JPH07300540A - Cycloolefin polymer composition and core-shell elastomer used therefor - Google Patents

Abstract

PURPOSE: To obtain the title composition improved in impact resistance without detriment to transparency by incorporating a specified cycloolefin polymer with a core/shell elastomer comprising a specified core component and a specified shell component.

CONSTITUTION: There is provided the title composition comprising (A) a cycloolefin ring-opening polymer hydrogenate being (a) a cycloolefin random copolymer obtained by copolymerizing a 2C or higher α-olefin with a cycloolefin of formula I or II, (b) a cycloolefin ring-opening polymer of formula I or II, and (c) a cycloolefin polymer being a cycloolefin ring opening polymer hydrogenate of formula I or II and (B) a core/shell elastomer comprising (d) 40-85 pts.wt. core component comprising a styrene/butadiene rubber, (e) 15-60 pts.wt. shell part comprising a copolymer of a (meth)acrylate monomer having a specified cycloaliphatic skeleton, a monovinyl aromatic monomer, another monovinyl monomer copolymerizable therewith, and a polyfunctional monomer and having an A/B weight ratio of 40/60 to 95/5.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cyclic olefin polymer composition and a core / shell elastomer used therein. More specifically, it relates to a composition comprising a core / shell elastomer containing a acrylate or methacrylate monomer having a specific alicyclic skeleton as a constituent in a shell component and a cyclic olefin polymer, and a core / shell elastomer used therein.

[0002]

BACKGROUND OF THE INVENTION The present applicant has previously found that a cyclic olefin-based random copolymer obtained by copolymerizing ethylene with a cyclic olefin such as tetracyclododecene or norbornene has excellent transparency and heat resistance. It is a synthetic resin that has a good balance of properties, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and rigidity, and exhibits excellent performance in the field of optical materials such as optical memory disks and optical fibers. Have already been found, and JP-A-60-168708, JP-A-61-98780 and JP-A-61-1
15912, JP-A-61-115916,
JP-A-61-120816, JP-A-62-252
No. 407 publication. The cyclic olefin random copolymers described in these publications are also known to exhibit excellent performance in the field of structural materials.

However, although these cyclic olefin-based copolymers have excellent heat resistance and rigidity, there is room for improvement in impact resistance, and the transparency possessed by these cyclic olefin-based copolymers is maintained. At the same time, further improvement in impact resistance is required.

Further, the applicant of the present invention has found that a specific softening temperature (TM
A composition comprising a cyclic olefin-based random copolymer having A) and a specific α-olefin-based elastic copolymer,
It has been found that a resin having improved impact resistance can be obtained without impairing excellent properties such as heat resistance, heat aging resistance, and chemical resistance, and it has already been proposed in JP-A-1-163241.

Further, the present applicant has proposed, as a cycloolefin polymer composition having improved impact resistance, a specific cyclic olefin random copolymer and a specific soft copolymer as an organic peroxide. A cyclic olefin-based copolymer composition comprising a product obtained by the reaction in the presence of the above has been already proposed in JP-A-2-167318.

However, the cycloolefin polymer compositions proposed in JP-A-1-163241 and JP-A-2-167318 have improved impact resistance, but are not sufficiently transparent. No, there was room for improvement.

[0007]

An object of the present invention is to provide a cyclic olefin polymer composition. Another object of the present invention is to provide a cyclic olefin polymer composition containing a core-shell elastomer containing an acrylate or methacrylate monomer having a specific alicyclic skeleton as a constituent component in a shell component. . Still another object of the present invention is to provide a polymer composition containing a cyclic olefin polymer having improved impact resistance and the above core / shell elastomer without impairing the original transparency of the cyclic olefin polymer. To provide. Still another object of the present invention is to provide a core-shell elastomer containing the above acrylate or methacrylate monomer having a specific alicyclic skeleton as a constituent in a shell component. Further objects and advantages of the present invention will be apparent from the following description.

