JP7321007B2 - Viscosity modifier for lubricating oil, additive composition for lubricating oil, and lubricating oil composition - Google Patents

Description

The present invention relates to a lubricating oil viscosity modifier, and a lubricating oil additive composition and a lubricating oil composition containing the same.

Petroleum products generally have so-called temperature dependence of viscosity, in which the viscosity changes greatly due to changes in temperature. It is practically desirable that the viscosity changes as little as possible over a wide range. A viscosity index is used as a measure of this, and the larger the viscosity index, the higher the stability against temperature changes. Therefore, in lubricating oils, certain polymers soluble in lubricating base oils such as mineral oils are used as viscosity index improvers for the purpose of reducing the temperature dependence of viscosity.

Ethylene/α-olefin copolymers are widely used as such viscosity modifiers for lubricating oils. Various methods have been tried so far, including a method of changing the monomer sequence such as blocks, a method of blending polymers with different compositions, and a method of graft copolymerizing a polar monomer to an ethylene/α-olefin copolymer.

The viscosity modifier described in Patent Document 1 reduces the low-temperature viscosity of the lubricating oil composition containing the modifier, and contributes to the improvement of fuel efficiency under conditions where the internal temperature of the engine is low (for example, when the engine is started). is done. However, as demand for fuel efficiency increases, further reduction in low-temperature viscosity is required.

As a method of improving the high-temperature properties and low-temperature properties of a lubricating oil composition in a well-balanced manner, there is a method of using an ethylene-propylene copolymer having a high ethylene content as a viscosity modifier (see, for example, Patent Document 2). is increased, the low-temperature properties are improved, but the ethylene chain portion of the viscosity modifier crystallizes at low temperatures, and the storage stability of the lubricating oil composition at low temperatures may be reduced. Under these circumstances, there is a demand for a lubricating oil viscosity modifier for obtaining a lubricating oil composition that has excellent low-temperature storage stability and excellent low-temperature viscosity properties.

As a method for improving the low-temperature storage stability and low-temperature properties of a lubricating oil composition, a method of using a blend of ethylene/α-olefin copolymers having different amounts of ethylene-derived structural units as a viscosity modifier for a lubricating oil (for example, Patent Document 3 , 4), and a method of using an olefin block copolymer having ethylene/α-olefin polymer blocks with different amounts of ethylene-derived structural units as a viscosity modifier for lubricating oils (see, for example, Patent Document 5). It is

WO2000/060032 WO 2000/034420 JP-A-2003-105365 U.S. Pat. No. 3,697,429 WO2008/047878

However, a lubricating oil composition using a lubricating oil viscosity modifier using a conventional ethylene/α-olefin copolymer has an insufficient balance between viscosity index and low-temperature viscosity.
An object of the present invention is to provide a lubricating oil viscosity modifier and a lubricating oil additive composition for obtaining a lubricating oil composition having an excellent balance between viscosity index and low-temperature viscosity.

As a result of intensive research, the present inventors have found that the above problems can be solved by using a lubricating oil viscosity modifier that satisfies specific requirements in a lubricating oil additive composition. That is, the present invention relates to the following [1] to [11].
[1] A lubricating oil viscosity modifier containing a resin (α) and a resin (β),
The resin (α) satisfies the following requirements (I)-1 and (I)-2,
The resin (β) satisfies the following requirements (II)-1 and (II)-2, and
A lubricating oil viscosity modifier, wherein both the resin (α) and the resin (β) satisfy the following requirement (III)-1.
(I)-1: A copolymer of ethylene and at least one α-olefin selected from α-olefins having 3 to 12 carbon atoms, containing 87 to 99 mol% of structural units derived from ethylene. in the range.
(I)-2: The melting point (Tm) measured by differential scanning calorimetry (DSC) is in the range of 50 to 100°C.
(II)-1: A copolymer of ethylene and at least one α-olefin selected from α-olefins having 3 to 12 carbon atoms, containing 30 to 65 mol% of structural units derived from ethylene. in the range.
(II)-2: Does not have a melting point (Tm) determined by differential scanning calorimetry (DSC).
(III)-1: The intrinsic viscosity [η] measured in decalin at 135° C. is in the range of 0.5 to 2.5 dl/g.
[2] 1 to 99 parts by mass of the resin (α) and 99 to 1 part by mass of the resin (β) (where the total of the resin (α) and the resin (β) is 100 parts by mass), The lubricating oil viscosity modifier according to [1] above.
[3] The lubricating oil viscosity according to [1] or [2] above, wherein both the resin (α) and the resin (β) consist of a structural unit derived from ethylene and a structural unit derived from propylene. regulator.
[4] The lubricating oil viscosity modifier according to any one of [1] to [3], wherein both the resin (α) and the resin (β) further satisfy the following requirement (III)-2.
(III)-2: Density measured by the density gradient tube method in accordance with JIS K7112 is in the range of 850 to 880 kg/m ³ .
[5] The lubricating oil viscosity modifier according to any one of [1] to [4], wherein the resin (α) further satisfies the following requirement (I)-3.
(I)-3: The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is in the range of 70,000 to 400,000.
[6] The lubricating oil viscosity modifier according to any one of [1] to [5], wherein the resin (β) further satisfies the following requirement (II)-3.
(II)-3: Weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is in the range of 1,000 to 70,000.
[7] 1 to 50 parts by mass of the lubricating oil viscosity modifier (A) according to any one of the above [1] to [6], and 50 to 99 parts by mass of the oil (B) (however, the lubricating oil viscosity A lubricating oil additive composition comprising a modifier (A) and an oil (B) totaling 100 parts by mass.
[8] 0.1 to 5 parts by mass of the lubricating oil viscosity modifier (A) according to any one of [1] to [6] above, and 95 to 99.9 parts by mass of the lubricating oil base (BB) A lubricating oil composition containing (however, the total of the lubricating oil viscosity modifier (A) and the lubricating oil base material (BB) is 100 parts by mass).
[9] The lubricating oil composition according to [8] above, which contains a pour point depressant (C) in an amount of 0.05 to 5% by mass based on 100% by mass of the lubricating oil composition.
[10] The lubricating oil composition according to [8] or [9] above, wherein the lubricating oil base (BB) is a mineral oil.
[11] The lubricating oil composition according to [8] or [9] above, wherein the lubricating oil base (BB) is a synthetic oil.

By using the viscosity modifier for lubricating oil of the present invention, it is possible to provide a lubricating oil composition that has excellent viscosity characteristics at high temperatures, excellent low temperature characteristics, and a good balance between viscosity index and low temperature viscosity. Moreover, according to this invention, the additive composition for lubricating oils which can provide the said lubricating oil composition can be provided.

The present invention will be specifically described below. In the following description, "-" indicating a numerical range represents from above to below unless otherwise specified.

<Viscosity modifier for lubricating oil>
The lubricating oil viscosity modifier of the present invention contains a resin (α) and a resin (β). Each component will be described in detail below.

Resin (α)
The resin (α) constituting the lubricating oil viscosity modifier of the present invention satisfies the following requirements (I)-1, (I)-2 and (III)-1. In addition to these requirements, the resin (α) preferably further satisfies at least one of requirements (I)-3, (I)-4 and (III)-2.

(I)-1: A copolymer of ethylene and at least one α-olefin selected from α-olefins having 3 to 12 carbon atoms, wherein the structural unit derived from ethylene is 87 to 99 mol%. in the range of

When the proportion of the structural unit derived from ethylene is equal to or less than the above upper limit value, the storage stability at low temperatures is excellent, and when it is equal to or more than the above lower limit value, the viscosity characteristics at low temperatures are excellent. When the ratio of structural units derived from α-olefins having 3 to 12 carbon atoms is equal to or less than the above upper limit, the viscosity characteristics at low temperatures are excellent, and when it is equal to or more than the above lower limit, storage stability at low temperatures is improved. Excellent. The molar ratio of the structural unit derived from ethylene and the structural unit derived from at least one α-olefin selected from α-olefins having 3 to 12 carbon atoms is within the above range by adjusting the monomer ratio of the raw materials. can be within

Structural units derived from ethylene in the resin (α) are determined by the method described in "Polymer Analysis Handbook" (Japan Society for Analytical Chemistry, Polymer Analysis Research Conference, published by Kinokuniya Shoten, published on January 12, 1995). can be measured by ¹³ C-NMR according to
The α-olefins having 3 to 12 carbon atoms that constitute the resin (α) can be used singly or in combination.

Examples of α-olefins having 3 to 12 carbon atoms include propylene, 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1- Butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1 -hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, 1-decene, 1- undecene, 1-dodecene and the like.

More preferably, the C3-C12 α-olefins are C3-C10 α-olefins, even more preferably C3-C8 α-olefins. Specifically, linear olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 1-decene, and 4-methyl-1-pentene, 3-methyl-1-pentene, Branched olefins such as 3-methyl-1-butene may be mentioned, among which propylene, 1-butene, 1-pentene, 1-hexene and 1-octene are preferred, and propylene is more preferred. It is preferable to use propylene from the viewpoint of excellent shear stability. That is, the resin (α) most preferably consists of structural units derived from ethylene and structural units derived from propylene.

(I)-2: The melting point (Tm) measured by differential scanning calorimetry (DSC) is in the range of 50 to 100°C.
The melting point (Tm) is adjusted by various factors, but it is mainly adjusted by the constitution of the structural units of the resin. As the content ratio decreases, the melting point (Tm) tends to decrease. That is, it can be adjusted within the above range by controlling the ratio of the concentration of ethylene and the concentration of α-olefin present in the polymerization reaction system when producing the resin (α). The melting point (Tm) tends to increase as the content of structural units derived from ethylene increases. The method of measuring the melting point (Tm) by differential scanning calorimetry (DSC) is detailed in the Examples section .

(I)-3: The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is in the range of 70,000 to 400,000. It is more preferably in the range of 80,000 to 300,000, still more preferably in the range of 100,000 to 250,000.
In the present invention, the weight average molecular weight indicates the polystyrene equivalent weight average molecular weight measured by GPC. The GPC measurement method will be described in detail in the Examples section.
The weight average molecular weight (Mw) can be set within the above range by controlling the polymerization temperature during polymerization of the resin (α), a molecular weight modifier such as hydrogen, and the like.

