JP5917927B2 - Laminate, side rubber for tire and tire - Google Patents

Description

  The present invention relates to a laminate, in particular, a laminate obtained by forming a UV curable ink layer on a vulcanized rubber layer, a tire side rubber using the laminate, and a tire using the side rubber. is there.

  UV curable ink (UV curable ink) is an ink that forms a film by causing a photochemical reaction with the energy of ultraviolet light and curing from liquid to solid in seconds. In recent years, UV curable inks have been used for various applications because they do not dry on a plate but have a property of quick drying after printing. One of the applications is a technique of applying to the surface of vulcanized rubber.

  For example, in Patent Document 1, a vulcanized rubber sheet for a shoe sole and a ground coat layer formed by adhesion on one surface thereof have a valley-dyed uneven shape in which a coating is applied to a recess on the side of the ground coat layer. A shoe sole sheet is disclosed in which a single-layer or multiple-layer design pattern printing layer and a transparent or translucent surface protective layer coated thereon are further provided.

  Patent Document 2 discloses that (a) a surface layer of a blanket for transferring an ultraviolet curable ink transferred from a printing plate to a printing substrate is made of a polyester-based polyol composed of a polybasic organic acid and a polyol and diisocyanate. Comprising a synthesized polyurethane rubber, (b) constituting a polybasic organic acid based on succinic acid, (c) constituting a polyol based on ethylene glycol, (d) 4- A method for producing an ultraviolet curable ink printing blanket comprising 4′diphenylmethane diisocyanate as a main component and constituting diisocyanate is disclosed.

Japanese Patent Publication No. 61-37112 JP 2010-094927 A

  However, both of the techniques of Patent Documents 1 and 2 have a problem in that the rubber of the base material deteriorates due to UV irradiation and the discoloration resistance deteriorates during the production. In consideration of using a vulcanized rubber having a UV curable ink layer as a tire member such as a sidewall portion, further improvement in peeling resistance and weather resistance has been desired.

  Accordingly, an object of the present invention is to provide a laminate and tire side rubber having excellent discoloration resistance and excellent peeling resistance and weather resistance, and a tire including the side rubber.

  As a result of intensive studies to achieve the above-mentioned object, the inventors of the present invention have made studies on a laminate obtained by forming a UV curable ink layer on a vulcanized rubber layer. It has been found that the discoloration resistance, peel resistance and weather resistance of the vulcanized rubber can be improved by incorporating the coalescence into the vulcanized rubber layer.

That is, the rubber laminate of the present invention is a laminate in which a UV curable ink layer is formed on a vulcanized rubber layer, and the vulcanized rubber layer has a conjugated diene compound-derived content of 30. It is characterized by containing a conjugated diene compound-nonconjugated olefin copolymer that is ˜80 mol% .

  Furthermore, the conjugated diene compound-nonconjugated olefin copolymer preferably has a polystyrene-equivalent weight average molecular weight of 10,000 to 10,000,000 and a molecular weight distribution (Mw / Mn) of 10 or less. Is preferred.

  The conjugated diene compound of the conjugated diene compound-nonconjugated olefin copolymer is preferably at least one selected from the group consisting of 1,3-butadiene and isoprene, and the nonconjugated olefin includes ethylene, propylene and It is preferably at least one selected from the group consisting of 1-butene, and among them, ethylene is more preferable.

  In the laminate of the present invention, the content of the conjugated diene compound-nonconjugated olefin copolymer in the vulcanized rubber layer is preferably 20 to 80 parts by mass with respect to 100 parts by mass of the rubber component.

  In the rubber composition of the present invention, the vulcanized rubber layer preferably further contains 3 parts by mass or less of an anti-aging agent with respect to 100 parts by mass of the rubber component. Moreover, it is preferable that the said vulcanized rubber layer contains 2 mass parts or less of wax with respect to 100 mass parts of rubber components further.

  The side rubber for tires of the present invention is characterized by using the laminate according to the present invention.

  The tire of the present invention is characterized by using the side rubber according to the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, while having favorable discoloration resistance, the laminated body and tire side rubber which were excellent in peeling resistance and a weather resistance, and the tire provided with this side rubber can be provided.

<Laminate>
Hereinafter, embodiments of the present invention will be specifically described.
The laminate of the present invention is a laminate obtained by forming a UV curable ink layer on a vulcanized rubber layer.

(Vulcanized rubber layer)
The vulcanized rubber layer constituting the laminate of the present invention is characterized by containing a conjugated diene compound-nonconjugated olefin copolymer.

O Conjugated diene compound-nonconjugated olefin copolymer By including a conjugated diene compound-nonconjugated olefin copolymer in the vulcanized rubber layer, the amount of anti-aging agent that causes discoloration can be reduced, so that the vulcanized rubber In addition to improving the discoloration resistance, excellent peeling resistance and weather resistance can be realized by the excellent weather resistance of the non-conjugated olefin copolymer and the excellent peeling resistance of the conjugated diene compound. Furthermore, since a low glass transition point (Tg) can be maintained, good low temperature characteristics can also be realized.

  Here, the conjugated diene compound-nonconjugated olefin copolymer is a copolymer of a conjugated diene compound and a nonconjugated olefin, and includes a nonconjugated olefin together with the conjugated diene compound as a monomer unit component in the copolymer. .

The conjugated diene compound - The content of the conjugated diene compound-derived moieties in the non-conjugated olefin copolymer is 30 mol% 80 mol%.
By setting the content of the conjugated diene compound-derived portion in the conjugated diene compound-nonconjugated olefin copolymer to 30 mol% or more, workability can be sufficiently secured, and by setting it to 80 mol% or less, the nonconjugated olefin can be reduced. Since a certain amount is included, an improvement in weather resistance (ozone resistance) can be expected.

There is no restriction | limiting in particular as content of the said nonconjugated olefin origin part in the said conjugated diene compound-nonconjugated olefin copolymer, Although it can select suitably according to the objective, 20 mol%-70 mol% are preferable.
The weather resistance can be improved by setting the content of the non-conjugated olefin-derived portion in the conjugated diene compound-non-conjugated olefin copolymer to 20 mol% or more, and maintaining the workability by setting the content to 70 mol% or less. In addition, the crack growth resistance can be further improved.

Further, the amount of cis-1,4 bonds in the conjugated diene compound-derived portion in the conjugated diene compound-nonconjugated olefin copolymer is not particularly limited and can be appropriately selected according to the purpose. % Or more is preferable, more than 92% is particularly preferable, and 95% or more is most preferable.
By setting the cis 1,4-bond amount of the conjugated diene compound-derived portion to 50% or more, a low glass transition point (Tg) can be maintained, and thereby physical properties such as low-temperature characteristics are improved. Furthermore, by making the amount of cis 1,4-bond of the conjugated diene compound-derived portion more than 92%, it becomes possible to improve crack growth resistance, weather resistance, and heat resistance, and by setting it to 95% or more. Further, the crack growth resistance, weather resistance, and heat resistance can be further improved.
The cis-1,4 bond amount is an amount in the conjugated diene compound-derived portion, and is not a ratio to the entire copolymer.

  On the other hand, in the conjugated diene compound-nonconjugated olefin copolymer, the nonconjugated olefin used as a monomer is a nonconjugated olefin other than the conjugated diene compound. It is possible to increase the degree of design freedom as an elastomer by reducing the crystallinity by reducing the heat resistance and the double bond ratio in the main chain of the copolymer. Moreover, as a nonconjugated olefin, it is preferable that it is an acyclic olefin, and it is preferable that carbon number of this nonconjugated olefin is 2-10.

Accordingly, preferred examples of the non-conjugated olefin include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene. Among these, ethylene, propylene And 1-butene are preferred, with ethylene being particularly preferred. Here, the non-conjugated olefin does not contain styrene. Since the α-olefin has a double bond at the α-position of the olefin, copolymerization with a conjugated diene can be performed efficiently. These non-conjugated olefins may be used alone or in combination of two or more. In addition, an olefin is an aliphatic unsaturated hydrocarbon and refers to a compound having one or more carbon-carbon double bonds.
In addition, when a block portion composed of a monomer unit of non-conjugated olefin is provided, it exhibits static crystallinity and is excellent in mechanical properties such as breaking strength.

  In the conjugated diene compound-nonconjugated olefin copolymer, the conjugated diene compound used as a monomer preferably has 4 to 12 carbon atoms. Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and among these, 1,3-butadiene and isoprene are preferable. Moreover, these conjugated diene compounds may be used independently and may be used in combination of 2 or more type.

  The copolymer of the present invention can be prepared by the same mechanism using any of the specific examples of the conjugated diene compound described above.

  In the conjugated diene compound-nonconjugated olefin copolymer, the weight average molecular weight (Mw) is not particularly limited, and the weight average molecular weight (Mw) is not particularly limited. From the viewpoint of application to a molecular structure material, the polystyrene-converted weight average molecular weight (Mw) of the copolymer is preferably 10,000 to 10,000,000, and is 10,000 to 1,000,000. It is more preferable, and it is especially preferable that it is 50,000-600,000. If the Mw exceeds 10,000,000, the moldability may be deteriorated.