[0008]

According to the present invention, the above objects and advantages of the present invention are as follows: [A], [A-1] (i) at least one α-olefin having 2 or more carbon atoms; (Ii) The following formula [I] or [II]

[0009]

[Chemical 27]

(In the formula [I], u is 0 or 1, and v
Is 0 or a positive integer, w is 0 or 1, and R
^{61 to} R ⁷⁸ and R ^a1 and R ^b1 are each independently
A hydrogen atom, a halogen atom or a hydrocarbon group, R ⁷⁵
To R ⁷⁸ may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and R ⁷⁵ and R ⁷⁶ are each represented by Alternatively, R ⁷⁷ and R ⁷⁸ may form an alkylidene group).

[0011]

[Chemical 28]

(In the formula [II], x and d are 0 or 1
Is an integer greater than or equal to y and z is 0, 1 or 2.
R⁸¹~ R⁹⁹Are independently hydrogen atom and halogen atom
Child, aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic carbonization
A hydrogen group or an alkoxy group, R⁸⁹Or R⁹⁰Concludes
A carbon atom and a R⁸³The carbon atom to which
Or R⁹¹The carbon atom to which is bound is directly or
Even if it is bonded through an alkylene group having 1 to 3 elementary atoms
Well, when y = z = 0, R⁸⁵And R⁸²Or R ⁸⁵When
R⁹⁹And are bonded to each other to form a monocyclic or polycyclic aromatic ring.
May be made. ) Represented by at least one
Cyclic olefin obtained by copolymerizing with cyclic olefin
-Based random copolymer [A-2] represented by the following formula [I] or [II],
A ring-opening polymer of at least one cyclic olefin [A-3] represented by the following formula [I] or [II],
It is a cyclic olefin polymer selected from the group consisting of hydrogenated products of at least one ring-opening polymer of cyclic olefin.
And the intrinsic viscosity [η] in decalin at 135 ° C is 0.0
5 to 5.0 dl / g, measured by DSC
The transition temperature (Tg) is 70 ℃ or higher, measured at 25 ℃
The cyclic olefin having a refractive index nD of 1.500 to 1.650
Fin-based polymer and [B], [B-1] Styrene unit of 50% by weight or less
Core component 40-85 composed of a ethylene-butadiene rubber
Parts by weight and [B-2] (b-1) the following general formula [III]

[0013]

[Chemical 29]

(In the formula [III], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a and R ^b are respectively Independently a hydrogen atom, a halogen atom or a hydrocarbon group,
R ^{15 to} R ¹⁸ may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and R ¹⁵ and R ¹⁶ are Or R ¹⁷ and R
^{And 18} may form an alkylidene group, ^one of X ¹ and X ² is an acryloyloxy group or a methacryloyloxy group represented by the following formula [X], and the other is a hydrogen atom or an alkyl group. Is. );

[0015]

[Chemical 30]

A compound represented by the formula (wherein R is a hydrogen atom or a methyl group), represented by the following general formula [IV]

[0017]

[Chemical 31]

(In the formula [IV], p and l are 0 or an integer of 1 or more, and r and s are 0, 1 or 2
And R ^{21 to} R ³⁹ each independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, and R ²⁹ and R ³⁰ are The carbon atom bonded to R ³³ and the carbon atom bonded to R ³³ or the carbon atom bonded to R ³¹ may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and , R = s = 0, R ³⁵
And R ³² or R ³⁵ and R ³⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring, and one of X ³ and X ⁴ is represented by the above formula [X]. Is an acryloyloxy group or a methacryloyloxy group, and the other is a hydrogen atom or an alkyl group. ); And a compound represented by the following formula [V]

[0019]

[Chemical 32]

(In the formula [V], t is 4 or 5, and R is
^{41 to} R ⁴³ each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group, and X ⁵ represents an acryloyloxy group or a methacryloyloxy group represented by the above formula [X]. 20-100% by weight of at least one kind of acrylate or methacrylate monomer having an alicyclic skeleton selected, (b-2) 0-70% by weight of monovinyl aromatic monomer (b-3) A monomer or monomer mixture consisting of 0 to 70% by weight of another polymerizable monovinyl monomer and 0 to 3% by weight of (b-4) a polyfunctional monomer is used as a constituent component (co). 15 to 60 parts by weight of a shell component made of a polymer, provided that the core component [B-1] and the shell component [B-
2] is 100 parts by weight, and the core / shell elastomer is characterized in that the average diameter of the primary particles is in the range of 100 to 300 nm, and the above [A] component vs. [B] Weight ratio of components is 40 /
It is achieved by the cycloolefin polymer composition characterized by being in the range of 60 to 95/5 and the core-shell elastomer [B].