(I)-4: The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC (molecular weight distribution, Mw/Mn) of the resin (α) exhibits the effects of the present invention. Although not particularly limited as long as the More preferred.

(III)-1: The intrinsic viscosity [η] measured in decalin at 135°C is in the range of 0.5 to 2.5 dl/g.
The intrinsic viscosity [η] of the resin (α) is preferably 0.55-2.0 dl/g, more preferably 0.6-1.8 dl/g. When the intrinsic viscosity [η] of the resin (α) is within the above range, the shear stability is excellent.
The intrinsic viscosity [η] can be set within the above range by controlling the polymerization temperature during polymerization of the resin (α), a molecular weight modifier such as hydrogen, and the like.

(III)-2: Preferably, the density measured by the density gradient tube method according to JIS K7112 is in the range of 850 to 880 kg/m ³ . The density of resin (α) is more preferably in the range of 850-877 kg/m ³ , particularly preferably in the range of 850-874 kg/m ³ . Being in the above range is preferable in that the viscosity at low temperature can be reduced.

A lubricating oil composition containing a lubricating oil viscosity modifier containing a resin (α) as described above has better storage stability at low temperatures than conventional lubricating oil compositions, and excellent viscosity characteristics at low temperatures. .

Resin (β)
The resin (β) constituting the lubricating oil viscosity modifier of the present invention satisfies the following requirements (II)-1, (II)-2 and (III)-1. The resin (β) preferably further satisfies at least one of the requirements (II)-3 and (III)-2.

(II)-1: A copolymer of ethylene and at least one α-olefin selected from α-olefins having 3 to 12 carbon atoms, wherein the structural unit derived from ethylene is 30 to 65 mol%. in the range of

In the resin (β), the proportion of structural units derived from ethylene is 30 to 65 mol% of all structural units, and the proportion of structural units derived from α-olefins having 3 to 12 carbon atoms is 35 to all structural units. ~70 mol% (provided that the total of structural units derived from ethylene and structural units derived from α-olefins having 3 to 12 carbon atoms is defined as 100 mol%). The proportion of structural units derived from ethylene is preferably 35 to 60 mol%, more preferably 40 to 58 mol%, and the proportion of structural units derived from α-olefins having 3 to 12 carbon atoms is preferably 40 to 65 mol %, more preferably 42 to 60 mol %.

The α-olefins having 3 to 12 carbon atoms that constitute the resin (β) can be used singly or in combination. Examples of the α-olefin having 3 to 12 carbon atoms constituting the resin (β) include those mentioned above as the α-olefin having 3 to 12 carbon atoms constituting the resin (α).

(II)-2: Does not have a melting point (Tm) measured by differential scanning calorimetry (DSC).
When the crystallinity of the resin is low (amorphous), it tends not to show a melting point peak observed by differential scanning calorimetry (DSC), and in this case it is evaluated as not having a melting point (Tm). be done. The resin (β) does not have a melting point (Tm) because the amount of structural units derived from ethylene is relatively large, and the structural units derived from ethylene and the structural units derived from α-olefin are randomly bonded. to cause.

(II)-3: Preferably, the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is in the range of 1,000 to 100,000. The weight average molecular weight (Mw) of the resin (β) is more preferably in the range of 5,000 to 100,000, more preferably in the range of 10,000 to 100,000.

(III)-1: The intrinsic viscosity [η] measured in decalin at 135°C is in the range of 0.5 to 2.5 dl/g.
When the intrinsic viscosity [η] of the resin (β) is within the above range, like the resin (α), the shear stability is excellent. The intrinsic viscosity [η] of the resin (β) is preferably 0.55-2.0 dl/g, more preferably 0.6-1.8 dl/g. The intrinsic viscosity [η] can be set within the above range by controlling the polymerization temperature during polymerization of the resin (β), a molecular weight modifier such as hydrogen, and the like.

(III)-2: Preferably, the density measured by the density gradient tube method according to JIS K7112 is in the range of 850 to 880 kg/m ³ . The density of resin (β) is more preferably in the range of 850-877 kg/m ³ , particularly preferably in the range of 850-874 kg/m ³ . It is preferable that the density of the resin (β) is within the above range in that the low-temperature viscosity can be reduced. In the present invention, it is more preferable that the densities of both resin (α) and resin (β) satisfy the above ranges.

<Preparation of resin (α) and resin (β)>
The resin (α) and the resin (β) can be obtained using known polymerization catalysts such as Ziegler catalysts and metallocene catalysts.
Catalysts capable of suitably producing the resin (α) include, for example, polymerization catalysts containing a crosslinked metallocene compound [A] described later. Preferably, a compound [C] described later is used together with the crosslinked metallocene compound [A]. polymerization catalyst containing. Further, examples of the catalyst that can suitably produce the resin (β) include a polymerization catalyst containing the transition metal compound [B] described later. Preferably, the transition metal compound [B] and the compound [C ] is mentioned.

（式［Ａ］中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁸、Ｒ⁹およびＲ¹²はそれぞれ独立に水素原子、炭化水素基、ケイ素含有基またはケイ素含有基以外のヘテロ原子含有基を示し、Ｒ¹～Ｒ⁴のうち相互に隣り合う二つの基同士は互いに結合して環を形成していてもよい。
Ｒ⁶およびＲ¹¹は水素原子、炭化水素基、ケイ素含有基およびケイ素含有基以外のヘテロ原子含有基から選ばれる同一の原子または同一の基であり、Ｒ⁷およびＲ¹⁰は水素原子、炭化水素基、ケイ素含有基およびケイ素含有基以外のヘテロ原子含有基から選ばれる同一の原子または同一の基であり、Ｒ⁶およびＲ⁷は互いに結合して環を形成していてもよく、Ｒ¹⁰およびＲ¹¹は互いに結合して環を形成していてもよく；ただし、Ｒ⁶、Ｒ⁷、Ｒ¹⁰およびＲ¹¹が全て水素原子であることはない。
Ｍ¹はジルコニウム原子またはハフニウム原子を示す。
Ｑはハロゲン原子、炭化水素基、ハロゲン化炭化水素基、炭素数４～１０の中性の共役もしくは非共役ジエン、アニオン配位子または孤立電子対で配位可能な中性配位子を示し、ｊは１～４の整数を示し、ｊが２以上の整数の場合は複数あるＱはそれぞれ同一でも異なっていてもよい。） - Bridged metallocene compound [A]
The crosslinked metallocene compound [A] that is preferably used for producing the resin (α) is a compound represented by the following general formula [A].

(In formula [A], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² are each independently a hydrogen atom, a hydrocarbon group, a silicon-containing group, or a group other than a silicon-containing group. It represents a heteroatom-containing group, and two groups adjacent to each other among R ¹ to R ⁴ may combine with each other to form a ring.
R ⁶ and R ¹¹ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, and R ⁷ and R ¹⁰ are a hydrogen atom, a hydrocarbon the same atom or the same group selected from a heteroatom-containing group other than a silicon-containing group, a ^silicon -containing group ^, and a ^silicon- containing group; R ¹¹ may combine with each other to form a ring; however, R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.
M ¹ represents a zirconium atom or a hafnium atom.
Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene having 4 to 10 carbon atoms, an anionic ligand or a neutral ligand capable of coordinating with a lone electron pair; , j represents an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Q may be the same or different. )

The crosslinked metallocene compound [A] is preferably combined with the compound [C] described later to form a polymerization catalyst for producing an ethylene/α-olefin resin (α) having a melting point (Tm) in the range of 50 to 100°C. It functions suitably as.
The chemical structural features of the bridged metallocene compound [A] that can be used in the present invention are described below.

The bridged metallocene compound [A] has the following structural features [m1] and [m2].
[m1] Of the two ligands, one is an optionally substituted cyclopentadienyl group, and the other is a fluorenyl group having a substituent (hereinafter also referred to as a "substituted fluorenyl group" ).
[m2] Two ligands are bound by an ethylene bridge (hereinafter also referred to as "bridge").

The cyclopentadienyl group which may have a substituent, the substituted fluorenyl group, the crosslinked portion and other features of the bridged metallocene compound [A] are sequentially described below.

(Optionally substituted cyclopentadienyl group)
In formula [A], R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a heteroatom-containing group other than a silicon-containing group, preferably All of R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, or a structure in which one or more of R ¹ , R ² , R ³ and R ⁴ is a methyl group and the rest are hydrogen atoms Especially preferred.

(substituted fluorenyl group)
In formula [A], R ⁵ , R ⁸ , R ⁹ and R ¹² each independently represents a hydrogen atom, a hydrocarbon group, a silicon-containing group, or a heteroatom-containing group other than a silicon-containing group, and a hydrogen atom, a hydrocarbon group Alternatively, silicon-containing groups are preferred. R ⁶ and R ¹¹ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, and the hydrogen atom, the hydrocarbon group and the silicon-containing group are Preferably; ^R7 and ^R10 are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, and a hydrogen atom, a hydrocarbon group and a silicon-containing groups are preferred; R ⁶ and R ⁷ may be bonded together to form a ring, and R ¹⁰ and R ¹¹ may be bonded together to form a ring; provided that R ⁶ , R ⁷ , All of R ¹⁰ and R ¹¹ are not hydrogen atoms.

From the viewpoint of polymerization activity, it is preferable that none of R ⁶ and R ¹¹ is a hydrogen atom; more preferably none of R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ is a hydrogen atom; R ⁶ and R ¹¹ is the same radical selected from hydrocarbon radicals and silicon-containing radicals, and R ⁷ and R ¹⁰ are the same radicals selected from hydrocarbon radicals and silicon-containing radicals. It is also preferred that R ⁶ and R ⁷ are bonded together to form an alicyclic or aromatic ring, and R ¹⁰ and R ¹¹ are bonded together to form an alicyclic or aromatic ring.

Preferred groups for R ⁵ to R ¹² include, for example, hydrocarbon groups (preferably hydrocarbon groups having 1 to 20 carbon atoms, hereinafter sometimes referred to as "hydrocarbon groups (f1)") or silicon-containing groups (preferably silicon-containing groups having 1 to 20 carbon atoms, hereinafter sometimes referred to as "silicon-containing groups (f2)"). In addition, heteroatom-containing groups (excluding silicon-containing groups (f2)) such as halogenated hydrocarbon groups, oxygen-containing groups, and nitrogen-containing groups can also be mentioned.

