R 12 、R 13 and R 18 It is a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms.

3. The silane coupling agent composition according to claim 1 or 2, wherein The second silane compound is a compound represented by the following formula (12): In formula (12), 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 of 0 or 1, b is an integer of 0 or 1, c are each independently an integer of 0 or 1, d are each 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 can form -(CH2) f - indicates the cross-linked structure, 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 can form -(CH2) g - indicates the cross-linked structure, 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.

4. The silane coupling agent composition according to claim 1 or 2, wherein The content of the second silane compound is 2 to 40% by mass relative to the total content of the first silane compound and the second silane compound.

5. The silane coupling agent composition according to claim 1 or 2, wherein The silane compound further includes other silane compounds in addition to the first silane compound and the second silane compound.

6. The silane coupling agent composition according to claim 5, wherein The other silane compound is a silane compound represented by formula (13), In formula (13), t and v are each independently an integer from 0 to 10, u is an integer from 2 to 10, q and r are each independently 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 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, R 22 and R 24 Each is independently hydrogen or alkyl.

7. The silane coupling agent composition according to claim 1 or 2, wherein The total content of the first silane compound and the second silane compound is 50 to 95% by mass based on the total mass of the silane coupling agent composition.

8. The silane coupling agent composition according to claim 1 or 2, wherein The total content of the protein modifying agent and the silylation reaction accelerator is 5 to 50% by mass based on the total mass of the silane coupling agent composition.

9. The silane coupling agent composition according to claim 1 or 2, wherein The urea compound is urea.

10. The silane coupling agent composition according to claim 1 or 2, wherein The guanidine compound is diphenylguanidine.

11. The silane coupling agent composition according to claim 1 or 2, wherein It further contains carbon black.

12. The silane coupling agent composition according to claim 1 or 2, wherein For use with natural rubber and / or synthetic isoprene rubber.

13. A rubber composition comprising the silane coupling agent composition according to any one of claims 1 to 12, a diene rubber, and silica. The diene rubber comprises at least natural rubber and / or synthetic isoprene rubber, The total content of the first silane compound and the second silane compound is 0.5 to 30 parts by mass relative to 100 parts by mass of the silica.

14. The rubber composition according to claim 13, wherein The content of the silica is 0.5 to 300 parts by mass relative to 100 parts by mass of the diene rubber.

15. The rubber composition according to claim 13 or 14, which is used for a tire.

16. A cross-linked product of the rubber composition according to any one of claims 13 to 15.

17. A pneumatic tire comprising a tread using the cross-linked product according to claim 16.

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