  Further, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably 10 or less, and more preferably 6 or less. This is because if the molecular weight distribution exceeds 10, the physical properties are not uniform. Here, the average molecular weight and the molecular weight distribution can be determined using polystyrene as a standard substance by gel permeation chromatography (GPC).

The content of 1,2 adducts (including 3,4 adducts) of the conjugated diene compound in the conjugated diene compound-derived part of the conjugated diene compound-nonconjugated olefin copolymer is not particularly limited and depends on the purpose. However, it is preferably 5% or less, more preferably 3% or less, and particularly preferably 2.5% or less.
When the content of 1,2 adducts (including 3,4 adducts) of the conjugated diene compound in the conjugated diene compound-derived part of the conjugated diene compound-nonconjugated olefin copolymer is 5% or less, The weather resistance and ozone resistance of the coalescence can be further improved.
On the other hand, the content of 1,2 adducts (including 3,4 adducts) of the conjugated diene compound in the conjugated diene compound-derived part of the conjugated diene compound-nonconjugated olefin copolymer is 2.5% or less. And the weather resistance and ozone resistance of the copolymer can be further improved.
The content of the 1,2-adduct portion (including the 3,4-adduct portion) is an amount in the portion derived from the conjugated diene compound, and is not a ratio to the whole copolymer.
The 1,2-adduct portion (including 3,4-adduct portion) content of the conjugated diene compound in the conjugated diene compound-derived portion has the same meaning as the 1,2-vinyl bond amount when the conjugated diene compound is butadiene. It is.

  The chain structure of the conjugated diene compound-nonconjugated olefin copolymer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a block copolymer, a random copolymer, a taper copolymer, An alternating copolymer etc. are mentioned.

Block copolymer The structure of the block copolymer is (AB) _x , A- (BA) _x, and B- (AB) _x (where A is a non-conjugated olefin unit). B is a block portion consisting of monomer units of a conjugated diene compound, and x is an integer of 1 or more. In addition, the block copolymer provided with two or more structures of (AB) or (BA) is called a multi-block copolymer.
When the conjugated diene compound-nonconjugated olefin copolymer is a block copolymer, the block portion composed of the monomer of the nonconjugated olefin exhibits static crystallinity, and thus has excellent mechanical properties such as breaking strength.

・ Random copolymer When the conjugated diene compound-nonconjugated olefin copolymer is a random copolymer, the arrangement of the monomer units of the nonconjugated olefin is irregular, and the copolymer causes phase separation. Without observing the crystallization temperature derived from the block portion. That is, since it becomes possible to introduce a non-conjugated olefin having properties such as heat resistance into the main chain of the copolymer, the heat resistance is improved.

Tapered copolymer The taper copolymer is a copolymer in which a random copolymer and a block copolymer are mixed, and a block portion and a non-conjugated olefin composed of monomer units of a conjugated diene compound. And at least one block part (also referred to as a block structure) of the monomer units, and a random part (also referred to as a random structure) in which monomer units of a conjugated diene compound and a non-conjugated olefin are irregularly arranged. And a copolymer composed of
The structure of the taper copolymer indicates that the composition of the conjugated diene compound component and the non-conjugated olefin component is distributed continuously or discontinuously. Here, it is preferable that the chain structure of the non-conjugated olefin component does not contain many long-chain (high molecular weight) non-conjugated olefin block components but contains many short-chain (low molecular weight) non-conjugated olefin block components.

-Alternating copolymer The alternating copolymer has a structure in which a conjugated diene compound and a non-conjugated olefin are alternately arranged (a molecular chain of -ABABABAB- where A is a non-conjugated olefin and B is a conjugated diene compound) A polymer having a structure).

  In the present invention, when the conjugated diene compound-nonconjugated olefin copolymer is a block copolymer, the block portion composed of the monomer of the nonconjugated olefin exhibits static crystallinity. In the case of an alternating copolymer, both flexibility and adhesiveness can be achieved. The copolymer is preferably at least one selected from a block copolymer and a tapered copolymer.

  Moreover, about content of the said conjugated diene compound-nonconjugated olefin copolymer in the said vulcanized rubber layer, it is the range of 20-80 mass parts with respect to 100 mass parts of rubber components in the said vulcanized rubber layer. It is preferable. When the content of the conjugated diene compound-nonconjugated olefin copolymer is less than 20 parts by mass, the amount of the conjugated diene compound-nonconjugated olefin copolymer is too small, so that the desired characteristics (discoloration resistance, peel resistance, weather resistance) On the other hand, if the content of the conjugated diene compound-nonconjugated olefin copolymer exceeds 80 parts by mass, the co-curability with the adjacent member may be reduced. It is.

-Manufacturing method of conjugated diene compound-nonconjugated olefin copolymer Next, the manufacturing method of said nonconjugated olefin-type copolymer is demonstrated in detail. However, the manufacturing method described in detail below is merely an example.
The method for producing a non-conjugated olefin copolymer includes a non-conjugated olefin and a conjugated diene compound in the presence of the first polymerization catalyst composition, the second polymerization catalyst composition, or the third polymerization catalyst composition shown below. It is preferable to include the process of superposing | polymerizing. As a polymerization method, any method such as a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. Moreover, when using a solvent for a polymerization reaction, the solvent used should just be inactive in a polymerization reaction, For example, toluene, hexane, cyclohexane, mixtures thereof etc. are mentioned.

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^a〜Ｒ^fは、それぞれ独立して炭素数１〜３のアルキル基又は水素原子を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体、及び下記一般式（ＩＩ）： First polymerization catalyst composition As the first polymerization catalyst composition (hereinafter also referred to as “first polymerization catalyst composition”), the following general formula (I):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^{a to} R ^f each independently represents an alkyl having 1 to 3 carbon atoms. A group or a hydrogen atom, L represents a neutral Lewis base, w represents an integer of 0 to 3), and the following general formula (II):

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｘ'は、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体、並びに下記一般式（ＩＩＩ）：

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and X ′ represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group. , A silyl group or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, and w represents an integer of 0 to 3), and the following general formula (III ):

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^R'は、無置換もしくは置換シクロペンタジエニル、インデニル又はフルオレニルを示し、Ｘは、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示し、［Ｂ］^-は、非配位性アニオンを示す）で表されるハーフメタロセンカチオン錯体からる群より選択される少なくとも１種類の錯体を含む重合触媒組成物が挙げられる。

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^{R ′} represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group or a thiolate group. , An amide group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, w represents an integer of 0 to 3, and [B] ⁻ represents a non-coordinating group. A polymerization catalyst composition containing at least one complex selected from the group consisting of half metallocene cation complexes represented by

The first polymerization catalyst composition may further contain other components contained in the polymerization catalyst composition containing a normal metallocene complex, such as a promoter. Here, the metallocene complex is a complex compound in which one or more cyclopentadienyl or a derivative thereof is bonded to a central metal, and in particular, one cyclopentadienyl or a derivative thereof bonded to the central metal. A certain metallocene complex may be called a half metallocene complex.
In the polymerization reaction system, the concentration of the complex contained in the first polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / L.

In the metallocene complexes represented by the above general formulas (I) and (II), Cp ^R in the formula is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7-X R _X or C ₉ H _11-X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl include 2-phenylindenyl and 2-methylindenyl. Note that the two Cp ^Rs in the general formulas (I) and (II) may be the same as or different from each other.

In the half metallocene cation complex represented by the general formula (III), Cp ^{R ′} in the formula is unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and among these, unsubstituted or substituted indenyl It is preferable that Cp ^{R ′} having a cyclopentadienyl ring as a basic skeleton is represented by C ₅ H _5-X R _X. Here, X is an integer of 0-5. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of Cp ^{R ′} having a cyclopentadienyl ring as a basic skeleton include the following.

（式中、Ｒは水素原子、メチル基又はエチル基を示す。）
一般式（ＩＩＩ）において、上記インデニル環を基本骨格とするＣｐ^R'は、一般式（Ｉ）のＣｐ^Rと同様に定義され、好ましい例も同様である。

(In the formula, R represents a hydrogen atom, a methyl group or an ethyl group.)
In the general formula (III), Cp ^{R ′} having the above indenyl ring as a basic skeleton is defined in the same manner as Cp ^{R in the} general formula (I), and preferred examples thereof are also the same.

In the general formula (III), Cp ^{R ′} having the fluorenyl ring as a basic skeleton can be represented by C ₁₃ H _9-X R _X or C ₁₃ H _17-X R _X. Here, X is an integer of 0-9 or 0-17. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group.

  The central metal M in the general formulas (I), (II) and (III) is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the central metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

The metallocene complex represented by the general formula (I) contains a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups contained in the silylamide ligand (R ^{a to} R ^f in the general formula (I)) are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Moreover, it is preferable that at least one of R ^{a to} R ^f is a hydrogen atom. By making at least one of R ^{a to} R ^f a hydrogen atom, the synthesis of the catalyst is facilitated, and the bulk height around silicon is reduced, so that non-conjugated olefin is easily introduced. From the same viewpoint, it is more preferable that at least one of R ^{a to} R ^c is a hydrogen atom and at least one of R ^{d to} R ^f is a hydrogen atom. Furthermore, a methyl group is preferable as the alkyl group.