Specific examples of the hydrocarbon group (f1) include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, Linear hydrocarbon groups such as n-nonyl group, n-decanyl group and allyl group; isopropyl group, isobutyl group, sec-butyl group, t-butyl group, amyl group, 3-methylpentyl group, neopentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1- branched hydrocarbon groups such as methyl-1-isopropyl-2-methylpropyl group; cyclic saturated hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group and adamantyl group; phenyl group, naphthyl cyclic unsaturated hydrocarbon groups such as groups, biphenyl groups, phenanthryl groups, and anthracenyl groups, and their nuclear alkyl substituents; saturated hydrocarbon groups such as benzyl groups and cumyl groups, at least one hydrogen atom of which is substituted with an aryl group and the groups described above.

The silicon-containing group (f2) for R ⁵ to R ¹² is preferably a silicon-containing group having 1 to 20 carbon atoms, for example, a silicon atom is directly covalently bonded to the ring carbon of a cyclopentadienyl group. Specific examples include groups in which an alkylsilyl group (eg, trimethylsilyl group) or an arylsilyl group (eg, triphenylsilyl group) is bonded to the ring carbon of a cyclopentadienyl group.

Specific examples of heteroatom-containing groups (excluding silicon-containing groups (f2)) include methoxy, ethoxy, phenoxy, N-methylamino, trifluoromethyl, tribromomethyl, and pentafluoroethyl groups. , a pentafluorophenyl group.

Among the hydrocarbon groups (f1), linear or branched aliphatic hydrocarbon groups having 1 to 20 carbon atoms, specifically methyl group, ethyl group, n-propyl group, isopropyl group, n- Preferable examples include butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, n-hexyl group and the like.

Substituted fluorenyl groups when R ⁶ and R ⁷ (R ¹⁰ and R ¹¹ ) are bonded to each other to form an alicyclic or aromatic ring include compounds represented by general formulas [II] to [VI] described below. Preferred examples include groups derived from

(Other features of bridged metallocene compound [A])
In formula [A], Q is a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene having 4 to 10 carbon atoms, an anionic ligand, or a lone electron pair capable of coordination represents a neutral ligand, j represents an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Q may be the same or different.

The hydrocarbon group for Q includes, for example, a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms and an alicyclic hydrocarbon group having 3 to 10 carbon atoms. Examples of aliphatic hydrocarbon groups include methyl group, ethyl group, n-propyl group, isopropyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,1- diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylbutyl group, 1,1,3 -Trimethylbutyl group, neopentyl group. Examples of alicyclic hydrocarbon groups include cyclohexyl, cyclohexylmethyl and 1-methyl-1-cyclohexyl groups.

Examples of the halogenated hydrocarbon group for Q include groups in which at least one hydrogen atom of the above hydrocarbon group for Q is substituted with a halogen atom.
M ¹ represents a zirconium atom or a hafnium atom, more preferably a zirconium atom.

(Examples of preferred bridged metallocene compounds [A])
Specific examples of the substituted fluorenyl group portion of the bridged metallocene compound [A] are shown below. Among the exemplary compounds, octamethyloctahydrodibenzofluorenyl refers to a group derived from a compound having a structure represented by formula [II], and octamethyltetrahydrodicyclopentafluorenyl is represented by formula [III]. dibenzofluorenyl refers to a group derived from a compound having a structure represented by formula [IV], 1,1′,3,6,8,8′-hexamethyl- 2,7-dihydrodicyclopentafluorenyl refers to a group derived from a compound having a structure represented by formula [V], 1,3,3′,6,6′,8-hexamethyl-2,7- Dihydrodicyclopentafluorenyl refers to a group derived from a compound having a structure represented by formula [VI].

Examples of the bridged metallocene compound [A] include:
Ethylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl)zirconium dichloride, Ethylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl)zirconium dichloride, Ethylene (cyclopentadiene) dienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, ethylene (cyclopentadienyl) (1,1′,3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl)zirconium dichloride, ethylene (cyclopentadienyl) ( 1,3,3′,6,6′,8-hexamethyl-2,7-dihydrodicyclopentafluorenyl)zirconium dichloride, ethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di tert-butylfluorenyl)zirconium dichloride, ethylene (cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluorenyl)zirconium dichloride, ethylene (cyclopentadienyl)(2,7 -(Trimethylphenyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride, ethylene (cyclopentadienyl) (2,7-(dimethylphenyl)-3,6-di-tert-butylfluorenyl) and zirconium dichloride.

Examples of the bridged metallocene compound [A] include compounds in which "dichloride" of the above-exemplified compounds is replaced with "difloride", "dibromide", "diaiodide", "dimethyl" or "methylethyl", and "cyclopentadienyl". "3-tert-butyl-5-methyl-cyclopentadienyl", "3,5-dimethyl-cyclopentadienyl", "3-tert-butyl-cyclopentadienyl" or "3-methyl-cyclo Pentadienyl” and the like can also be mentioned.

The above bridged metallocene compound [A] can be produced by a known method, and the production method is not particularly limited. Known methods include, for example, the methods described in International Publication No. 01/27124 and International Publication No. 04/029062 by the present applicant.

The above bridged metallocene compounds [A] may be used singly or in combination of two or more.

・Transition metal compound [B]
Transition metal compound [B] is a transition metal compound of Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton. The transition metal compound [B] preferably functions as a polymerization catalyst for producing the resin (β) according to the present invention, preferably in combination with the compound [C] described below.

As the transition metal compound [A] of Group 4 of the periodic table containing a ligand having a dimethylsilylbisnindenyl skeleton, Resconi, L. et al. Compounds exemplified in JACS 1992, 114, 1025-1032, etc. are known, and olefin polymerization catalysts for producing terminally unsaturated amorphous polymers can be suitably used.

In addition, as a transition metal compound [B] of Group 4 of the periodic table containing a ligand having a dimethylsilylbisnindenyl skeleton, Compounds disclosed in JP-A-2009-299046, JP-A-11-130807, JP-A-2008-285443, etc. can be preferably used.

More specifically, the transition metal compound [B] of Group 4 of the periodic table containing a ligand having a dimethylsilylbisnindenyl skeleton is selected from the group consisting of bridged bis(indenyl)zirconocenes and hafnocenes. can be mentioned as a suitable example. More preferred are dimethylsilyl-bridged bis(indenyl)zirconocene or hafnocene. More preferably, dimethylsilyl-bridged bis(indenyl)zirconocene is selected. By selecting zirconocene, the formation of long-chain branched polymers caused by the insertion reaction of the terminally unsaturated ethylene/α-olefin copolymer is suppressed.

More specifically, dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride or dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl is used as a suitable transition metal compound [B]. be able to.

・Compound [C]
The resin (α) in the present invention can be suitably produced by using the compound [C] together with the above-described bridged metallocene compound [A] as a polymerization catalyst. Moreover, the resin (β) in the present invention can be suitably produced by using the compound [C] together with the transition metal compound [B] described above as a polymerization catalyst. The compound [C] will be specifically described below.

The compound [C] functions as an olefin polymerization catalyst by reacting with the bridged metallocene compound [A] or the transition metal compound [B]. It is selected from organoaluminum oxy compounds and [C3] compounds that react with the bridged metallocene compound [A] or the transition metal compound [B] to form an ion pair. The compounds [C1] to [C3] are described below in order.

([C1] organometallic compound)
As the [C1] organometallic compound used in the present invention, specifically, an organoaluminum compound represented by the following general formula (C1-a), a Group 1 metal of the periodic table represented by the general formula (C1-b), and Complex alkylates with aluminum and dialkyl compounds of Group 2 or Group 12 metals of the periodic table represented by the general formula (C1-c) can be mentioned. [C1] organometallic compound does not include [C2] organoaluminum oxy compound described later.

上記一般式（Ｃ１－ａ）中、Ｒ^aおよびＲ^bは、互いに同一でも異なっていてもよく、炭素原子数が１～１５、好ましくは１～４の炭化水素基を示し、Ｙはハロゲン原子を示し、ｐは０＜ｐ≦３、ｑは０≦ｑ＜３、ｒは０≦ｒ＜３、ｓは０≦ｓ＜３の数であり、かつｐ＋ｑ＋ｒ＋ｓ＝３である。）

In the above general formula (C1-a), R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and Y is a halogen atom. where p is 0<p≤3, q is 0≤q<3, r is 0≤r<3, s is a number satisfying 0≤s<3, and p+q+r+s=3. )

上記一般式（Ｃ１－ｂ）中、Ｍ³はＬｉ、ＮａまたはＫを示し、Ｒ^cは炭素原子数が１～１５、好ましくは１～４の炭化水素基を示す。）

In general formula (C1-b) above, M ³ represents Li, Na or K, and R ^c represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. )

上記一般式（Ｃ１－ｃ）中、ＲdおよびＲeは、互いに同一でも異なっていてもよく、炭素原子数が１～１５、好ましくは１～４の炭化水素基を示し、Ｍ⁴はＭｇ、ＺｎまたはＣｄである。

In general formula (C1-c) above, R and Re may be the same or different and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ⁴ is Mg, Zn. or Cd.

Examples of the organoaluminum compound represented by the general formula (C1-a) include compounds represented by the following general formulas (C-1a-1) to (C-1a-4).

（式中、Ｒ^aおよびＲ^bは、互いに同一でも異なっていてもよく、炭素原子数が１～１５、好ましくは１～４の炭化水素基を示し、ｐは好ましくは１．５≦ｐ≦３の数である。）

(Wherein, R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably 1.5 ≤ p ≤ is the number of 3.)

（式中、Ｒ^aは炭素原子数が１～１５、好ましくは１～４の炭化水素基を示し、Ｙはハロゲン原子を示し、ｐは好ましくは０＜ｐ＜３の数である。）

(In the formula, R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p is preferably a number of 0<p<3.)

（式中、Ｒ^aは炭素原子数が１～１５、好ましくは１～４の炭化水素基を示し、ｐは好ましくは２≦ｐ＜３の数である。）

(In the formula, R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably a number satisfying 2≦p<3.)