According to the present invention, the core / shell elastomer [B] component used in the present invention is [B-1 '].
A styrene-butadiene rubber latex having a styrene unit of 50% by weight or less is added to 40 to 85 parts by weight of [B-
2 ′] at least 1 of an acrylate or methacrylate monomer having an alicyclic skeleton selected from the group consisting of compounds represented by the above formulas [III], [IV] and [V]
Species 20 to 100% by weight, (b-2) Monovinyl aromatic monomer 0 to 70% by weight (b-3) Other monovinyl type copolymerizable with these 0 to 70% by weight and (b- 4) Polyfunctional monomer Obtained by graft-polymerizing 15 to 60 parts by weight of a monomer or monomer mixture consisting of 0 to 3% by weight. However, latex [B-
1 '] and the monomer or the monomer mixture [B-2''] are 100 parts by weight in total. Hereinafter, this method is referred to as a first manufacturing method.

According to the present invention, as another method for producing the core-shell elastomer [B], [B-1]
40 to 85 parts by weight of a core component composed of a styrene-butanediene rubber having a styrene unit of 50% by weight or less and [B-2 ″] (b-2) monovinyl aromatic monomer 2
0-80% by weight, (b-3) 20-80% by weight of another monovinyl-based monomer copolymerizable therewith and (b-
4) Polyfunctional monomer Shell component 1 made of a copolymer having a monomer mixture of 0 to 3% by weight as a constituent component
Core-shell elastomer consisting of 5 to 60 parts by weight
With respect to 100 parts by weight, however, the total of the core component [B-1 ′] and the shell component [B-2 ″] is 100 parts by weight,
[B-2 ″ ′] At least one acrylate or methacrylate monomer having an alicyclic skeleton selected from the group consisting of compounds represented by the above formulas [III], [IV] and [V] 5 A method of graft polymerizing 100 parts by weight is provided. Hereinafter, this method is referred to as a second manufacturing method.

First, the first manufacturing method will be described.
The latex [B-1 '] of a styrene-butadiene rubber having a styrene unit of 50% by weight or less is usually obtained by emulsion polymerization. The content of styrene units is 50% by weight or less, preferably 30% by weight or less. Known emulsion polymerization methods also include seed polymerization methods. Further, known molecular weight modifiers and cross-linking agents can be added when producing the rubber latex. Examples of the cross-linking agent include cross-linking monomers such as divinylbenzene; polyvinyl esters of polybasic acids such as divinyl adipate; di- and trimethacrylates of polyhydric alcohols such as mono- or polyethylene glycol dimethacrylate (or polyhydric alcohols). Di- and triacrylates); divinyl ethers of polyhydric alcohols such as ethylene glycol divinyl ether, diallyl phthalate,
Di- or triallyl esters of polybasic acids such as diallyl maleate, diallyl fumarate, diallyl sebacate; triallyl compounds such as diallyl ether, triallyl cyanurate, triallyl isocyanurate; allyl methacrylate, allyl acrylate, allyl itaconate , Allyl esters of polymerizable carboxylic acids such as monoallyl fumarate and monoallyl allate. The crosslinkable polymer is preferably used in a proportion of 3% by weight or less. Further, other vinyl-based monomers copolymerizable with styrene and butadiene, for example, vinyl cyan compounds such as acrylonitrile, alkyl esters of acrylic acid or methacrylic acid, and the like can be used in a proportion of 3% by weight or less.

The rubber latex used in the present invention [B-
1 ′] preferably has a primary particle average particle diameter in the range of 50 to 250 nm, more preferably in the range of 60 to 200 nm. In addition, a monomer or a monomer mixture [B-
2 ′] is at least one acrylate or methacrylate monomer having an alicyclic skeleton selected from the group consisting of compounds represented by the above formulas [III], [IV] and [V], or Contains at least one.