The metallocene complex represented by the general formula (II) includes a silyl ligand [—SiX ′ ₃ ]. X ′ contained in the silyl ligand [—SiX ′ ₃ ] is a group defined in the same manner as X in the general formula (III) described below, and preferred groups are also the same.

  In the general formula (III), X is a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, and a hydrocarbon group having 1 to 20 carbon atoms. Here, examples of the alkoxide group include aliphatic alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group; a phenoxy group and 2,6-dioxy -Tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dinepentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, Examples include aryloxide groups such as 2-isopropyl-6-neopentylphenoxy group, and among these, 2,6-di-tert-butylphenoxy group is preferable.

  In the general formula (III), the thiolate group represented by X includes a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thio n-butoxy group, a thioisobutoxy group, a thiosec-butoxy group, a thiotert-butoxy group and the like Group thiolate group; thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropyl Arylthiolate groups such as thiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group, etc. Among these, 2,4,6-triisopropylthiophenoxy group Preferred.

  In the general formula (III), examples of the amide group represented by X include aliphatic amide groups such as a dimethylamide group, a diethylamide group, and a diisopropylamide group; a phenylamide group, a 2,6-di-tert-butylphenylamide group, 2 , 6-diisopropylphenylamide group, 2,6-dineopentylphenylamide group, 2-tert-butyl-6-isopropylphenylamide group, 2-tert-butyl-6-neopentylphenylamide group, 2-isopropyl- Arylamide groups such as 6-neopentylphenylamide group and 2,4,6-tri-tert-butylphenylamide group; and bistrialkylsilylamide groups such as bistrimethylsilylamide group. Among these, bistrimethylsilylamide Groups are preferred.

  In the general formula (III), examples of the silyl group represented by X include trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (bistrimethylsilyl) silyl group, and the like. Among these, a tris (trimethylsilyl) silyl group is preferable.

  In the general formula (III), the halogen atom represented by X may be any of a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, but a chlorine atom or a bromine atom is preferred. Moreover, as a C1-C20 hydrocarbon group which X represents, specifically, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Linear or branched aliphatic hydrocarbon groups such as butyl group, neopentyl group, hexyl group, octyl group; aromatic hydrocarbon groups such as phenyl group, tolyl group, naphthyl group; aralkyl groups such as benzyl group, etc. Others: Examples include hydrocarbon groups containing silicon atoms such as trimethylsilylmethyl group and bistrimethylsilylmethyl group. Among these, methyl group, ethyl group, isobutyl group, trimethylsilylmethyl group and the like are preferable.

  In the general formula (III), X is preferably a bistrimethylsilylamide group or a hydrocarbon group having 1 to 20 carbon atoms.

In the general formula (III), [B] ^- The non-coordinating anion represented by, for example, a tetravalent boron anion. Specific examples of the tetravalent boron anion include tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Decahydride-7,8-dicarbaoundecaborate and the like can be mentioned, and among these, tetrakis (pentafluorophenyl) borate is preferable.

  The metallocene complex represented by the general formulas (I) and (II) and the half metallocene cation complex represented by the general formula (III) are further 0 to 3, preferably 0 to 1 neutral. Contains Lewis base L. Here, examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like. Here, when the complex includes a plurality of neutral Lewis bases L, the neutral Lewis bases L may be the same or different.

  Further, the metallocene complex represented by the general formula (I) and the formula (II) and the half metallocene cation complex represented by the general formula (III) may exist as a monomer, It may exist as a body or higher multimer.

（式中、Ｘ''はハライドを示す。）
上記一般式（ＩＩ）で表されるメタロセン錯体は、例えば、溶媒中でランタノイドトリスハライド、スカンジウムトリスハライド又はイットリウムトリスハライドを、インデニルの塩（例えばカリウム塩やリチウム塩）及びシリルの塩（例えばカリウム塩やリチウム塩）と反応させることで得ることができる。なお、反応温度は室温程度にすればよいので、温和な条件で製造することができる。また、反応時間は任意であるが、数時間〜数十時間程度である。反応溶媒は特に限定されないが、原料及び生成物を溶解する溶媒であることが好ましく、例えばトルエンを用いればよい。以下に、一般式（ＩＩ）で表されるメタロセン錯体を得るための反応例を示す。 The metallocene complex represented by the general formula (I) includes, for example, a lanthanoid trishalide, scandium trishalide, or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt) and bis (trialkylsilyl). It can be obtained by reacting with an amide salt (for example, potassium salt or lithium salt). In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. Below, the reaction example for obtaining the metallocene complex represented by general formula (I) is shown.

(In the formula, X ″ represents a halide.)
The metallocene complex represented by the general formula (II) includes, for example, a lanthanoid trishalide, a scandium trishalide, or a yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt), and a silyl salt (for example, potassium). Salt or lithium salt). In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. Below, the reaction example for obtaining the metallocene complex represented by general formula (II) is shown.

（式中、Ｘ''はハライドを示す。）

(In the formula, X ″ represents a halide.)

  The half metallocene cation complex represented by the general formula (III) can be obtained, for example, by the following reaction.

Here, in the compound represented by the general formula (IV), M represents a lanthanoid element, scandium or yttrium, and Cp ^{R ′} independently represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl. , X represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, and w represents 0 to 3 Indicates an integer. In the ionic compound represented by the general formula [A] ⁺ [B] ⁻ , [A] ⁺ represents a cation, and [B] ⁻ represents a non-coordinating anion.

Examples of the cation represented by [A] ⁺ include a carbonium cation, an oxonium cation, an amine cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Examples of the carbonium cation include trisubstituted carbonium cations such as a triphenylcarbonium cation and a tri (substituted phenyl) carbonium cation. The tri (substituted phenyl) carbonyl cation is specifically exemplified by tri (methylphenyl). ) Carbonium cation and the like. Examples of amine cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N- N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation. Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. Among these cations, N, N-dialkylanilinium cation or carbonium cation is preferable, and N, N-dialkylanilinium cation is particularly preferable.

The ionic compound represented by the general formula [A] ⁺ [B] ⁻ used for the above reaction is a compound selected and combined from the above non-coordinating anions and cations, which is N, N-dimethylaniline. Preference is given to nium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like. Further, the ionic compound represented by the general formula [A] + [B]-is preferably added in an amount of 0.1 to 10 times, more preferably about 1 time, with respect to the metallocene complex. When the half metallocene cation complex represented by the general formula (III) is used for the polymerization reaction, the half metallocene cation complex represented by the general formula (III) may be provided as it is in the polymerization reaction system, or the compound represented by the general formula (IV) and the general formula used in the reaction [a] ⁺ [B] ^- provides an ionic compound represented separately into the polymerization reaction system, the general formula in the reaction system (III You may form the half metallocene cation complex represented by this. Further, by using a combination of the metallocene complex represented by the general formula (I) or the formula (II) and the ionic compound represented by the general formula [A] ⁺ [B] ⁻ , A half metallocene cation complex represented by the formula (III) can also be formed.

  The structures of the metallocene complexes represented by the general formulas (I) and (II) and the half metallocene cation complex represented by the general formula (III) are preferably determined by X-ray structural analysis.

  The co-catalyst that can be used in the first polymerization catalyst composition can be arbitrarily selected from components used as a co-catalyst for a polymerization catalyst composition containing a normal metallocene complex. Suitable examples of the cocatalyst include aluminoxanes, organoaluminum compounds, and the above ionic compounds. These promoters may be used alone or in combination of two or more.

  The aluminoxane is preferably an alkylaminoxan, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane. As the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem Co., Ltd.) and the like are preferable. The content of aluminoxane in the first polymerization catalyst composition is such that the element ratio Al / M between the central metal M of the metallocene complex and the aluminum element Al of the aluminoxane is about 10 to 1000, preferably about 100. It is preferable to make it.

  On the other hand, as the organoaluminum compound, the general formula AlRR′R ″ (wherein R and R ′ are each independently a C1-C10 hydrocarbon group or a hydrogen atom, and R ″ is a C1-C10 An organoaluminum compound represented by (a hydrocarbon group) is preferable. Examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, and dialkylaluminum hydride. Among these, trialkylaluminum is preferable. Examples of the trialkylaluminum include triethylaluminum and triisobutylaluminum. In addition, it is preferable that it is 1-50 times mole with respect to a metallocene complex, and, as for content of the organoaluminum compound in the said polymerization catalyst composition, it is still more preferable that it is about 10 times mole.

  Further, in the above polymerization catalyst composition, the metallocene complex represented by the general formula (I) and the formula (II) and the half metallocene cation complex represented by the above general formula (III) are each used as an appropriate promoter. By combining, the amount of cis-1,4 bonds and the molecular weight of the resulting polymer can be increased.