（式中、Ｒ^aおよびＲ^bは、互いに同一でも異なっていてもよく、炭素原子数が１～１５、好ましくは１～４の炭化水素基を示し、Ｙはハロゲン原子を示し、ｐは０＜ｐ≦３、ｑは０≦ｑ＜３、ｓは０≦ｓ＜３の数であり、かつｐ＋ｑ＋ｓ＝３である。）

(Wherein, R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, Y represents a halogen atom, p is 0 <p≤3, q is 0≤q<3, s is a number satisfying 0≤s<3, and p+q+s=3.)

More specific examples of organoaluminum compounds belonging to the general formula (C1-a) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum. tri-n-alkylaluminum such as;
triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4 - tri-branched alkyl aluminum such as methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum;
tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum;

triarylaluminum such as triphenylaluminum and tritolylaluminum; dialkylaluminum hydride such as diisobutylaluminum hydride;
(iC ₄ H ₉ ) _{x Aly} (C ₅ H ₁₀ ) _z (wherein x, y and z are positive numbers and z≧2x), etc. trialkenyl aluminum such as; alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, isobutyl aluminum isopropoxide;
dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide;
A partially alkoxylated aluminum alkyl having an average composition represented by R ^a _2.5 Al(OR ^b ) _0.5 , wherein R ^a and R ^b can be the same or different and have the number of carbon atoms 1 to 15, preferably 1 to 4 hydrocarbon groups);

diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis(2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6- dialkylaluminum aryloxides such as di-t-butyl-4-methylphenoxide), isobutylaluminum bis(2,6-di-t-butyl-4-methylphenoxide);
dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
partially halogenated aluminum alkyls such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide;
dialkylaluminum hydride such as diethylaluminum hydride, dibutylaluminum hydride;
Other partially hydrogenated aluminum alkyls such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Partially alkoxylated and halogenated aluminum alkyls such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide, and the like can be mentioned.

Compounds similar to (C1-a) can also be used in the present invention, and examples of such compounds include organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such compounds include (C ₂ H ₅ ) ₂ AlN(C ₂ H ₅ )Al(C ₂ H ₅ ) ₂ and the like.

Examples of compounds belonging to the general formula (C1-b) include LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ .
Compounds belonging to the general formula (C1-c) include dimethylmagnesium, diethylmagnesium, dibutylmagnesium, butylethylmagnesium, dimethylzinc, diethylzinc, diphenylzinc, di-n-propylzinc, diisopropylzinc, di-n- Butyl zinc, diisobutyl zinc, bis(pentafluorophenyl) zinc, dimethylcadmium, diethylcadmium and the like can be mentioned.

In addition, [C1] organometallic compounds include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, Butylmagnesium bromide, butylmagnesium chloride, and the like can also be used.

Also, a compound that forms the above organoaluminum compound in the polymerization system, such as a combination of an aluminum halide and an alkyllithium, or a combination of an aluminum halide and an alkylmagnesium, is used as the above [C1] organometallic compound. You can also
The above [C1] organometallic compounds may be used singly or in combination of two or more.

([C2] organoaluminum oxy compound)
The [C2] organoaluminumoxy compound used in the present invention may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminumoxy compound as exemplified in JP-A-2-78687. good. Specific examples of the [C2] organoaluminumoxy compound include methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.
Conventionally known aluminoxanes can be produced, for example, by the following method, and are usually obtained as a solution in a hydrocarbon solvent.

(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerous chloride hydrate, etc. A method of adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension of (1) and reacting the adsorbed water or water of crystallization with the organoaluminum compound.

(2) A method in which water, ice or steam is directly acted on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of organometallic components. After removing the solvent or unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, the obtained aluminoxane may be redissolved in the solvent or suspended in a poor solvent for the aluminoxane.

Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the general formula (C1-a).

Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred.
The above organoaluminum compounds may be used singly or in combination of two or more.

Solvents used in the preparation of aluminoxanes include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; , cyclohexane, cyclooctane, methylcyclopentane and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbon halides. and hydrocarbon solvents such as sulfides and bromides. Ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferred.

In the benzene-insoluble organoaluminumoxy compound used in the present invention, the Al component dissolved in benzene at 60° C. is usually 10% or less, preferably 5% or less, and particularly preferably 2% or less in terms of Al atoms. That is, it is preferably insoluble or sparingly soluble in benzene.

As the [C2] organoaluminumoxy compound used in the present invention, an organoaluminumoxy compound containing boron represented by the following general formula (III) can also be mentioned.

（一般式（ＩＩＩ）中、Ｒ¹⁷は炭素原子数が１～１０の炭化水素基を示し、４つのＲ¹⁸は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数が１～１０の炭化水素基を示す。）

(In the general formula (III), R ¹⁷ represents a hydrocarbon group having 1 to 10 carbon atoms, and the four R ¹⁸ may be the same or different, and may contain a hydrogen atom, a halogen atom, or a 1 to 10 hydrocarbon groups are shown.)

The organoaluminumoxy compound containing boron represented by the above general formula (III) is obtained by dissolving an alkylboronic acid represented by the following general formula (IV) and an organoaluminum compound in an inert gas atmosphere in an inert solvent. It can be produced by reacting at a temperature of −80° C. to room temperature for 1 minute to 24 hours.

（一般式（ＩＶ）中、Ｒ¹⁹は上記一般式（ＩＩＩ）におけるＲ¹⁷と同じ基を示す。）

(In general formula (IV), R ¹⁹ represents the same group as R ¹⁷ in general formula (III) above.)

Specific examples of alkylboronic acids represented by the general formula (IV) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, acids, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, 3,5-bis(trifluoromethyl)phenylboronic acid and the like. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid and pentafluorophenylboronic acid are preferred. These are used individually by 1 type or in combination of 2 or more types.

Specific examples of the organoaluminum compound to be reacted with such an alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the general formula (C1-a).

As the organic aluminum compound, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These are used individually by 1 type or in combination of 2 or more types.
The above [C2] organoaluminumoxy compounds may be used singly or in combination of two or more.

([C3] A compound that forms an ion pair by reacting with a bridged metallocene compound [A] or a transition metal compound [B])
The compound [C3] (hereinafter referred to as "ionized ionic compound") that reacts with the bridged metallocene compound [A] or the transition metal compound [B] to form an ion pair includes those described in JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106, etc. Examples include Lewis acids, ionic compounds, borane compounds and carborane compounds. In addition, heteropolycompounds and isopolycompounds may also be mentioned.

Specifically, the Lewis acid is a compound represented by BR ₃ (R is a phenyl group or fluorine optionally having a substituent such as fluorine, a methyl group, a trifluoromethyl group, etc.). trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron, tris(3,5-dimethylphenyl)boron and the like.

Examples of the ionic compound include compounds represented by the following general formula (V).

（一般式（Ｖ）中、Ｒ²⁰はＨ⁺、カルボニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオンまたは遷移金属を有するフェロセニウムカチオンであり、Ｒ²¹～Ｒ²⁴は、互いに同一でも異なっていてもよく、有機基、好ましくはアリール基または置換アリール基である。）。

(In general formula (V), R ²⁰ is H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation or ferrocenium cation having a transition metal, and R ²¹ to R ²⁴ are the same or different and are organic groups, preferably aryl or substituted aryl groups).

Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, tri(n-butyl)ammonium cation; N,N-dimethylanilinium cation, N,N-dialkylanilinium cations such as N,N-diethylanilinium cations and N,N-2,4,6-pentamethylanilinium cations; dialkylammonium cations such as di(isopropyl)ammonium cations and dicyclohexylammonium cations etc.

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.

As R ²⁰ , carbonium cations and ammonium cations are preferred, and triphenylcarbonium cations, N,N-dimethylanilinium cations and N,N-diethylanilinium cations are particularly preferred.

Examples of ionic compounds include trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

Specific examples of the trialkyl-substituted ammonium salts include triethylammoniumtetra(phenyl)boron, tripropylammoniumtetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammoniumtetra(p-tolyl ) boron, trimethylammonium tetra(o-tolyl) boron, tri(n-butyl) ammonium tetra(pentafluorophenyl) boron, tripropylammonium tetra(o,p-dimethylphenyl) boron, tri(n-butyl) ammonium tetra (m,m-dimethylphenyl) boron, tri(n-butyl) ammonium tetra(p-trifluoromethylphenyl) boron, tri(n-butyl) ammonium tetra(3,5-ditrifluoromethylphenyl) boron, tri( and n-butyl)ammonium tetra(o-tolyl)boron.

Specific examples of the N,N-dialkylanilinium salts include N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron, N,N,2,4, 6-pentamethylaniliniumtetra(phenyl)boron and the like.

Specific examples of the dialkylammonium salts include di(1-propyl)ammoniumtetra(pentafluorophenyl)boron, dicyclohexylammoniumtetra(phenyl)boron and the like.

Furthermore, as ionic compounds, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, ferroceniumtetra(pentafluorophenyl)borate, triphenylcarbeniumpentaphenyl Cyclopentadienyl complexes, N,N-diethylanilinium pentaphenylcyclopentadienyl complexes, boron compounds represented by the following formula (VI) or (VII), and the like can also be mentioned.

（式（ＶＩ）中、Ｅｔはエチル基を示す。）

(In formula (VI), Et represents an ethyl group.)

（式（ＶＩＩ）中、Ｅｔはエチル基を示す。）

(In formula (VII), Et represents an ethyl group.)

Specific examples of borane compounds that are examples of ionized ionic compounds (compound [C3]) include decaborane;
Bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, bis[tri(n-butyl)ammonium]dodecaborate , salts of anions such as bis[tri(n-butyl)ammonium]decachlorodecaborate, bis[tri(n-butyl)ammonium]dodecachlorododecaborate;
metal borane anions such as tri(n-butyl)ammonium bis(dodecahydride dodecaborate) cobaltate (III) and bis[tri(n-butyl)ammonium]bis(dodecahydride dodecaborate) nickelate (III); Examples include salt.