The compounds represented by the formulas [III], [IV] and [V] will be described below. Formula [II
I], n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. When q is 1, the ring represented by q is a 6-membered ring, and when q is 0, this ring is a 5-membered ring.

R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group. Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The hydrocarbon group is usually an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group. Is mentioned. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group. These alkyl groups may be substituted with a halogen atom.

The cycloalkyl group includes a cyclohexyl group, and the aromatic hydrocarbon group includes a phenyl group and a naphthyl group. Further, the above formula [II
I], R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ are R ¹⁵
And R ¹⁷ , R ¹⁶ and R ¹⁸ , R ¹⁵ and R ¹⁸ , or R ¹⁶ and R ¹⁷ are respectively bonded (cooperatively) to form a monocyclic or polycyclic group. And the monocycle or polycycle thus formed may have a double bond. Specific examples of the monocycle or polycycle formed here include the following.

[0029]

[Chemical 33]

In the above exemplification, the carbon atoms numbered 1 or 2 are each represented by R in the formula [III].
^It represents a carbon atom to which ¹⁵ (R ¹⁶ ) or R ¹⁷ (R ¹⁸ ) is bonded. Further, R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include an ethylidene group, a propylidene group and an isopropylidene group.

Further, ^one of X ¹ and X ² is an acryloyloxy group or a methacryloyloxy group represented by the above formula [X], and the other is a hydrogen atom or an alkyl group.

In the formula [IV], p and l are 0 or a positive integer, and r and s are 0, 1 or 2. R ^{21 to} R ³⁹ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group.

The halogen atom is represented by the above formula [III]
The same thing as the halogen atom in the inside can be illustrated. The aliphatic hydrocarbon group usually includes an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group. These alkyl groups may be substituted with a halogen atom.

Examples of the cycloalkyl group include a cyclohexyl group. Examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group, and specific examples thereof include a phenyl group, a tolyl group, a funatyl group, a benzyl group and a phenylethyl group.

Examples of the alkoxy group include methoxy group and eth
Examples thereof include a xy group and a propoxy group. Where R²⁹
And R³⁰The carbon atom to which R is attached, and R³³Combined with
Carbon atom or R³¹The carbon atom to which is bound is
Directly or through an alkylene group having 1 to 3 carbon atoms
May be combined. That is, the above two carbon atoms are
When linked via an alkylene group, R²⁹And R
³³Or or R³⁰And R ³¹Together with each other,
Ren group (-CH₂-), Ethylene group (-CH₂CH₂-) Or propylene
Group (-CH₂CH₂CH₂-) Form any alkylene group
Is made.

Further, when r = s = 0, R ³⁵ and R ³² or R ³⁵ and R ³⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Specifically, r = s = 0
In this case, the following aromatic ring formed by R ³⁵ and R ³² can be mentioned.

[0037]

[Chemical 34]

Here, l is the same as l in the formula [IV]. Moreover, one of X ³ and X ⁴ is an acryloyloxy group or a methacryloyloxy group represented by the above formula [X], and the other is a hydrogen atom or an alkyl group. Further, in the formula [V], t is 4 or 5. When t is 4, the compound of formula [V] is a compound having a 5-membered ring, and when t is 5, the compound of formula [V] is a compound having a 6-membered ring.

R ⁴¹ , R ⁴² and R ⁴³ are each independently a hydrogen atom, a halogen atom or a hydrocarbon group. Examples of the halogen atom are the same as those exemplified for the formula [III]. Examples of the hydrocarbon group generally include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. Specific examples of these groups are the same as those exemplified for R ^{21 to} R ^{39 in} the formula [IV].

X ⁵ is an acryloyloxy group or a methacryloyloxy group represented by the above formula [X]. The following compounds may be mentioned as specific examples of the compound represented by the above formula [III].

[0041]

[Chemical 35]

[0042]

[Chemical 36]

[0043]

[Chemical 37]

[0044]

[Chemical 38]

[0045]

[Chemical Formula 39]

[0046]

[Chemical 40]

[0047]

[Chemical 41]

[0048]

[Chemical 42]

[0049]

[Chemical 43]

[0050]

[Chemical 44]

[0051]

[Chemical formula 45]

[0052]

[Chemical formula 46]

[0053]

[Chemical 47]

[0054]

[Chemical 48]

[0055]

[Chemical 49]

The compound represented by the above formula [III] is known, and is disclosed in, for example, JP-A-3-79611. The following compounds may be mentioned as specific examples of the compound represented by the above formula [IV].