Second Polymerization Catalyst Composition Next, the second polymerization catalyst composition (hereinafter also referred to as “second polymerization catalyst composition”) will be described.
As the second polymerization catalyst composition,
(A) component: a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base, the rare earth element compound or the reaction product having no bond between the rare earth element and carbon,
Component (B): Contains ionic compound (B-1) composed of non-coordinating anion and cation, aluminoxane (B-2), Lewis acid, complex compound of metal halide and Lewis base, and active halogen. At least one selected from the group consisting of at least one halogen compound (B-3) among organic compounds;
The polymerization catalyst composition containing is mentioned.
When the second polymerization catalyst composition contains at least one of the ionic compound (B-1) and the halogen compound (B-3), the polymerization catalyst composition further comprises:
(C) Component: The following general formula (X):
YR ¹ _a R ² _b R ³ _c (X)
[Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R1 and R2 are the same or different and have 1 to 10 carbon atoms. R ³ is a group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is 1 in the periodic table. When the metal is selected from the group, a is 1, and b and c are 0, and when Y is the metal selected from groups 2 and 12 of the periodic table, a and In the case where b is 1 and c is 0, and Y is a metal selected from Group 13 of the Periodic Table, a, b, and c are 1].

Since the ionic compound (B-1) and the halogen compound (B-3) do not have a carbon atom to be supplied to the component (A), the carbon source for the component (A) is the above ( Component C) is required. In addition, even if it is a case where the said polymerization catalyst composition contains the said aluminoxane (B-2), this polymerization catalyst composition can contain the said (C) component. The second polymerization catalyst composition may contain other components, such as a promoter, contained in a normal rare earth element compound-based polymerization catalyst composition.
In the polymerization reaction system, the concentration of the component (A) contained in the second polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / l.

The component (A) used in the second polymerization catalyst composition is a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base. Here, the reaction of the rare earth element compound and the rare earth element compound with a Lewis base is performed. The object does not have a bond between rare earth element and carbon. When the rare earth element compound and the reactant do not have a rare earth element-carbon bond, the compound is stable and easy to handle. Here, the rare earth element compound is a compound containing a lanthanoid element or scandium or yttrium composed of the elements of atomic numbers 57 to 71 in the periodic table.
Specific examples of the lanthanoid element include lanthanium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. In addition, the said (A) component may be used individually by 1 type, and may be used in combination of 2 or more type.

The rare earth element compound is preferably a divalent or trivalent salt or complex compound of a rare earth metal, and one or more coordinations selected from a hydrogen atom, a halogen atom and an organic compound residue. More preferably, the rare earth element compound contains a child. Furthermore, the reaction product of the rare earth element compound or the rare earth element compound and a Lewis base is represented by the following general formula (XI) or (XII):
M ¹¹ X ¹¹ ₂ · L ¹¹ w (XI)
M ¹¹ X ¹¹ ₃ · L ¹¹ w (XII)
(In the formula, M ¹¹ represents a lanthanoid element, scandium or yttrium, and X ¹¹ independently represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, an aldehyde residue, a ketone residue. A group, a carboxylic acid residue, a thiocarboxylic acid residue or a phosphorus compound residue, L ¹¹ represents a Lewis base, and w represents 0 to 3).

  Specific examples of the group (ligand) bonded to the rare earth element of the rare earth element compound include a hydrogen atom; a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert- Aliphatic alkoxy groups such as butoxy group; phenoxy group, 2,6-di-tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6- Isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, 2-isopropyl-6-neopentylphenoxy group; thiomethoxy group, thioethoxy group, thiopropoxy group, thio n-butoxy group, thioisobutoxy group, thio aliphatic thiolate groups such as sec-butoxy group and thio-tert-butoxy group; Noxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropylthiophenoxy group, 2 Arylthiolate groups such as -tert-butyl-6-thioneopentylphenoxy, 2-isopropyl-6-thioneopentylphenoxy, 2,4,6-triisopropylthiophenoxy; dimethylamide, diethylamide, diisopropyl Aliphatic amide group such as amide group; phenylamide group, 2,6-di-tert-butylphenylamide group, 2,6-diisopropylphenylamide group, 2,6-dineopentylphenylamide group, 2-tert- Butyl-6-isopropylphenylamide group, 2-tert-butyl Arylamide groups such as ru-6-neopentylphenylamide group, 2-isopropyl-6-neopentylphenylamide group, 2,4,6-tert-butylphenylamide group; bistrialkylsilylamides such as bistrimethylsilylamide group Groups: silyl groups such as trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (bistrimethylsilyl) silyl group; fluorine atom, chlorine atom, bromine atom, iodine And halogen atoms such as atoms. Furthermore, residues of aldehydes such as salicylaldehyde, 2-hydroxy-1-naphthaldehyde, 2-hydroxy-3-naphthaldehyde; 2′-hydroxyacetophenone, 2′-hydroxybutyrophenone, 2′-hydroxypropiophenone, etc. Hydroxyphenone residues of: acetylacetone, benzoylacetone, propionylacetone, isobutylacetone, valerylacetone, ethylacetylacetone, etc. diketone residues; isovaleric acid, caprylic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, Stearic acid, isostearic acid, oleic acid, linoleic acid, cyclopentanecarboxylic acid, naphthenic acid, ethylhexanoic acid, bivaric acid, versatic acid [trade name of Shell Chemical Co., Ltd., mixture of isomers of C10 monocarboxylic acid Synthetic acids comprised of, carboxylic acid residues such as phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid, succinic acid; hexanethioic acid, 2,2-dimethylbutanethioic acid, decanethioic acid, thiobenzoic acid Thiocarboxylic acid residues such as dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, bis (2-ethylhexyl phosphate), bis (1-methylheptyl phosphate), dilauryl phosphate Dioleyl phosphate, diphenyl phosphate, bis (p-nonylphenyl) phosphate, bis (polyethylene glycol-p-nonylphenyl) phosphate, (butyl) phosphate (2-ethylhexyl), phosphoric acid (1-methylheptyl) ) (2-ethylhexyl), phosphoric acid esters such as phosphoric acid (2-ethylhexyl) (p-nonylphenyl) Residues; monobutyl 2-ethylhexylphosphonate, mono-2-ethylhexyl 2-ethylhexylphosphonate, mono-2-ethylhexyl phenylphosphonate, mono-p-nonylphenyl 2-ethylhexylphosphonate, mono-2-ethylhexyl phosphonate, Phosphonic acid ester residues such as mono-1-methylheptyl phosphonate, mono-p-nonylphenyl phosphonate, dibutylphosphinic acid, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, di Laurylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, bis (p-nonylphenyl) phosphinic acid, butyl (2-ethylhexyl) phosphinic acid, (2-ethylhexyl) (1-methylheptyl) phosphinic acid, (2-ethylhexyl) Phosphinic acids such as (p-nonylphenyl) phosphinic acid, butylphosphinic acid, 2-ethylhexylphosphinic acid, 1-methylheptylphosphinic acid, oleylphosphinic acid, laurylphosphinic acid, phenylphosphinic acid, p-nonylphenylphosphinic acid Can also be mentioned. In addition, these ligands may be used individually by 1 type, and may be used in combination of 2 or more type.

In the component (A) used in the second polymerization catalyst composition, examples of the Lewis base that reacts with the rare earth element compound include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, Diolefins and the like. Here, when the rare earth element compound reacts with a plurality of Lewis bases (in the formulas (XI) and (XII), when w is 2 or 3), the Lewis base L ¹¹ is the same or different. It may be.

  The component (B) used in the second polymerization catalyst composition is at least one compound selected from the group consisting of an ionic compound (B-1), an aluminoxane (B-2), and a halogen compound (B-3). is there. In addition, it is preferable that content of the sum total of (B) component in said 2nd polymerization catalyst composition is 0.1-50 times mole with respect to (A) component.

  The ionic compound represented by the above (B-1) is composed of a non-coordinating anion and a cation, and reacts with a reaction product of the rare earth element compound or its Lewis base as the component (A) to be cationic. Examples thereof include ionic compounds capable of generating a transition metal compound. Here, as the non-coordinating anion, for example, tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Decahydride-7,8-dicarboundecaborate and the like can be mentioned. On the other hand, examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation and tri (substituted phenyl) carbonium cation, and more specifically, as tri (substituted phenyl) carbonyl cation, Examples include tri (methylphenyl) carbonium cation, tri (dimethylphenyl) carbonium cation, and the like. Specific examples of ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation (for example, tri (n-butyl) ammonium cation); N, N-dimethylanilinium N, N-dialkylanilinium cation such as cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation; dialkylammonium cation such as diisopropylammonium cation and dicyclohexylammonium cation Is mentioned. Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. Accordingly, the ionic compound is preferably a compound selected and combined from the above-mentioned non-coordinating anions and cations, specifically, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbohydrate. Preferred is nitrotetrakis (pentafluorophenyl) borate. Moreover, these ionic compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them. In addition, it is preferable that it is 0.1-10 times mole with respect to (A) component, and, as for content of the ionic compound in the said 2nd polymerization catalyst composition, it is still more preferable that it is about 1 time mole.