Specific carborane compounds that are examples of ionizable ionic compounds include, for example, 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3- dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydrite-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2 ,7-dicarboundecaborane, undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri(n-butyl)ammonium 1-carbadecaborate, tri(n-butyl)ammonium 1-carbaundecaborate, tri(n-butyl)ammonium 1-carbadodecaborate, tri(n-butyl)ammonium 1-trimethylsilyl-1-carbadecaborate, tri(n-butyl)ammonium bromo-1-carbadodecaborate, tri(n-butyl)ammonium 6-carbadecaborate, tri(n-butyl)ammonium 6-carbadecaborate, tri(n-butyl)ammonium 7 -Carbaundecaborate, tri(n-butyl)ammonium 7,8-dicarbaundecaborate, tri(n-butyl)ammonium 2,9-dicarbaundecaborate, tri(n-butyl)ammonium dodecahydride-8- methyl-7,9-dicarboundecaborate, tri(n-butyl)ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-8-butyl- 7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7, salts of anions such as 8-dicarboundecaborate, tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carboundecaborate;

Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate) Ferrate (III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarboundecaborate) cobaltate (III), tri(n-butyl)ammonium bis(undecahydride-7 ,8-dicarbaundecaborate)nickelate (III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate)cuprate(III), tri(n-butyl) Ammonium bis(undecahydride-7,8-dicarbaundecaborate)aurate (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) ferrate (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) chromate (III), tri(n-butyl)ammonium bis( Tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate) chromate (III) , bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboundecaborate) manganate (IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbohydrate) boundecaborate) cobaltate (III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboundecaborate)nickelate (IV), and the like salts of metal carborane anions; be done.

Heteropolycompounds, which are examples of ionizable ionic compounds, contain atoms selected from silicon, phosphorus, titanium, germanium, arsenic and tin and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. is a compound. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus tungstic acid, germanotungstic acid, stannotungstic acid, phosphomolybdovanadate, phosphotungstovanadate, germanotungstovanadate, phosphomolybdotungstovanadate, germanomolybdotungstovanadate, phosphomolybdotungstic acid , phosphomolybdoniobic acid, and salts of these acids. Further, as the above-mentioned salt, the above-mentioned acid is, for example, a group 1 or 2 metal of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc. organic salts such as salts and triphenylethyl salts;

Isopolycompounds, examples of ionized ionic compounds, are compounds composed of metal ions of one atom selected from vanadium, niobium, molybdenum and tungsten, and are considered molecular ionic species of metal oxides. can be done. Specific examples include, but are not limited to, vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids. The above salts include salts of the above acids with, for example, metals of Group 1 or Group 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc. and organic salts such as triphenylethyl salts.

The above ionized ionic compounds ([C3] bridged metallocene compound [A] or a compound that forms an ion pair by reacting with the transition metal compound [B]) are used singly or in combination of two or more. .

In addition to the bridged metallocene compound [A] or the transition metal compound [B], when a [C2] organoaluminumoxy compound such as methylaluminoxane is used as a cocatalyst component, very high polymerization activity is exhibited for olefin compounds.

The [C3] ionized ionic compound as described above may be used alone or in combination of two or more.
The organometallic compound [C1] is a transition metal atom in the transition metal compound [A] in a reaction (hereinafter also referred to as reaction (A)) using the organometallic compound [C1] and the transition metal compound [A] as a catalyst. (M) is a transition metal atom (M ) and the molar ratio (C1/M) is generally 0.01 to 100,000, preferably 0.05 to 50,000.

The organoaluminumoxy compound [C2] is the molar ratio (C2/M) between the aluminum atom in the organoaluminumoxy compound [C2] and the transition metal atom (M) in the bridged metallocene compound [A], and the transition metal They are used in amounts such that the molar ratio (C2/M) to the transition metal atom (M) in compound [B] is usually 10 to 500,000, preferably 20 to 100,000.

The ionized ionic compound [C3] is the molar ratio (C3/M) between the ionized ionic compound [C3] and the transition metal atom (M) in the bridged metallocene compound [A], and the transition metal compound [B] to the transition metal atom (M) (zirconium atom or hafnium atom) (C3/M) is usually 1-10, preferably 1-5.

The polymerization method in the present invention can be carried out in any of gas phase polymerization, slurry polymerization, bulk polymerization, and solution (dissolution) polymerization, and the polymerization form is not particularly limited, but from the viewpoint of efficiently obtaining a graft copolymer. solution polymerization is more preferred.

When solution polymerization is carried out, the polymerization solvent includes, for example, aliphatic hydrocarbons, aromatic hydrocarbons, and the like. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; and benzene, toluene, and xylene. and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, which can be used singly or in combination of two or more. Of these, heptane or hexane is preferred from the viewpoint of reducing the load in post-treatment steps.

The polymerization temperature is generally 50°C to 200°C, preferably 80°C to 150°C, more preferably 80°C to 130°C.
The polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous processes. In the present invention, among these methods, it is preferable to employ a method in which monomers are continuously supplied to a reactor for copolymerization.

Reaction time (average residence time when copolymerization is carried out by a continuous method) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours. is.

The polymer concentration is 5 to 50% by mass, preferably 10 to 40% by mass, during steady operation. It is preferably 15 to 50% by mass from the viewpoint of the viscosity limitation in the polymerization ability, the load of the post-treatment step (desolvation), and the productivity.

The molecular weight of the resulting copolymer can be adjusted by varying the polymerization temperature. Furthermore, it can also be adjusted by the amount of the aforementioned compound [C1] used. Specifically, the molecular weight is lowered by increasing the amount of triisobutylaluminum, methylaluminoxane, diethylzinc, or the like.

Although it is possible to adjust the molecular weight by adding hydrogen, the polymerization in the presence of hydrogen reduces the degree of terminal unsaturation of the macromonomer, so production under hydrogen-free conditions is preferred.
In addition to the polymerization reaction step, the method for producing the resin composition of the present invention may include, if necessary, a step of recovering the produced polymer. This reaction is a reaction in which the organic solvent used in the polymerization reaction is separated and the polymer is taken out and converted into a product form. If it is a process for manufacturing existing polyolefin resins such as solvent concentration, extrusion degassing, pelletizing, etc., there are special restrictions. no.

Viscosity Modifier for Lubricating Oil The viscosity modifier for lubricating oil of the present invention contains the above resin (α) and resin (β). The lubricating oil viscosity modifier of the present invention preferably contains 1 to 99 parts by weight of the resin (α) and 99 to 99 parts by weight of the resin (β) when the total of the resin (α) and the resin (β) is 100 parts by mass. 1 part by weight, more preferably 5 to 95 parts by weight of resin (α) and 95 to 5 parts by weight of resin (β).
Such a lubricating oil viscosity modifier of the present invention, when used by being added to a lubricating oil base (lubricating oil base oil), has a good balance between the viscosity index and the low-temperature viscosity of the resulting lubricating oil composition. can be

The lubricating oil composition containing the lubricating oil viscosity modifier of the present invention, which contains the resin (α) and the resin (β), has excellent viscosity characteristics at high temperatures and excellent low temperature characteristics, and has a viscosity index and a low temperature viscosity. The inventor of the present invention considers the reason why the balance is good as follows. That is, it is presumed that the resin (α) forms aggregates in the lubricating oil composition at low temperatures, thereby reducing the flow rate (effective volume) and resulting in excellent viscosity characteristics at low temperatures. Further, by containing the resin (β), the aggregates are less likely to precipitate out of the lubricating oil composition or gel due to crystallization between aggregates, and the lubricating oil composition has excellent low-temperature storage stability. We estimate that It is presumed that the blending of both the highly crystalline resin (α) and the low crystalline resin (β) improves the balance between the viscosity index and the low temperature period.

The lubricating oil viscosity modifier of the present invention may be used by being added directly to a lubricating oil base, or a lubricating oil additive composition containing the oil (B) described later together with the lubricating oil viscosity modifier. may be added to the lubricating oil base material in the form of

<Additive composition for lubricating oil>
The lubricating oil additive composition of the present invention comprises 1 to 50 parts by mass of the lubricating oil viscosity modifier (A) of the present invention and 50 to 99 parts by mass of the oil (B) (however, the lubricating oil viscosity modifier (A) and oil (B) totaling 100 parts by mass). Preferably, the lubricating oil viscosity modifier (A) is in the range of 2 to 40 parts by mass, the oil (B) is in the range of 60 to 98 parts by mass, more preferably the lubricating oil viscosity modifier (A) is in the range of 3 to 30 parts by mass. , containing the oil (B) in the range of 70 to 97 parts by mass.

The oil (B) contained in the lubricating oil additive composition includes mineral oils; and synthetic oils such as poly-α-olefins, diesters and polyalkylene glycols.
Oil (B) may be mineral oil, synthetic oil, or a blend of mineral oil and synthetic oil. Examples of diesters include polyol esters, dioctyl phthalate, dioctyl sebacate and the like.

Mineral oil is generally used after a refining process such as dewaxing, and there are several grades depending on the refining method. Mineral oils with a wax content of 0.5 to 10% are generally used. For example, a highly refined oil having a low pour point, a high viscosity index, and a composition mainly composed of isoparaffins produced by a hydrocracking refining method can also be used. Mineral oils with kinematic viscosities from 10 to 200 cSt at 40° C. are commonly used.

As described above, mineral oil is generally used after undergoing a refining process such as dewaxing, and there are several grades depending on the method of refining, and this grade is defined by the API (American Petroleum Institute) classification. Table 1 shows the properties of the lubricating oil bases classified into each group.

The poly-α-olefin in Table 1 is a hydrocarbon-based polymer obtained by polymerizing an α-olefin having at least 10 carbon atoms or more as one of raw material monomers, such as polydecene obtained by polymerizing 1-decene. are exemplified.

The oil (B) used in the present invention is preferably a mineral oil belonging to any one of the above groups (i) to (iv). Particularly preferred among mineral oils are those having a kinematic viscosity at 100° C. of 1 to 50 mm ² /s and a viscosity index of 80 or more, or poly-α-olefins. As the oil (B), a mineral oil belonging to group (ii) or group (iii), or a poly-α-olefin belonging to group (iv) is preferable. Groups (ii) and (iii) tend to have lower wax concentrations than group (i). In particular, the oil (B) is a mineral oil having a kinematic viscosity at 100° C. of 1 to 50 mm ² /s and a viscosity index of 80 or more and belonging to group (ii) or group (iii); Alternatively, poly-α-olefins belonging to group (iv) are preferred.