[0057]

[Chemical 50]

[0058]

[Chemical 51]

[0059]

[Chemical 52]

[0060]

[Chemical 53]

[0061]

[Chemical 54]

[0062]

[Chemical 55]

Aromatic group represented by the above general formula [IV]
Is a polycyclic acrylate compound having an IR (infrared)
Identified by spectroscopic and NMR (nuclear magnetic resonance)
You can For example, in formula [IV], p,
l, r and s are 0 and R ^{twenty one}~ R³⁹And X^FourHaso
Each is a hydrogen atom, and X³Is methacryloyl oki
5-phenyl-bicyclo [2.2.1] hepti which is a cis group
For IR-2-methacrylate, the IR spectrum
1725 cm at tor^-1And 1635 cm^-1To it
Due to the C = O bond and C = C bond of the methacryloyl group, respectively.
The coming peak is again 700 cm^-1Derived from the phenyl group
Peaks are observed. Also in the NMR spectrum,
The peak derived from the phenyl group at 7.1 to 7.3 ppm,
Peak derived from norbornene ring at 4.7-5.1 ppm
Is due to methacrylic acid ester at 5.5 to 6.5 ppm.
There is an upcoming peak.

The monocyclic acrylate compound having an aromatic group represented by the above general formula [IV] is known,
For example, it is disclosed in JP-A-5-140231. The polycyclic acrylate compound having an aromatic group represented by the general formula [IV] is produced, for example, as follows. That is, acrylic acid, methacrylic acid or their ester-forming derivatives, and the following general formula [IV] -a having a structure corresponding to a polycyclic acrylate compound
Is reacted with a polycyclic alcohol represented by or an ester-forming derivative thereof.

[0065]

[Chemical 56]

In the above formula [IV] -a, the meanings of the respective symbols other than Y ¹ and Y ² are the same as in the formula [IV]. Y ¹
One of Y ² and Y ² is a hydroxyl group, and the other is a hydrogen atom or an alkyl group.

The polycyclic alcohol represented by the general formula [IV] -a or the ester-forming derivative thereof has the following general formula having a structure corresponding to the alcohol compound represented by the above general formula [IV] -a. A formic acid is added to an unsaturated bond of a polycyclic olefin represented by [IV] -b to form a formic acid ester of the polycyclic olefin, and then the formic acid ester is hydrolyzed. You can

[0068]

[Chemical 57]

The definition of each symbol in the above formula [IV] -b is the same as that in the above formula [IV]. The method for preparing such a cyclic olefin will be described in detail later. General formula [I
V] -b is reacted with formic acid by reacting the polycyclic olefin with the polycyclic olefin in a molar ratio of usually 1 to 10 times, preferably 2 to 6 times the formic acid. The mixture with is usually 50 to 200 ° C., preferably 70 to 200 ° C.
It is carried out at 150 ° C., particularly preferably under the condition that formic acid is refluxed. In this reaction, formic acid is added to the double bond site of the cyclic olefin represented by the general formula [IV] -b to form a formic acid ester of polycyclic olefin. Then, the formic acid ester of the polycyclic olefin is hydrolyzed in a mixed solvent of water and ethanol using a caustic alkali such as caustic soda at room temperature to 100 ° C. to give a compound represented by the general formula [IV] -a. A polycyclic alcohol is obtained. At this time, the caustic alkali is usually used in a molar ratio of 0.7 to 2 with respect to the formic acid ester of the polycyclic olefin,
It is desirable to use it in an amount of preferably 1.0 to 1.5.

Then, the above-mentioned general formula [IV] -a
When a polycyclic alcohol represented by the following is reacted with (i) acrylic acid or methacrylic acid, or (ii) an ester-forming derivative of acrylic acid or methacrylic acid to form an ester, the compound of the general formula [IV] A polycyclic acrylate compound represented by is obtained.