  The aluminoxane represented by the above (B-2) is a compound obtained by bringing an organoaluminum compound and a condensing agent into contact with each other. For example, the repetition represented by the general formula: (—Al (R ′) O—) A chain aluminoxane or cyclic aluminoxane having a unit (wherein R ′ is a hydrocarbon group having 1 to 10 carbon atoms, and some hydrocarbon groups may be substituted with a halogen atom and / or an alkoxy group) The degree of polymerization of the unit is preferably 5 or more, and more preferably 10 or more. Here, specific examples of R ′ include a methyl group, an ethyl group, a propyl group, and an isobutyl group. Among these, a methyl group is preferable. Examples of the organoaluminum compound used as an aluminoxane raw material include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof, and trimethylaluminum is particularly preferable. For example, an aluminoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be preferably used. The aluminoxane content in the second polymerization catalyst composition is such that the element ratio Al / M of the rare earth element M constituting the component (A) and the aluminum element Al of the aluminoxane is about 10 to 1000. It is preferable to do.

  The halogen compound represented by (B-3) is composed of at least one of a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing an active halogen, and is, for example, the component (A). By reacting with a rare earth element compound or a reaction product thereof with a Lewis base, a cationic transition metal compound, a halogenated transition metal compound, or a compound in which the transition metal center is deficient in charge can be generated. In addition, it is preferable that content of the sum total of the halogen compound in the said 2nd polymerization catalyst composition is 1-5 times mole with respect to (A) component.

As the Lewis acid, boron-containing halogen compounds such as B (C ₆ F ₅ ) ₃ and aluminum-containing halogen compounds such as Al (C ₆ F ₅ ) ₃ can be used. A halogen compound containing an element belonging to the group V, VI or VIII can also be used. Preferably, aluminum halide or organometallic halide is used. Moreover, as a halogen element, chlorine or bromine is preferable. Specific examples of the Lewis acid include methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl aluminum bromide, diethyl Aluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, phosphorus trichloride , Pentachloride , Tin tetrachloride, titanium tetrachloride, tungsten hexachloride, etc., among which diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide, ethylaluminum dibromide preferable.

  The metal halide constituting the complex compound of the above metal halide and Lewis base includes beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, iodine. Calcium chloride, barium chloride, barium bromide, barium iodide, zinc chloride, zinc bromide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride, Manganese bromide, manganese iodide, rhenium chloride, rhenium bromide, rhenium iodide, copper chloride, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, gold bromide, etc. Of these, magnesium chloride, calcium chloride, barium chloride, manganese chloride, zinc chloride, and copper chloride are preferred. , Magnesium chloride, manganese chloride, zinc chloride, copper chloride being particularly preferred.

  Moreover, as a Lewis base which comprises the complex compound of the said metal halide and a Lewis base, a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, alcohol, etc. are preferable. Specifically, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, acetylacetone, benzoylacetone , Propionitrile acetone, valeryl acetone, ethyl acetylacetone, methyl acetoacetate, ethyl acetoacetate, phenyl acetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethyl-hexanoic acid, olein Acid, stearic acid, benzoic acid, naphthenic acid, versatic acid, triethylamine, N, N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethyl-hexyl alcohol Examples include oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, and lauryl alcohol. Among these, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2 -Ethylhexyl alcohol, 1-decanol and lauryl alcohol are preferred.

  The Lewis base is reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per mol of the metal halide. When the reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced.

  Examples of the organic compound containing the active halogen include benzyl chloride.

The component (C) used in the second polymerization catalyst composition is the general formula (X):
YR ¹ _a R ² _b R ³ _c (X)
(In the formula, Y is a metal selected from Group 1, Group 2, Group 12, and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1). Yes, the following general formula (Xa):
AlR ¹ R ² R ³ (Xa)
[Wherein, R ¹ and R ² are the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ represents the above It may be the same as or different from R ¹ or R ² ]. Examples of the organoaluminum compound represented by the general formula (X) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, and tripentylaluminum. , Trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diiso hydrogenated Hexyl aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl aluminum Muzi hydride, isobutylaluminum dihydride and the like. Among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. The organoaluminum compound as component (C) described above can be used alone or in combination of two or more. In addition, it is preferable that it is 1-50 times mole with respect to (A) component, and, as for content of the organoaluminum compound in the said 2nd polymerization catalyst composition, it is still more preferable that it is about 10 times mole.

Next, the structure and performance of the compound contained in the second catalyst composition as a polymerization catalyst will be described.
As a polymerization catalyst, it is for superposition | polymerization, and following formula (A):
R _a MX _b QY _b (A)
[In the formula, each R independently represents an unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium; 20 represents a hydrocarbon group, X is μ-coordinated to M and Q, Q represents a group 13 element of the periodic table, and Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or A hydrogen atom, wherein Y is coordinated to Q and a and b are 2].

（式中、Ｍ¹は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^A及びＲ^Bは、それぞれ独立して炭素数１〜２０の炭化水素基を示し、該Ｒ^A及びＲ^Bは、Ｍ¹及びＡｌにμ配位しており、Ｒ^C及びＲ^Dは、それぞれ独立して炭素数１〜２０の炭化水素基又は水素原子を示す）で表されるメタロセン系複合触媒が挙げられる。
上記メタロセン系重合触媒を用いることで、重合体を製造することができる。また、上記メタロセン系複合触媒、例えば予めアルミニウム触媒と複合させてなる触媒を用いることで、重合体合成時に使用されるアルキルアルミニウムの量を低減したり、無くしたりすることが可能となる。なお、従来の触媒系を用いると、重合体合成時に大量のアルキルアルミニウムを用いる必要がある。例えば、従来の触媒系では、金属触媒に対して１０当量以上のアルキルアルミニウムを用いる必要があるところ、上記メタロセン系複合触媒であれば、５当量程度のアルキルアルミニウムを加えることで、優れた触媒作用が発揮される。 In a preferred example of the metallocene composite catalyst, the following formula (XV):

(In the formula, M ¹ represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents an unsubstituted or substituted indenyl group, and R ^A and R ^B each independently have 1 to 20 carbon atoms. R ^A and R ^B are μ-coordinated to M ¹ and Al, and R ^C and R ^D each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Metallocene-based composite catalysts represented by
A polymer can be produced by using the metallocene polymerization catalyst. In addition, by using the above metallocene composite catalyst, for example, a catalyst previously combined with an aluminum catalyst, the amount of alkylaluminum used during the synthesis of the polymer can be reduced or eliminated. If a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum at the time of polymer synthesis. For example, in the conventional catalyst system, it is necessary to use 10 equivalents or more of alkylaluminum with respect to the metal catalyst. If the metallocene composite catalyst is used, an excellent catalytic action can be obtained by adding about 5 equivalents of alkylaluminum. Is demonstrated.

  In the metallocene composite catalyst, the metal M in the formula (A) is a lanthanoid element, scandium, or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

  In the formula (A), each R is independently an unsubstituted indenyl or a substituted indenyl, and the R is coordinated to the metal M. Specific examples of the substituted indenyl group include 1,2,3-trimethylindenyl group, heptamethylindenyl group, 1,2,4,5,6,7-hexamethylindenyl group, and the like. It is done.

  In the above formula (A), Q represents a group 13 element in the periodic table, and specific examples include boron, aluminum, gallium, indium, thallium and the like.

  In the above formula (A), each X independently represents a hydrocarbon group having 1 to 20 carbon atoms, and X is μ-coordinated to M and Q. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. Note that the μ coordination is a coordination mode having a crosslinked structure.

  In the formula (A), each Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and the Y is coordinated to Q. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

In the above formula (XV), the metal M ¹ is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the metal M ¹ include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

In the above formula (XV), Cp ^R is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7X R _X or C ₉ H _11X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group.
Specific examples of the substituted indenyl include 2-phenylindenyl and 2-methylindenyl. Incidentally, the two Cp ^R in the formula (XV) may each be the same or different from each other.

In the above formula (XV), R ^A and R ^B each independently represent a hydrocarbon group having 1 to 20 carbon atoms, said R ^A and R ^B is coordinated μ to M ¹及A ^l . Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. Note that the μ coordination is a coordination mode having a crosslinked structure.

In the above formula (XV), R ^C and R ^D are each independently a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

（式中、Ｍ²は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^E〜Ｒ^Jは、それぞれ独立して炭素数１〜３のアルキル基又は水素原子を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体を、ＡｌＲ^KＲ^LＲ^Mで表される有機アルミニウム化合物と反応させることで得られる。なお、反応温度は室温程度にすればよいので、温和な条件で製造することができる。また、反応時間は任意であるが、数時間〜数十時間程度である。反応溶媒は特に限定されないが、原料及び生成物を溶解する溶媒であることが好ましく、例えばトルエンやヘキサンを用いればよい。なお、上記メタロセン系複合触媒の構造は、¹Ｈ−ＮＭＲやＸ線構造解析により決定することが好ましい。 The metallocene composite catalyst is, for example, in a solvent in the following formula (XVI):

(In the formula, M ² represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and R ^{E to} R ^J each independently represents a group having 1 to 3 carbon atoms. an alkyl group or a hydrogen atom, L is a neutral Lewis base, w is, the metallocene complex represented by an integer of 0 to 3), an organoaluminum compound represented by AlR ^K R ^L R ^M It is obtained by reacting with. In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene or hexane may be used. The structure of the metallocene composite catalyst is preferably determined by ¹ H-NMR or X-ray structural analysis.