In addition, the lubricating oil additive composition of the present invention may contain components (additives) other than the lubricating oil viscosity modifier (A) and the oil (B). Other components may specifically include one or more additives as described below.

One such additive is a detergent. Many of the conventional detergents used in the engine lubrication field are based on basic metal compounds (typically metal hydroxides, oxides and carbonates based on metals such as calcium, magnesium and sodium). salt) imparts basicity or TBN to the lubricating oil. Such metallic overbased detergents (also called overbased salts or overbased salts) are generally neutralized according to the stoichiometry of the metal and the specific acidic organic compound that reacts with the metal. It is a single phase homogeneous Newtonian system characterized by a metal content in excess of what is believed to be present. Overbased materials combine acidic materials (typically inorganic acids and lower carboxylic acids such as carbon dioxide) with acidic organic compounds (also called substrates) and a stoichiometric excess of metals. It is typically prepared by reacting a mixture of salts, typically in an organic solvent inert to acidic organic substrates (eg mineral oil, naphtha, toluene, xylene, etc.). Accelerators such as phenols and alcohols are optionally present in small amounts. Acidic organic matrices will usually have a sufficient number of carbon atoms to confer some degree of solubility in oil.

Such conventional overbased materials and methods for their preparation are well known to those skilled in the art. Patents describing techniques for making basic metal salts of sulfonic acids, carboxylic acids, phenols, phosphoric acids, and mixtures of two or more thereof include U.S. Pat. Nos. 2,501,731; 2,616,925; 2,777,874; 3,256,186; 3,384,585; 3,365,396 3,320,162; 3,318,809; 3,488,284; and 3,629,109. Salixarate detergents are described in US Pat. No. 6,200,936 and WO 01/56968. Saligenin detergents are described in US Pat. No. 6,310,009.

The amount of a typical detergent in the lubricating oil additive composition is not particularly limited as long as the effect of the present invention is exhibited, but is usually 1 to 10% by mass, preferably 1.5 to 9.0% by mass, more preferably is 2.0 to 8.0% by mass. It should be noted that all such amounts are based on no oil (ie, no diluent oil as they are conventionally supplied).

Another additive is a dispersant. Dispersants are well known in the lubricating art and primarily include what are known as ashless dispersants, polymeric dispersants. Ashless dispersants are characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include nitrogen-containing dispersants such as N-substituted long chain alkenyl succinimides, also known as succinimide dispersants. Succinimide dispersants are more fully described in US Pat. Nos. 4,234,435 and 3,172,892. Another class of ashless dispersants are high molecular weight esters prepared by the reaction of polyhydric fatty alcohols such as glycerol, pentaerythritol and sorbitol with hydrocarbyl acylating agents. Such materials are described in more detail in US Pat. No. 3,381,022. Another class of ashless dispersants are Mannich bases. These are materials formed by the condensation of high molecular weight alkyl-substituted phenols, alkylene polyamines, and aldehydes such as formaldehyde, and are described in more detail in US Pat. No. 3,634,515. Other dispersants include polyhydric dispersant additives, which are generally hydrocarbon-based polymers containing polar functionalities that impart dispersant properties to the polymer.

Dispersants may be post-treated by reacting with any of a variety of substances. These include urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, and phosphorus compounds. is given. A reference detailing such processing is found in US Pat. No. 4,654,403. The amount of the dispersant in the composition of the present invention is not particularly limited as long as the effect of the present invention is exhibited, but typically 1 to 10% by mass, preferably 1.5 to 9.0% by mass, more preferably can range from 2.0 to 8.0% by weight (all on an oil-free basis).

Another component is an antioxidant. Antioxidants include phenolic antioxidants, which may include butyl-substituted phenols having 2-3 t-butyl groups. The para position may be occupied by a hydrocarbyl group or a group linking two aromatic rings. The latter antioxidants are described in more detail in US Pat. No. 6,559,105. Antioxidants also include aromatic amines such as nonylated diphenylamine. Other antioxidants include sulfurized olefins, titanium compounds, and molybdenum compounds. For example, US Pat. No. 4,285,822 discloses a lubricating oil composition comprising a composition containing molybdenum and sulfur. Typical amounts of antioxidants will of course depend on the specific antioxidants and their individual effectiveness, but an exemplary total amount is 0.01 to 5% by weight, preferably 0.15%. It can be up to 4.5% by weight, more preferably 0.2-4% by weight. Additionally, one or more antioxidants may be present, and certain combinations of these may be synergistic to their combined overall effect.

The lubricating oil additive compositions of the present invention may also include thickeners (sometimes referred to as viscosity index improvers or viscosity modifiers). Thickeners are usually polymeric and include polyisobutenes, polymethacrylates, diene polymers, polyalkylstyrenes, esterified styrene-maleic anhydride copolymers, alkenylarene conjugated diene copolymers and Polyolefins are mentioned. Multifunctional thickeners that also have dispersant and/or antioxidant properties are known and may optionally be used.

Another additive is an antiwear agent. Examples of antiwear agents include metal thiophosphates, phosphate esters and their salts, phosphorus-containing carboxylic acids, esters, ethers, amides; and phosphorus-containing antiwear agents such as phosphites. / extreme pressure agents. In a specific embodiment, the phosphorus wear inhibitor is not particularly limited as long as the effect of the present invention is exhibited, but is usually 0.01 to 0.2% by mass, preferably 0.015 to 0.15% by mass, more preferably It may be present in an amount to provide 0.02 to 0.1 wt%, more preferably 0.025 to 0.08 wt% phosphorous.

Often the antiwear agent is a zinc dialkyldithiophosphate (ZDP). A typical ZDP may contain 11 wt% P (calculated on an oil-free basis), and a suitable amount may include 0.09-0.82 wt%. Phosphorus-free antiwear agents include borate esters (including borate epoxides), dithiocarbamate compounds, molybdenum-containing compounds, and sulfurized olefins.
Other additives that may optionally be used in the lubricating oil additive composition include the above-described extreme pressure agents and antiwear agents, as well as pour point depressants, friction modifiers, color stabilizers, and antifoam agents. and each may be used in conventional amounts.

The lubricating oil additive composition of the present invention preferably contains the lubricating oil viscosity modifier (A) and the oil (B) in the above ranges. When producing a lubricating oil composition using the lubricating oil additive composition containing the lubricating oil viscosity modifier (A) and the oil (B) in the above range, the lubricating oil additive composition, By mixing with other components of the lubricating oil composition, it is possible to obtain a lubricating oil composition having an excellent balance between viscosity index and low-temperature viscosity with a small content of viscosity modifier for lubricating oil (A).

In addition, since the additive composition for lubricating oil of the present invention contains the oil (B), it has good workability when producing the lubricating oil composition, and can be easily mixed with other components of the lubricating oil composition. can do.

The lubricating oil additive composition of the present invention can be prepared by mixing the lubricating oil viscosity modifier (A) and the oil (B), optionally with other desired ingredients, in a conventionally known manner. can. Here, the lubricating oil viscosity modifier (A) may be prepared in advance, and each component constituting the lubricating oil viscosity modifier (A) may be added to the lubricating oil additive of the present invention. It may be used directly in the manufacture of compositions. That is, the lubricating oil additive composition of the present invention is obtained by sequentially adding each component constituting the lubricating oil viscosity modifier (A) and the oil (B) optionally together with other desired components by a conventionally known method. Or it can be prepared by mixing at the same time.

<Lubricating oil composition>
The lubricating oil composition of the present invention comprises 0.1 to 5 parts by mass of the lubricating oil viscosity modifier (A) of the present invention and 95 to 99.9 parts by mass of the lubricating oil base (BB) (however, the lubricating oil and a viscosity modifier for lubricating oil, and a lubricating oil base (BB), the total of which is 100 parts by mass). Lubricating oil viscosity modifier (A) is preferably 0.2 to 4 parts by mass, more preferably 0.4 to 3 parts by mass, still more preferably 0.6 to 2 parts by mass, lubricating oil base (BB) is preferably contained in a proportion of 96 to 99.8 parts by mass, more preferably 97 to 99.6 parts by mass, still more preferably 98 to 99.4 parts by mass. The lubricating oil viscosity modifier (A) may be used alone or in combination of multiple types.

The lubricating oil composition of the present invention may further contain a pour point depressant (C). The content of the pour point depressant (C) is not particularly limited as long as the effect of the present invention is exhibited, but usually 0.05 to 5% by mass, preferably 0.05 to 3% by mass in 100% by mass of the lubricating oil composition %, more preferably 0.05 to 2 mass %, and still more preferably 0.05 to 1 mass %.

In the lubricating oil composition of the present invention, when the content of the lubricating oil viscosity modifier (A) of the present invention is within the above range, the lubricating oil composition has excellent low-temperature storage stability and low-temperature viscosity, and has a viscosity index and It is particularly useful because of its excellent balance in low temperature years.

The lubricating oil base (BB) contained in the lubricating oil composition includes mineral oils and synthetic oils such as poly-α-olefins, diesters and polyalkylene glycols.
Mineral oil or blends of mineral and synthetic oils may also be used. Examples of diesters include polyol esters, dioctyl phthalate, dioctyl sebacate and the like.

Mineral oil is generally used after a refining process such as dewaxing, and there are several grades depending on the refining method. Mineral oils with a wax content of 0.5 to 10% by weight are generally used. For example, a highly refined oil having a low pour point, a high viscosity index, and a composition mainly composed of isoparaffins produced by a hydrocracking refining method can also be used. Mineral oils with kinematic viscosities from 10 to 200 cSt at 40° C. are commonly used.

As described above, mineral oil is generally used after undergoing a refining process such as dewaxing, and there are several grades depending on the method of refining, and this grade is defined by the API (American Petroleum Institute) classification. The properties of the lubricating oil bases classified into each group are as shown in Table 1 above.

Polyα-olefin in Table 1 is a hydrocarbon-based polymer obtained by polymerizing at least one α-olefin having 10 or more carbon atoms as a raw material monomer, such as polydecene obtained by polymerizing 1-decene. are exemplified.

The lubricating oil base (BB) used in the present invention may be an oil belonging to any of groups (i) to (iv). In one embodiment, the oil is a mineral oil having a kinematic viscosity at 100° C. of 1 to 50 mm ² /s and a viscosity index of 80 or more, or a poly-α-olefin. As the lubricating oil base (BB), mineral oils belonging to group (ii) or group (iii), or poly-α-olefins belonging to group (iv) are preferable. Groups (ii) and (iii) tend to have lower wax concentrations than group (i).