This esterification reaction is carried out under the following conditions. When the polycyclic alcohol represented by the general formula [IV] -a is directly esterified with (i) (meth) acrylic acid, the alcohol and (meth) acrylic acid are reacted in the presence of an acidic catalyst. , Normal pressure, 60 ℃ ~ 150
It is preferable to carry out the esterification reaction under the condition of ° C while removing the produced water. Specific examples of the acidic catalyst include sulfuric acid, p-toluenesulfonic acid, sulfonic acid type ion exchange resin, hydrochloric acid and the like.

When an esterification reaction is carried out using a polycyclic alcohol [IV] -a and (ii) an ester-forming derivative of (meth) acrylic acid, the alcohol and (meth) acrylic acid An ester-forming derivative,
It is preferable to carry out the esterification reaction at −10 ° C. to 30 ° C. at atmospheric pressure for several hours. At this time, an alkali such as triethylamine or sodium hydroxide may be added as a receptor for the generated hydrochloric acid. Specific examples of the ester-forming derivative of (meth) acrylic acid include acrylic acid halides such as acrylic acid chloride and methacrylic acid chloride, and methacrylic acid halides.

The compound of the above formula [IV] can be further produced by the second production method as described below.
That is, it can be obtained by addition-reacting acrylic acid or methacrylic acid with a polycyclic olefin represented by the above general formula [IV] -b having a structure corresponding to the desired polycyclic acrylate compound.

The polycyclic olefin represented by the above general formula [IV] -b is an aromatic olefin (or a norbornene ring carbon atom having a reactive double bond site) with a cyclopentadiene compound as described below. And a norbornene derivative having an aromatic group) are subjected to a Diels-Alder reaction.

This reaction is specifically represented by the following formula. In the polycyclic olefin represented by the above general formula [IV] -b, when p is 0, it is represented by the following formula.

[0076]

[Chemical 58]

In the polycyclic olefin represented by the above general formula [IV] -b, when p is 1 or more, it is represented by the following formula.

[0078]

[Chemical 59]

The reaction between the compound represented by the general formula [IV] -b and acrylic acid or methacrylic acid is carried out at 60 ° C. to 150 ° C. for several hours at atmospheric pressure or under pressure using an acidic catalyst.

Specific examples of the acidic catalyst include sulfuric acid, boron trifluoride, perfluoroacetic acid, polyphosphoric acid, activated clay, and acidic ion exchange resins. The polycyclic acrylate or methacrylate having an aromatic group represented by the general formula [IV] according to the present invention can be obtained by the first or second production method as described above.

The following compounds may be mentioned as specific examples of the compound represented by the above formula [V].

[0082]

[Chemical 60]

The compound represented by the above formula [V] is obtained by reacting the corresponding alicyclic alcohol or its ester-forming derivative with acrylic acid, methacrylic acid or their ester-forming derivative, or by reacting them. It can be produced by addition reaction of alicyclic olefin with acrylic acid or methacrylic acid.

The above formulas [III], [IV] and [V]
At least one acrylate or methacrylate monomer having an alicyclic skeleton selected from the group consisting of compounds [B-2 ′] is a latex of a styrene-butadiene rubber having a styrene unit content of 50% by weight or less. [B-
1 '] is graft-polymerized. During the graft polymerization, together with the acrylate or methacrylate monomer, a monovinyl aromatic monomer (b-2), another monovinyl monomer (b-3) copolymerizable therewith and a polyvinyl aromatic monomer (b-3) A monomer or monomer mixture composed of the functional monomer (b-4) can be used in combination. As the monovinyl aromatic monomer (b-2), a compound represented by the following formula is preferably used.

[0085]

[Chemical formula 61]

In the above formula, R ⁵² , R ⁵³ and R ⁵⁴ may be the same or different and each is a hydrogen atom or a lower alkyl group. ) Specifically, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, m-ethylstyrene, p-ethylstyrene, o-isopropylstyrene,
Examples thereof include m-isopropylstyrene and p-isopropylstyrene.

The above compounds may be used alone or
Used in combination of two or more species. As other copolymerizable monovinyl-based monomer (b-3), (meth) acrylate, α, β-unsaturated carboxylic acid, vinyl ether and ethylene derivative having a halogen atom or a cyano group are preferable. Can be mentioned.
Examples of the (meth) acrylate include monomers represented by the following general formula.