In the metallocene complex represented by the above formula (XVI), Cp ^R is unsubstituted indenyl or substituted indenyl, and has the same meaning as Cp ^R in the above formula (XV). In the above formula (XVI), the metal M ² is a lanthanoid element, scandium or yttrium, and has the same meaning as the metal M ¹ in the above formula (XV).

The metallocene complex represented by the above formula (XVI) contains a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups (R ^{E to} R ^J groups) contained in the silylamide ligand are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Moreover, it is preferable that at least one of R ^{E to} R ^J is a hydrogen atom. By making at least one of R ^{E to} R ^J a hydrogen atom, the catalyst can be easily synthesized. Furthermore, a methyl group is preferable as the alkyl group.

  The metallocene complex represented by the above formula (XVI) further contains 0 to 3, preferably 0 to 1, neutral Lewis bases L. Here, examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like. Here, when the complex includes a plurality of neutral Lewis bases L, the neutral Lewis bases L may be the same or different.

  In addition, the metallocene complex represented by the above formula (XVI) may exist as a monomer, or may exist as a dimer or a higher multimer.

On the other hand, the organoaluminum compound used for the production of the metallocene composite catalyst is represented by AlR ^K R ^L R ^M , where R ^K and R ^L are each independently a monovalent carbon atom having 1 to 20 carbon atoms. R ^M is a hydrogen group or a hydrogen atom, and R ^M is a monovalent hydrocarbon group having 1 to 20 carbon atoms, provided that R ^M may be the same as or different from R ^K or R ^L described above. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group and tetradecyl group. , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

  Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, Hexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride , Dioctylaluminum hydride, diisooctylaluminum hydride; ethylaluminum dihydride, n-propylaluminium Dihydride, isobutyl aluminum dihydride and the like. Among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. Moreover, these organoaluminum compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them. In addition, the amount of the organoaluminum compound used for the production of the metallocene composite catalyst is preferably 1 to 50 times mole, more preferably about 10 times mole relative to the metallocene complex.

Third polymerization catalyst composition The third polymerization catalyst composition (hereinafter also referred to as “third polymerization catalyst composition”) includes the metallocene composite catalyst and a boron anion. Furthermore, it is preferable that other components contained in the polymerization catalyst composition containing a normal metallocene catalyst, for example, a co-catalyst and the like are included. The metallocene composite catalyst and boron anion are also referred to as a two-component catalyst. According to the third polymerization catalyst composition, since the boron anion is further contained in the same manner as the metallocene composite catalyst, the content of each monomer component in the polymer can be arbitrarily controlled. It becomes.

  In the third polymerization catalyst composition, specific examples of the boron anion constituting the two-component catalyst include a tetravalent boron anion. For example, tetraphenylborate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethyl) Phenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tridecahydride-7,8-dicarboundecaborate Among these, tetrakis (pentafluorophenyl) borate is preferable.

  In addition, the said boron anion can be used as an ionic compound combined with the cation. Examples of the cation include a carbonium cation, an oxonium cation, an amine cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Examples of the carbonium cation include trisubstituted carbonium cations such as a triphenylcarbonium cation and a tri (substituted phenyl) carbonium cation. The tri (substituted phenyl) carbonyl cation is specifically exemplified by tri (methylphenyl). ) Carbonium cation and the like. Examples of amine cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N- N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation. Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. Among these cations, N, N-dialkylanilinium cation or carbonium cation is preferable, and N, N-dialkylanilinium cation is particularly preferable. Therefore, as the ionic compound, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like are preferable. In addition, it is preferable to add 0.1-10 times mole with respect to the said metallocene type composite catalyst, and, as for the ionic compound which consists of a boron anion and a cation, it is still more preferable to add about 1 time mole.

  In the third polymerization catalyst composition, it is necessary to use the metallocene composite catalyst and the boron anion, but a reaction system for reacting the metallocene catalyst represented by the formula (XVI) with an organoaluminum compound. If a boron anion is present, the metallocene composite catalyst of the above formula (XV) cannot be synthesized. Therefore, for the preparation of the third polymerization catalyst composition, it is necessary to synthesize the metallocene composite catalyst in advance, isolate and purify the metallocene composite catalyst, and then combine with the boron anion.

Examples of the third polymerization catalyst co-catalyst which can be used in the compositions, for example, other organic aluminum compound represented by AlR ^K R ^L R ^M described above, aluminoxane can be preferably used. The aluminoxane is preferably an alkylaminoxan, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane. As the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem Co., Ltd.) and the like are preferable. These aluminoxanes may be used alone or in combination of two or more.

-Polymerization process In the production of the non-conjugated olefin copolymer in the rubber composition according to the present invention, when the polymerization catalyst or the polymerization catalyst composition is used, for example, a polymer by a polymerization reaction using a conventional coordination ion polymerization catalyst. It can carry out similarly to the manufacturing method of. Here, when the method for producing a copolymer uses the above-described polymerization catalyst composition, for example, (1) the configuration of the polymerization catalyst composition in a polymerization reaction system containing a non-conjugated olefin and a conjugated diene compound as monomers. The components may be provided separately and the polymerization catalyst composition may be prepared in the reaction system, or (2) a previously prepared polymerization catalyst composition may be provided in the polymerization reaction system. Moreover, (2) includes providing a metallocene complex (active species) activated by a cocatalyst. In addition, the usage-amount of the metallocene complex contained in a polymerization catalyst composition has the preferable range of 0.0001-0.01 times mole with respect to the sum total of a nonconjugated olefin and a conjugated diene compound.

  In the method for producing a copolymer, the polymerization may be stopped using a polymerization terminator such as ethanol or isopropanol.

  The polymerization reaction is preferably performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas. The polymerization temperature of the polymerization reaction is not particularly limited, but is preferably in the range of −100 ° C. to 200 ° C., for example, and can be about room temperature. If the polymerization temperature is raised, the cis-1,4 selectivity of the polymerization reaction may be lowered. Further, the pressure of the polymerization reaction is preferably in the range of 0.1 to 10 MPa in order to sufficiently incorporate the non-conjugated olefin and the conjugated diene compound into the polymerization reaction system. Further, the reaction time of the above polymerization reaction is not particularly limited, and is preferably in the range of 1 second to 10 days, for example. it can.

Further, when the non-conjugated olefin and the conjugated diene compound are polymerized, the concentration of the conjugated diene compound (mol / l) and the concentration of the non-conjugated olefin (mol / l) at the start of polymerization are expressed by the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.0
It is preferable to satisfy the relationship:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.3
And more preferably the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.7
Satisfy the relationship. By setting the value of the concentration of the non-conjugated olefin / the concentration of the conjugated diene compound to 1 or more, the non-conjugated olefin can be efficiently introduced into the reaction mixture.

-Other rubber component The said vulcanized rubber layer can further contain rubber components (other rubber components) other than the said conjugated diene compound-nonconjugated olefin copolymer.

  The type of the other rubber component is not particularly limited. When a diene rubber is included, the compatibility with the conjugated diene compound-nonconjugated olefin copolymer described above is good, and the peel resistance and weather resistance can be further improved. Examples of the diene rubber include natural rubber (NR), various butadiene rubbers (BR), isoprene rubber (IR), and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, natural rubber is preferable because it can further improve crack growth resistance.

  When the diene rubber is included, the content thereof is preferably 10 parts by mass or more and more preferably 20 parts by mass or more with respect to 100 parts by mass of the rubber component. When the amount is less than 10 parts by mass, the above characteristics may not be obtained. The upper limit of the content of the diene rubber is not particularly limited, but is preferably 80 parts by mass or less with respect to 100 parts by mass of the rubber component from the viewpoint of ensuring weather resistance.

Further, when non-diene rubber is used as the other rubber component, discoloration resistance can be improved. Here, the “non-diene rubber” refers to a rubber component containing almost no double bonds in the main chain (specifically, 2.5 mol% or less).
The non-diene rubber is not particularly limited and can be appropriately selected depending on the purpose. For example, ethylene propylene rubber (EPDM), butyl rubber (IIR), silicone rubber (Q), fluorine rubber (FKM), urethane rubber (U) and the like can be mentioned. These may be used individually by 1 type and may use 2 or more types together.

  The rubber component can be contained in rubbers other than the conjugated diene compound-nonconjugated olefin copolymer and diene rubber described above. For example, non-diene rubber (butyl rubber (IIR), ethylene / propylene rubber (EPM, EPDM), urethane rubber (U), silicone rubber (Q), chlorosulfonated rubber (CSM), acrylic rubber (ACM), fluoro rubber (FKM), chlorosulfonated polyethylene, etc.) may be included in a small amount.