In particular, the lubricating oil base (BB) is a mineral oil having a kinematic viscosity at 100° C. of 1 to 50 mm ² /s and a viscosity index of 80 or more and belonging to group (ii) or group (iii). or polyα-olefins belonging to group (iv) are preferred.

Pour point depressants (C) that the lubricating oil composition may contain include alkylated naphthalenes, (co)polymers of alkyl methacrylates, (co)polymers of alkyl acrylates, alkyl fumarates and vinyl acetate. copolymers, α-olefin polymers, copolymers of α-olefins and styrene, and the like. In particular, alkyl methacrylate (co)polymers and alkyl acrylate (co)polymers may be used.

The lubricating oil composition of the present invention may contain compounding agents (additives) in addition to the lubricating oil viscosity modifier (A), the lubricating oil base (BB) and the pour point depressant (C).

When the lubricating oil composition of the present invention contains a compounding agent, the content is not particularly limited, but when the total of the lubricant base (BB) and the compounding agent is 100% by mass, The content is usually more than 0% by mass, preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more. The content of the compounding agent is usually 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.

As a compounding agent (additive), it is different from the lubricating oil base (BB) and the pour point depressant (C), and an addition such as that described in detail in the section of the additive composition for lubricating oil (A) For example, hydrogenated SBR (styrene-butadiene rubber), SEBS (styrene-ethylene-butylene-styrene block copolymer), additives that improve the viscosity index, detergents, anti-rust additives, dispersants, extreme pressure agents, antifoaming agents, antioxidants, metal deactivators, and the like.

The lubricating oil composition of the present invention is prepared by a conventionally known method, the viscosity modifier for lubricating oil of the present invention (A), the lubricating oil base (BB) and optionally the pour point depressant (C), and optionally the pour point depressant (C). It can be prepared by mixing or dissolving other compounding agents (additives) depending on the conditions.
Further, the lubricating oil composition of the present invention comprises the lubricating oil additive composition of the present invention containing the lubricating oil viscosity modifier (A) of the present invention, a lubricating oil base (BB) and, if necessary, It can also be prepared by mixing or dissolving the pour point depressant (C) and, if necessary, other compounding agents (additives).

The lubricating oil composition of the present invention is excellent in low-temperature storage stability and low-temperature viscosity. Accordingly, the lubricating oil composition of the present invention can be used, for example, in automobile engine oils, lubricating oils for diesel engines for heavy-duty vehicles, lubricating oils for marine diesel engines, lubricating oils for two-stroke engines, lubricating oils for automatic transmissions and It can be used to lubricate any of a variety of known mechanical devices, such as lubricating oils for manual transmissions, gear lubricating oils and greases.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.
Measurement/evaluation method
In the following examples and comparative examples, each physical property was measured or evaluated by the following methods.

[Melting point (Tm) (°C)]
The resin produced in Examples or Comparative Examples is subjected to DSC measurement using a differential scanning calorimeter manufactured by SII (X-DSC7000) calibrated with an indium standard to determine the melting point (Tm).

Weigh approximately 10 mg of the above measurement sample onto an aluminum DSC pan. A lid is crimped onto the pan to provide a closed atmosphere and a sample pan.
Place the sample pan in the DSC cell and place an empty aluminum pan as a reference. The DSC cell is heated from 30° C. (room temperature) to 150° C. at a rate of 10° C./min in a nitrogen atmosphere (first temperature rising process).

After holding the temperature at 150° C. for 5 minutes, the temperature is lowered at 10° C./min to cool the DSC cell to −100° C. (temperature lowering process). After holding at −100° C. for 5 minutes, the temperature of the DSC cell is raised to 150° C. at 10° C./min (second temperature raising process).

Let the melting peak top temperature of the enthalpy curve obtained in the second heating process be the melting point (Tm). If more than one melting peak is present, the one with the largest peak is defined as the melting point (Tm). In addition, those in which no melting peak is observed are evaluated as having no melting point.

[Crystallization temperature (Tc) (° C.)]
The crystallization temperature Tc was measured using the DSC used to measure the melting point (Tm) described above. Specifically, first, the temperature of the measurement sample was raised to 200° C. and held for 5 minutes. Thereafter, the temperature was lowered at a rate of 2° C./min, and the temperature at the exothermic peak of the obtained DSC curve was defined as the crystallization temperature (Tc).

[Intrinsic viscosity [η] (dL/g)]
The intrinsic viscosity [η] was measured at 135°C using decalin solvent. Specifically, about 20 mg of polymerized powder, pellets or resin lumps were dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135°C. 5 ml of the decalin solvent was added to the decalin solution to dilute it, and then the specific viscosity ηsp was measured in the same manner. This dilution operation was repeated twice, and the value of ηsp/C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity (see the following formula).
[η]=lim(ηsp/C) (C→0)

[density]
The density of resins produced or used in Examples or Comparative Examples is measured according to the method described in JIS K7112.

[Weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn)]
The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the copolymers produced or used in Examples or Comparative Examples are measured by gel permeation chromatography (GPC) by the following methods.

(Pretreatment of sample)
After dissolving 30 mg of the copolymer produced or used in Examples or Comparative Examples in 20 ml of o-dichlorobenzene at 145° C., the solution was filtered through a sintered filter with a pore size of 1.0 μm to prepare an analysis sample.

(GPC analysis)
Gel permeation chromatography (GPC) is used to determine weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution curve. Calculations are made in terms of polystyrene. A molecular weight distribution (Mw/Mn) is calculated from the obtained weight average molecular weight (Mw) and number average molecular weight (Mn).

(measuring device)
Gel permeation chromatograph HLC-8321 GPC/HT type (manufactured by Tosoh Corporation)
(Analysis device)
Data processing software Empower2 (Waters, registered trademark)
(Measurement condition)
Columns: 2 columns of TSKgel GMH ₆ -HT and 2 columns of TSKgel GMH ₆ -HTL (both diameter 7.5 mm x length 30 cm, Tosoh Corporation)
Column temperature: 140°C
Mobile phase: o-dichlorobenzene (containing 0.025% BHT)
Detector: Differential refractometer Flow rate: 1 mL/min Sample concentration: 0.15% (w/v)
Injection volume: 0.4 mL
Sampling time interval: 1 second Column calibration: Monodisperse polystyrene (Tosoh Corporation)
Molecular weight conversion: PS conversion / standard conversion method

[Structural unit derived from ethylene]
The ethylene- and α-olefin-derived structural units (mol %) of the copolymers produced or used in Examples or Comparative Examples are determined by ¹³ C-NMR spectrum analysis.
(measuring device)
AVANCEIII500CryoProbe Prodigy type nuclear magnetic resonance apparatus manufactured by Bruker Biospin

(Measurement condition)
Measurement nucleus: ¹³ C (125 MHz), measurement mode: single pulse proton broadband decoupling, pulse width: 45° (5.00 μs), number of points: 64 k, measurement range: 250 ppm (-55 to 195 ppm), repetition time: 5.5 seconds, number of accumulations: 512 times, measurement solvent: ortho-dichlorobenzene/benzene-d ₆ (4/1 v/v), sample concentration: ca. 60 mg/0.6 mL, measurement temperature: 120° C., window function: exponential (BF: 1.0 Hz), chemical shift standard: benzene-d ₆ (128.0 ppm).

[Viscosity characteristics (kinematic viscosity, viscosity index)]
The kinematic viscosity at 100°C and 40°C was measured by the method described in JIS K2283, and the viscosity index was calculated. A larger value of the viscosity index indicates a smaller change in viscosity with temperature.

[Cold Cranking Simulator (CCS) viscosity]
The CCS viscosity (−30° C.) of the mineral oil-blended lubricating oil composition prepared in Examples or Comparative Examples is measured according to ASTM D2602. The CCS viscosity is used to evaluate the low temperature slidability (startability) of the crankshaft. A smaller value indicates better low-temperature viscosity (low-temperature properties) of the lubricating oil.
In addition, when blending as a lubricating oil composition so that the 100 ° C. kinematic viscosity is about the same, and comparing the lubricating oil composition having the same SSI, the lower the CCS viscosity of the lubricating oil composition, the more the lubricating The oil composition is excellent in fuel economy at low temperatures (low temperature startability).

The production of the resin used in Examples and Comparative Examples and the production of a lubricating oil composition containing the lubricating oil viscosity modifier using the resin are described below. In order to secure the necessary amount for analysis and evaluation, polymerization may be carried out multiple times.

In the following polymerization examples, compound (1) represented by the following formula used as a catalyst component was synthesized according to a known method.
Dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride (compound (2)) used as a catalyst component was synthesized according to the method disclosed in Japanese Patent No. 3737134.

[Polymerization Example 1] (Production of resin α-1 (crystalline EPR))
A toluene solution (compound (1): 0.055 mmol) of compound (1) and triisobutylaluminum (also referred to as iBu ₃ Al) mixed with 1457 mL/hr of heptane was placed in a 1 L stainless steel autoclave equipped with a pressure control valve. /L, iBu ₃ Al: 8.25 mmol/L) to 41 mL/hr, and a toluene solution (0.4 mmol) of triphenylcarbenium tetrakis(pentafluorophenyl)borate (Ph ₃ CB(C ₆ F ₅ ) ₄ ). /L) was continuously charged at 68 mL/hr, ethylene at 200 g/L, and propylene at 247 g/L. , the polymerization reaction liquid was continuously withdrawn so that the liquid volume in the polymerization vessel became 950 mL. Two hours after starting charging of all the above solvents, monomers, catalysts, etc., the polymerization reaction solution was sampled for 50 minutes. The resulting polymerization reaction solution was added to a mixture of 1.5 liters of methanol (750 mL) and acetone (750 mL) containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 140° C. for 10 hours to obtain 80.1 g of olefinic resin (α-1). Table 2 shows the analysis results of the obtained olefin resin (α-1).