[0088]

[Chemical formula 62]

In the above formula, R ⁵⁵ represents a hydrogen atom or a methyl group, R ⁵⁶ is a hydrocarbon group having 1 to 10 carbon atoms, and these may have a substituent. Examples of this substituent include a hydroxyl group (—OH), an epoxy group, a halogen, an oxymethylene group, and an oxyethylene group.

Specific examples of such (meth) acrylates include (meth) acrylic acid esters shown below. Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth)
Acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth)
Acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylolethane mono (meth) acrylate, butenediol Mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2- (6
-Hydroxyhexanoyloxy) ethyl acrylate, glycidyl (meth) acrylate and the like.

The above compounds may be used alone or in combination with 2
Used in combination of two or more species. Specific examples of the α, β-unsaturated carboxylic acid or derivative thereof include the following compounds.

Acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endocis-bicyclo [2.2.1.] Hept-
5-ene-2,3-dicarboxylic acid (Nadic acid TM),
Methyl-endocis-bicyclo [2.2.1.] Hept-5-
En-2,3-dicarboxylic acid (methyl nadic acid T
M), or the above carboxylic acid halide.

Examples of the α, β-unsaturated carboxylic acid derivative include amides, imides and acid anhydrides of α, β-unsaturated carboxylic acids. Specifically, maleenyl chloride,
Maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, etc. can be mentioned. Compounds such as the above may be used alone or
Used in combination of two or more species. As the vinyl ether, a monomer represented by the following formula can be exemplified. CH ₂ ═CH—O—R ^{57 In the} above formula, R ⁵⁷ is an alkyl group having 1 to 20 carbon atoms. Specific examples of such vinyl ethers include the following compounds.

Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, isoamyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, n- Decyl vinyl ether, 2,2-dimethylhexyl vinyl ether, 2,2-dimethyloctyl vinyl ether, 2,2-dimethyldecyl vinyl ether,
2,2-dimethyl dodecyl vinyl ether, 2,2-dimethyl tetradecyl vinyl ether, sec-butyl vinyl ether, n-amyl vinyl ether, 1-methyl-
2-methylpropyl vinyl ether, 1-methyl-2,
2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, diisopropylmethyl vinyl ether, 1,3-dimethylbutyl vinyl ether, 2,2-dimethylbutyl vinyl ether, neopentyl vinyl ether, 1-methylheptyl vinyl ether, n-nonyl vinyl ether, 1-methyl -4-ethyloctyl vinyl ether, n-tetradecyl vinyl ether, n-hexadecyl vinyl ether, n-octadecyl vinyl ether, n-dodecyl vinyl ether, n-heptadecyl vinyl ether, n-tridecyl vinyl ether, n
-Pentyl vinyl ether and the like.

The above compounds may be used alone or in combination with 2
Used in combination of two or more species. Examples of the ethylene derivative having a halogen or a cyano group include monomers represented by the following formula.

[0096]

[Chemical formula 63]

In the above formula, one or both of G and J is F, Cl, Br, I or -C≡N, and the other is H.
Or CH ₃ . Specific examples of such a monomer include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, and vinylidene fluoride.

The above compounds may be used alone or in combination with 2
Used in combination of two or more species. Furthermore, as the polyfunctional monomer (b-4), the same compounds as those exemplified as the crosslinkable monomer for the rubber latex [B-1 ′] can be exemplified. In the monomer or monomer mixture used in the graft polymerization, the acrylate or methacrylate monomer having an alicyclic skeleton is 20 to
100% by weight, the monovinyl aromatic monomer (b-2) is 0 to 70% by weight, preferably 0 to 55% by weight, and other monovinyl type monomers (b-3) copolymerizable with these are 0 to
70% by weight, preferably 0-50% by weight, and the polyfunctional monomer (b-4) is 0-3% by weight, preferably 0-2.
It can account for weight percent.