  When the non-diene rubber is included, the content thereof is preferably 5 parts by mass or more and more preferably 10 parts by mass or more with respect to 100 parts by mass of the rubber component. When the amount is less than 5 parts by mass, the above characteristics may not be obtained. The upper limit of the content of the non-diene rubber is not particularly limited, but is preferably 50 parts by mass or less with respect to 100 parts by mass of the rubber component from the viewpoint of peel resistance.

○ Other components other than rubber component In addition, the vulcanized rubber layer may be provided with reinforcing fillers such as carbon black, silica, clay, etc .; crosslinking agent; vulcanization accelerator; poly (2,2,4- Anti-aging agents such as amines such as trimethyl-1,2-dihydroquinoline) and phenyl-α-naphthylamine; plasticizers; waxes; antioxidants; softeners such as aroma oils; lubricants; ultraviolet absorbers; A compatibilizer; a homogenizer; a vulcanization accelerator such as stearic acid and zinc white, and the like.

Carbon black is not particularly limited, and a commonly used one may be adopted.
There is no restriction | limiting in particular as content of the said carbon black, Although it can select suitably according to the objective, 10 mass parts-80 mass parts are preferable with respect to 100 mass parts of rubber components. If the carbon black content is less than 10 parts by mass, the state physical properties and crack growth properties may be reduced. On the other hand, when it exceeds 80 mass parts, workability and dynamic magnification may be deteriorated.

There is no restriction | limiting in particular as said crosslinking agent, According to the objective, it can select suitably, For example, a sulfur type crosslinking agent, an organic peroxide type crosslinking agent, an inorganic crosslinking agent, a polyamine crosslinking agent, a resin crosslinking agent, sulfur Compound-based crosslinking agents, oxime-nitrosamine-based crosslinking agents and the like can be mentioned, and among these, sulfur-based crosslinking agents are more preferable as the rubber composition.
There is no restriction | limiting in particular as content of the said crosslinking agent, Although it can select suitably according to the objective, 0.3 mass part-10 mass parts are preferable with respect to 100 mass parts of rubber components. When the content of the cross-linking agent is 0.3 parts by mass or more, the cross-linking can surely proceed. It is possible to prevent deterioration of physical properties of the vulcanizate.

There is no restriction | limiting in particular as said sulfur type crosslinking agent, According to the objective, it can select suitably, For example, sulfur etc. are mentioned.
There is no restriction | limiting in particular as content of the said sulfur, Although it can select suitably according to the objective, 0.3 mass part-5 mass parts are preferable with respect to 100 mass parts of rubber components. If the sulfur content is less than 0.3 parts by mass, a sufficient vulcanization effect may not be obtained, and the target performance may not be achieved. If it exceeds 5 parts by mass, the rubber becomes brittle, and the rubber The fatigue performance may be reduced.

  The vulcanization accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include guanidine series such as diphenylguanidine, aldehyde-amine series, aldehyde-ammonia series, and thiazole series such as mercaptobenzothiazole. Compounds such as sulfenamides such as N, N′-dicyclohexyl-2-benzothiazolylsulfenamide, thiurams such as thiourea and tetramethylthiuram disulfide, dithiocarbamates, and xanthates can be used.

There is no restriction | limiting in particular also about the said anti-aging agent, According to the objective, it can select suitably. Examples thereof include amine-ketone, aromatic secondary amine, monophenol, bisphenol, and polyphenol antioxidants.
However, in the non-black rubber composition of the present invention, it is preferable to reduce the content of the anti-aging agent for the purpose of securing higher discoloration resistance, and specifically, with respect to 100 parts by mass of the rubber component. 3 parts by mass or less is preferable. In addition, the lower limit value of the anti-aging agent is preferably 0.1 parts by mass or more from the viewpoint of maintaining flex resistance.

Moreover, there is no restriction | limiting in particular also about the said wax, According to the objective, it can select suitably. Examples thereof include paraffin wax, microcrystalline wax, and polyethylene wax.
However, in the non-black rubber composition of the present invention, it is preferable to reduce the content of waxes for the purpose of securing higher discoloration resistance. Specifically, with respect to 100 parts by mass of the rubber component It is preferable to be 2 parts by mass or less. The lower limit of the waxes is preferably 0.1 parts by mass or more from the viewpoint of obtaining a desired effect.

Production of vulcanized rubber layer The vulcanized rubber layer constituting the laminate of the present invention can be obtained by vulcanizing a rubber composition containing the conjugated diene compound-nonconjugated olefin copolymer. The method for adjusting the rubber composition is not particularly limited and may be prepared by a known method. For example, it can be obtained by kneading the above components with a kneader such as a Banbury mixer, a kneader, a roll, or an internal mixer.

  Thereafter, the rubber composition prepared as described above is molded and vulcanized to produce a vulcanized rubber layer. Vulcanization conditions can be selected as appropriate, but it is preferably performed at a normal temperature of 120 ° C. to 200 ° C. and a heating time of 1 minute to 900 minutes.

(UV curable ink layer)
The laminate of the present invention is formed by forming a UV curable ink layer on the vulcanized rubber layer.
Here, the UV curable ink is a coating that is cured by irradiating with ultraviolet rays, and usually contains a photopolymerization initiator, oligomer, monomer, and colorant as main components, and further, an ultraviolet absorber if necessary. , Antioxidants, light stabilizers, adhesion promoters, rheology modifiers, dispersants and the like are blended. Further, the UV curable ink used as a raw material for the ink layer of the tire of the present invention may be diluted with a solvent for viscosity adjustment.

  In general, a radical photopolymerization initiator is used as the photopolymerization initiator. Here, as the photopolymerization initiator, more specifically, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl sulfide, isopropylthioxanthone, diethylthioxanthone, methyl 4- (diethylamino) benzoate, etc. A hydrogen abstraction type initiator; an intramolecular cleavage type initiator such as benzoin ether, benzoylpropyl ether, benzyl dimethyl ketal; 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, Α-hydroxyalkylphenone type initiators such as alkylphenylglyoxylate and diethoxyacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethyla Roh-1- (4-morpholinophenyl) alpha-aminoalkylphenone type initiators such as butanone -1; and acyl phosphine oxide, and the like. These photopolymerization initiators may be used alone or in combination of two or more. In addition, the usage-amount of a photoinitiator has the preferable range of 0.1-10.0 mass% of the total amount of the oligomer and monomer mentioned later.

  As the oligomer, in addition to reactive oligomers such as urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and acrylic resin (meth) acrylate, compounds having no reactive functional group are also used as appropriate. be able to. Here, “(meth) acrylate” includes both acrylate and methacrylate. The oligomer content in the UV curable ink is preferably in the range of 20 to 80% by mass.

  As said monomer, an acrylate monomer and a methacrylate monomer are preferable. Here, the acrylate monomer and the methacrylate monomer play a role of improving adhesion to the vulcanized rubber layer and controlling the elastic modulus, and are also necessary for adjusting the viscosity of the coating liquid of the UV curable ink. The blending amount is determined by appropriately adjusting depending on the oligomer used. Specific examples of the monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-ethylhexyl polyethoxy (meth) acrylate, and benzyl (meth) acrylate. , Isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane mono (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholine acrylate (acryloylmorpholine), N- Vinyl caprolactam, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, o-phenylphenyloxyethyl (meth) acrylate, isobonyl (meth) acrylate Monofunctional monomers such as rate; neopentyl glycol di (meth) acrylate, neopentyl glycol dipropoxy di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate Bifunctional monomers such as 1,6-hexanediol di (meth) acrylate and nonanediol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Multifunctional monomers such as acrylate, dipentaerythritol hexaacrylate, tris [(meth) acryloxyethyl] isocyanurate, ditrimethylolpropane tetra (meth) acrylate It can be mentioned. The monomer content in the UV curable ink is preferably in the range of 10 to 80% by mass.

  The colorant is blended to make the colored layer different from the color of the vulcanized rubber layer. For example, when the vulcanized rubber layer is black, a colorant other than black is used. Here, an organic or inorganic pigment or dye can be used as the colorant. For example, titanium oxide etc. are mentioned as an inorganic pigment. For example, white colorants include titanium oxide, antimony white, zinc sulfide and the like, and red colorants include bengara, cadmium red, red lead, mercury sulfide, cadmium, permanent red 4R, risor red, pyrazolone red, Watching Red, Calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B, C.I. I. Pigment red 2 and the like, and examples of the blue colorant include C.I. I. Pigment blue 15: 3, C.I. I. Pigment Blue 15, Bituminous Blue, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Metal-free Phthalocyanine Blue, Partially Chlorinated Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue BC, etc. , Yellow lead, zinc yellow, cadmium yellow, yellow iron oxide, mineral first yellow, nickel titanium yellow, navel yellow, naphthol yellow S, hansa yellow G, hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent Yellow NCG, Tartrazine Lake, C.I. I. Pigment yellow 12 and the like. In addition, the usage-amount of a coloring agent has the preferable range of 1-50 mass% of the total amount of an oligomer and a monomer.

  Further, other compounding agents blended in the UV curable ink are appropriately blended for improving weather resistance, heat resistance, etc., adjusting viscosity, and the like.