[Polymerization Example 2] (Production of resin α-2 (crystalline EPR))
In a 1 L stainless steel autoclave equipped with a pressure control valve, 1672 mL/hr of heptane, compound (1) and triisobutylaluminum (also referred to as iBu ₃ Al) mixed toluene solution (compound (1): 0.040 mmol /L, iBu ₃ Al: 6.0 mmol/L) at 114 mL/hr, and a toluene solution (0.5 mmol) of triphenylcarbenium tetrakis(pentafluorophenyl)borate (Ph ₃ CB(C ₆ F ₅ ) ₄ ). /L) was continuously charged at 36 mL/hr, ethylene at 250 g/L, and propylene at 190 g/L. , the polymerization reaction liquid was continuously withdrawn so that the liquid volume in the polymerization vessel became 950 mL. Two hours after starting charging of all the above solvents, monomers, catalysts, etc., the polymerization reaction solution was sampled for 50 minutes. The resulting polymerization reaction solution was added to a mixture of 1.5 liters of methanol (750 mL) and acetone (750 mL) containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 140° C. for 10 hours to obtain 43.3 g of olefinic resin (α-2). Table 2 shows the analysis results of the obtained olefin resin (α-2).

[Polymerization Example 3] (Production of resin β-1 (amorphous EPR))
In a 1 L stainless steel autoclave equipped with a pressure control valve, 1614 mL/hr of heptane, 95 mL/hr of a toluene solution of triisobutylaluminum (also referred to as iBu ₃ Al) (iBu ₃ Al: 2.0 mmol/L), A toluene solution (0.05 mmol/L) of compound (2) was added at 38 mL/hr, and a toluene solution (0.05 mmol/L) of triphenylcarbenium tetrakis(pentafluorophenyl)borate (Ph ₃ CB(C ₆ F ₅ ) ₄ ) was added. 5 mmol/L) was continuously charged at 38 mL/hr, ethylene at 245 g/L, and propylene at 300 g/L, respectively. Meanwhile, the polymerization reaction liquid was continuously withdrawn so that the liquid volume in the polymerization vessel became 950 mL. Two hours after starting charging of all the solvents, monomers, catalysts, etc., the polymerization reaction solution was sampled for 30 minutes. The resulting polymerization reaction solution was added to a mixture of 1.5 liters of methanol (750 mL) and acetone (750 mL) containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 140° C. for 10 hours to obtain 80 g of olefinic resin (β-1). Table 2 shows the analysis results of the obtained olefin resin (β-1).

[Example 1]
A blend of 80 parts by mass of the olefinic resin (α-1) obtained in Polymerization Example 1 and 20 parts by mass of the olefinic resin (β-1) obtained in Polymerization Example 3 was used to improve the viscosity index for lubricating oils. A lubricating oil composition is prepared using Agent-1.

(1) Preparation of polymer concentrate Yubase-4 (manufactured by SK Lubricants) is used as a base oil, and a 10% by mass solution of the viscosity index improver for lubricating oil-1 is prepared to obtain a polymer concentrate that is a lubricating oil additive composition. -1 was obtained.

(2) Preparation of lubricating oil composition Using Yubase-4 (manufactured by SK Lubricants) as a base oil, pour point depressant (Leblanc 165, manufactured by Toho Chemical Co., Ltd.), additives (Ca and Na overbased detergent , N-containing dispersants, aminic and phenolic antioxidants, zinc dialkyldithiophosphates, friction modifiers, and defoamers), after the addition of A blending amount of Polymer Concentrate-1 was adjusted so as to give a constant viscosity (about 8 mm ² /s) at 100° C., and a lubricating oil composition was prepared. Performance evaluation of the obtained lubricating oil composition was performed. Table 3 shows the compounding ratio and evaluation results.

[Example 2]
A blend of 60 parts by mass of the olefinic resin (α-1) obtained in Polymerization Example 1 and 40 parts by mass of the olefinic resin (β-1) obtained in Polymerization Example 3 was used to obtain a lubricating oil viscosity index. A polymer concentrate and lubricating oil composition were prepared and evaluated in the same manner as in Example 1, except that they were used as improvers. Table 3 shows the compounding ratio and evaluation results.

[Example 3]
A blend of 40 parts by mass of the olefinic resin (α-1) obtained in Polymerization Example 1 and 60 parts by mass of the olefinic resin (β-1) obtained in Polymerization Example 3 was used to obtain a lubricating oil viscosity index. A polymer concentrate and lubricating oil composition were prepared and evaluated in the same manner as in Example 1, except that they were used as improvers. Table 3 shows the compounding ratio and evaluation results.

[Example 4]
A blend of 20 parts by mass of the olefinic resin (α-1) obtained in Polymerization Example 1 and 80 parts by mass of the olefinic resin (β-1) obtained in Polymerization Example 3 was used to obtain a lubricating oil viscosity index. A polymer concentrate and lubricating oil composition were prepared and evaluated in the same manner as in Example 1, except that they were used as improvers. Table 3 shows the compounding ratio and evaluation results.

[Example 5]
A blend of 80 parts by mass of the olefinic resin (α-2) obtained in Polymerization Example 2 and 20 parts by mass of the olefinic resin (β-1) obtained in Polymerization Example 3 was used to obtain a lubricating oil viscosity index. A polymer concentrate and lubricating oil composition were prepared and evaluated in the same manner as in Example 1, except that they were used as improvers. Table 3 shows the compounding ratio and evaluation results.

[Example 6]
A blend of 60 parts by mass of the olefinic resin (α-2) obtained in Polymerization Example 2 and 40 parts by mass of the olefinic resin (β-1) obtained in Polymerization Example 3 was used to obtain a lubricating oil viscosity index. A polymer concentrate and lubricating oil composition were prepared and evaluated in the same manner as in Example 1, except that they were used as improvers. Table 3 shows the compounding ratio and evaluation results.

[Example 7]
A blend of 40 parts by mass of the olefinic resin (α-2) obtained in Polymerization Example 2 and 60 parts by mass of the olefinic resin (β-1) obtained in Polymerization Example 3 was used to obtain a lubricating oil viscosity index. A polymer concentrate and lubricating oil composition were prepared and evaluated in the same manner as in Example 1, except that they were used as improvers. Table 3 shows the compounding ratio and evaluation results.

[Example 8]
A blend of 20 parts by mass of the olefinic resin (α-2) obtained in Polymerization Example 2 and 80 parts by mass of the olefinic resin (β-1) obtained in Polymerization Example 3 was used to obtain a lubricating oil viscosity index. A polymer concentrate and lubricating oil composition were prepared and evaluated in the same manner as in Example 1, except that they were used as improvers. Table 3 shows the compounding ratio and evaluation results.

[Comparative Example 1]
A polymer concentrate and a lubricating oil composition were prepared in the same manner as in Example 1, except that 100 parts by mass of the olefin resin (α-1) obtained in Polymerization Example 1 was used as a viscosity index improver for lubricating oil. ,evaluated. Table 3 shows the compounding ratio and evaluation results.

[Comparative Example 2]
A polymer concentrate and a lubricating oil composition were prepared in the same manner as in Example 1, except that 100 parts by mass of the olefinic resin (α-2) obtained in Polymerization Example 2 was used as a viscosity index improver for lubricating oil. ,evaluated. Table 3 shows the compounding ratio and evaluation results.

Claims (11)

A lubricating oil viscosity modifier containing a resin (α) and a resin (β),
The resin (α) satisfies the following requirements (I)-1 and (I)-2,
The resin (β) satisfies the following requirements (II)-1 and (II)-2, and
A lubricating oil viscosity modifier, wherein both the resin (α) and the resin (β) satisfy the following requirement (III)-1.
(I)-1: A copolymer of ethylene and at least one α-olefin selected from α-olefins having 3 to 12 carbon atoms, containing 87 to 99 mol% of structural units derived from ethylene. in the range.
(I)-2: Melting point (Tm) measured by differential scanning calorimetry (DSC) is in the range of 50 to 100°C.
(II)-1: A copolymer of ethylene and at least one α-olefin selected from α-olefins having 3 to 12 carbon atoms, containing 30 to 65 mol% of structural units derived from ethylene. in the range.
(II)-2: Does not have a melting point (Tm) determined by differential scanning calorimetry (DSC).
(III)-1: The intrinsic viscosity [η] measured in decalin at 135° C. is in the range of 0.5 to 2.5 dl/g. Claim 1, containing 1 to 99 parts by mass of the resin (α) and 99 to 1 part by mass of the resin (β) (where the total of the resin (α) and the resin (β) is 100 parts by mass) The viscosity modifier for lubricating oil according to . The lubricating oil viscosity modifier according to claim 1 or 2, wherein both the resin (α) and the resin (β) consist of structural units derived from ethylene and structural units derived from propylene. The lubricating oil viscosity modifier according to any one of claims 1 to 3, wherein both the resin (α) and the resin (β) further satisfy the following requirement (III)-2.
(III)-2: Density measured by the density gradient tube method in accordance with JIS K7112 is in the range of 850 to 880 kg/m ³ . The lubricating oil viscosity modifier according to any one of claims 1 to 4, wherein the resin (α) further satisfies the following requirement (I)-3.
(I)-3: The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is in the range of 70,000 to 400,000. The lubricating oil viscosity modifier according to any one of claims 1 to 5, wherein the resin (β) further satisfies the following requirement (II)-3.
(II)-3: Weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is in the range of 1,000 to 100,000 . 1 to 50 parts by mass of the lubricating oil viscosity modifier (A) according to any one of claims 1 to 6, and 50 to 99 parts by mass of the oil (B) (however, the lubricating oil viscosity modifier (A) , the total of oil (B) being 100 parts by mass). 0.1 to 5 parts by mass of the lubricating oil viscosity modifier (A) according to any one of claims 1 to 6, and 95 to 99.9 parts by mass of the lubricating oil base (BB) (however, for lubricating oil A lubricating oil composition comprising a viscosity modifier (A) and a lubricating oil base (BB) (total of 100 parts by mass). 9. The lubricating oil composition according to claim 8, comprising a pour point depressant (C) in an amount of 0.05 to 5% by weight in 100% by weight of said lubricating oil composition. 10. A lubricating oil composition according to claim 8 or 9, wherein the lubricating oil base (BB) is a mineral oil. 10. A lubricating oil composition according to claim 8 or 9, wherein the lubricating oil base (BB) is a synthetic oil.