  In the present invention, the above-described UV curable ink is applied to the vulcanized rubber layer of a vulcanized tire having a vulcanized rubber layer, for example, by screen printing, ink jet printing, letterpress printing, tampo printing, etc. After coating by the method, the coated layer may be cured by irradiating with ultraviolet rays to form a colored layer on the outer surface of the tire. In addition, a colored layer is applied to the outer surface of the tire by in-mold molding in which a UV curable ink is applied on a release film in advance and cured by irradiating with ultraviolet rays to insert a film obtained when the tire is vulcanized. It may be provided.

<Side rubber for tires>
The tire side rubber of the present invention is characterized by using the above-described laminate.
This is effective in that desired design properties can be secured and excellent discoloration resistance, peel resistance, and weather resistance can be realized.

<Tire>
The tire of the present invention uses the above-described side rubber.
As a method for manufacturing the tire, a conventional method can be used. For example, on a tire molding drum, members normally used for manufacturing a tire such as a carcass layer, a belt layer, and a tread layer containing unvulcanized rubber are sequentially laminated, and the drum is removed to obtain a green tire. Then, a desired tire (for example, a pneumatic tire) can be manufactured by heating and vulcanizing the green tire according to a conventional method.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

Preparation Example 1 Preparation of ethylene-butadiene copolymer (EBR1) After adding 2,000 g of a toluene solution containing 120 g (2.22 mol) of 1,3-butadiene to a sufficiently dry 4 L stainless steel reactor, ethylene was added. It was introduced at 1.72 MPa. On the other hand, in a glove box under a nitrogen atmosphere, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 28.5 μmol in a glass container. , 28.5 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] and 2.00 mmol of diisobutylaluminum hydride were prepared and dissolved in 40 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, an amount of 25.0 μmol in terms of gadolinium was added to the monomer solution, and polymerization was performed at 50 ° C. for 90 minutes. After the polymerization, 5 ml of 2,2′methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) isopropanol solution (5 ml) was added to stop the reaction, and the copolymer was further added with a large amount of methanol. Separation and vacuum drying at 70 ° C. gave a polymer. The yield of the obtained copolymer EBR1 was 98 g.

(Examples 1-2 and Comparative Examples 1-2)
(1) Preparation of UV curable ink 50 parts by mass of urethane acrylate (UV2000B, manufactured by Nippon Synthetic Chemical Co., Ltd.), 25 parts by mass of phenyl glycidyl ether epoxy acrylate (R-128H; manufactured by Nippon Kayaku Co., Ltd.), 25 parts by mass of phenoxyethyl acrylate (R-561; manufactured by Nippon Kayaku Co., Ltd.), 1 part by mass of 1-hydroxycyclohexyl phenyl ketone (Irgacure 184; manufactured by Ciba Geigy) and 20 parts by mass of titanium oxide were mixed. Thus, a UV curable ink was prepared.

(2) Preparation of Vulcanized Rubber Layer and Laminate The raw materials shown in Table 1 were mixed with a Banbury mixer to prepare a rubber composition, and the obtained rubber composition was vulcanized (160 ° C.) A vulcanized rubber layer was produced.
Next, the UV curable ink adjusted as described above was applied onto the obtained vulcanized rubber layer by an ink jet method so that the film thickness was 25 μm.
Then, using SUBZERO 085 (UV lamp system, manufactured by Integration Co., Ltd., output 100 W / cm), the ink composition was cured under the conditions of an integrated light amount of 200 mJ / cm ² and a peak illuminance of 1200 mW / cm ² . The measurement of the integrated light quantity and peak illuminance was performed using an ultraviolet light quantity meter Power Pack (manufactured by EIT). Thereby, a UV curable ink layer was prepared, and a laminate (size: 20 cm × 20 cm × 2 mm) as a sample was prepared.

(Evaluation)
About the sample of the laminated body obtained by each Example and the comparative example, according to the following method, peeling resistance, a weather resistance, and discoloration resistance (index) were measured.

(1) Peel resistance For the laminates of each Example and Comparative Example, vulcanization of the specimen was measured by measuring the drag force when the colored layer was peeled off from the rubber layer at 100 mm / min using a strograph. The peel resistance at the interface between the rubber layer and the colored layer was evaluated.
About evaluation, it displayed as an index when the value of the peeling resistance of the comparative example 1 was set to 100. It shows that peeling resistance is so large that an index value is large.
About evaluation of a measured value, it displays as an index value when the value of peeling resistance of the comparative example 1 is set to 100, and it shows that peeling resistance is so large that a numerical value is large, and it is a favorable result. The evaluation results are shown in Table 1.

(2) Ozone resistance (weather resistance)
About the sample of the laminated body obtained in each Example and Comparative Example, it was set as a test piece of 20 mm × 100 mm × 1.0 mm and left in a constant temperature bath at 40 ° C. and an ozone concentration of 50 pphm while giving 50% elongation. The time until cracks could be confirmed with the naked eye was measured.
The evaluation of ozone resistance is expressed as an index when the time until the crack of Comparative Example 1 can be confirmed is taken as 100. The larger the city value, the longer the time until the crack can be confirmed and the better the weather resistance. It shows that. The evaluation results are shown in Table 1.

(3) Discoloration resistance (contamination resistance)
The samples of the laminates obtained in each Example and Comparative Example were subjected to exposure evaluation outdoors, and the magnitude of change in color difference after 30 days of exposure and the initial color difference was measured to evaluate stain resistance. . A spectrocolorimeter (Konica Minolta Co., Ltd. CM-700D) was used for the measurement.
About evaluation, it displays as an index value when the color difference of the comparative example 1 is set to 100, A color difference is so small that a numerical value is large, and stain resistance becomes favorable. The evaluation results are shown in Table 1.

* 1: RSS # 1
* 2: BR01 made by JSR
* 3: Carbon black, FEF, iodine adsorption amount = 43 g / kg, DBP oil absorption amount = 121 ml / 100 g, N ₂ SA (nitrogen adsorption specific surface area) = 42 m ² / g, “Asahi # 65” manufactured by Asahi Carbon Co., Ltd.
* 4: MXST made by Miyoshi Oil
* 5: N- (1,3-dimethylbutyl) -N′-p-phenylenediamine, knock rack 6C manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 6: Nippon Seiwa Co., Ltd. Ozoace-0701
* 7: “Hakusuitec” manufactured by Kyushu Hakusui
* 8: N-cyclohexyl-2-benzothiazolylsulfenamide, Noxeller CZ-G manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 9: Dibenzothiazyl disulfide, Nouchira DM-P manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 10: Mikulon OT-20, manufactured by Shikoku Chemicals Co., Ltd.

  From Table 1, the samples according to Examples 1 and 2 of the present invention are excellent in balance in all of the peel resistance, weather resistance, and discoloration resistance, while the samples of Comparative Examples 1 and 2 are discoloration resistance. It turned out that it becomes a result inferior to an Example about the item of property and peeling resistance.

  The present invention uses a laminate having excellent discoloration resistance and excellent peeling resistance and weather resistance for the tire side rubber, and therefore, discoloration resistance, peeling resistance and weather resistance compared to conventional tires. It is industrially useful in that it can be used for a long time.

Claims (12)

A laminate in which a UV curable ink layer is formed on a vulcanized rubber layer,
The vulcanized rubber layer contains a conjugated diene compound -nonconjugated olefin copolymer having a conjugated diene compound- derived content of 30 to 80 mol% .   The laminate according to claim 1, wherein the copolymer of the conjugated diene compound and the non-conjugated olefin has a cis-1,4 bond content of a conjugated diene compound-derived portion of 50% or more.   The laminate according to claim 1, wherein the conjugated diene compound-nonconjugated olefin copolymer has a polystyrene-reduced weight average molecular weight of 10,000 to 10,000,000.   2. The laminate according to claim 1, wherein the conjugated diene compound-nonconjugated olefin copolymer has a molecular weight distribution (Mw / Mn) of 10 or less.   The laminate according to claim 1, wherein the conjugated diene compound of the conjugated diene compound-nonconjugated olefin copolymer is at least one selected from the group consisting of 1,3-butadiene and isoprene.   The laminate according to claim 1, wherein the non-conjugated olefin of the conjugated diene compound-non-conjugated olefin copolymer is at least one selected from the group consisting of ethylene, propylene, and 1-butene. The laminate according to claim 6 , wherein the non-conjugated olefin is ethylene.   The lamination according to claim 1, wherein the content of the conjugated diene compound-nonconjugated olefin copolymer in the vulcanized rubber layer is 20 to 80 parts by mass with respect to 100 parts by mass of the rubber component. body.   The laminated body according to claim 1, wherein the vulcanized rubber layer further contains an anti-aging agent in an amount of 3 parts by mass or less based on 100 parts by mass of the rubber component.   The laminate according to claim 1, wherein the vulcanized rubber layer further contains 2 parts by mass or less of wax with respect to 100 parts by mass of the rubber component. Side rubber tires, characterized in that it comprises a laminate according to claim 1. A tire characterized by comprising a tire side rubber according to claim 11.