As a method of graft polymerization, for example, an aqueous dispersion of latex [B-1 '] of styrene-butadiene rubber is mixed with the above-mentioned monomer or monomer mixture [B-
2 '] and a polymerization initiator can be preferably used. Aqueous dispersions of styrene / butadiene rubber latex [B-1 ′] are disclosed in, for example, JP-A-51-
It can be obtained by the method disclosed in Japanese Patent No. 62890. In the case of graft polymerization, it is usually preferable to use persulfate, organic peroxide, etc. as the polymerization initiator. Examples of such a polymerization initiator include ammonium persulfate,
Examples thereof include potassium persulfate and benzoyl peroxide-dimethylaniline type. Further, it is preferable to use a surfactant in order to stabilize the reaction system, and for example, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium oleate and the like can be used.

The reaction temperature can be appropriately selected within the range of 0 ° C to 150 ° C. Further, in order to control the graft chain length as necessary, thiols such as tert-butyl mercaptan, n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, lauryl mercaptan and p-toluene thiol; carbon tetrabromide Halogenated hydrocarbons such as; trisubstituted aromatic hydrocarbons such as trinitrotoluene; acrolein such as acrolein oxime; metal halides such as iron chloride and copper chloride; chain transfer agents such as organic metals such as diethylzinc Can be added to the polymerization system.

Next, the second manufacturing method for manufacturing the core-shell elastomer will be described. In the second manufacturing method, [B
-1] Core component consisting of styrene-butanediene rubber having styrene unit of 50% by weight or less 40 to 85 parts by weight and [B-2 ''] (b-2) monovinyl aromatic monomer 20 to 80% by weight , (B-3) 20 to 80% by weight of another monovinyl-based monomer copolymerizable therewith and (b
-4) Polyfunctional Monomer A core / shell elastomer comprising 15 to 60 parts by weight of a shell component comprising a copolymer comprising a monomer mixture comprising 0 to 3% by weight as a constituent component is prepared. In this elastomer powder, the total of the core component and the shell component is 100 parts by weight.

The above-mentioned core-shell elastomer is seeded with styrene-butadiene rubber particles according to a seed polymerization method known per se, and the seeds (b-2) and (b) are added thereto.
It can be manufactured by emulsion-polymerizing the monomer mixture of -3) and (b-4). 50 styrene units
As the styrene-butadiene rubber [B-1] in an amount of not more than wt%, one having the same composition as the rubber latex [B-1 '] exemplified in the first production method is used. In addition, as the monovinyl aromatic monomer, other monovinyl monomers and polyfunctional monomers copolymerizable therewith,
The same thing as illustrated about the manufacturing method can be illustrated here.

In the monomer mixture for forming the shell component, the monovinyl aromatic monomer is 20 to 80% by weight, preferably 30 to 70% by weight, and the other monovinyl monomers are 20 to 80% by weight. % By weight, preferably 30 to 70% by weight and 0 to 3% by weight of polyfunctional monomers, preferably 0.
~ 2% by weight. In the second production method, [B-
2 ″ ′] at least one acrylate or methacrylate monomer having an alicyclic skeleton selected from the group consisting of the compounds represented by the above formulas [III], [IV] and [V] 5 to 100 weight Parts, preferably 7 to 50 parts by weight, are graft polymerized.

As the compounds represented by the formulas [III], [IV] and [V], the same compounds as those exemplified in the first production method can be mentioned, and the graft polymerization in the first production method can also be mentioned as the graft polymerization. It can be done in the same way as legal. Thus, according to the present invention, the core-shell elastomer used in the present invention is provided by the above manufacturing method.

The core-shell elastomer has an average primary particle diameter of 100 to 300 nm, preferably 150 to 250 nm. The refractive index n _D of the core-shell elastomer is preferably 1.52 to 1.
56, and more preferably 1.525 to 1.555.

Next, the other component [A] constituting the polymer composition of the present invention will be described. The cyclic olefin polymer has the following [A-1], [A-2] and [A-
It is a polymer specified in 3]. [A-1] Copolymerizing (i) at least one α-olefin having 2 or more carbon atoms with (ii) at least one cyclic olefin represented by the following formula [I] or [II]: A cyclic olefin random copolymer obtained by [A-2] represented by the following formula [I] or [II],
A ring-opening polymer of at least one cyclic olefin [A-3] represented by the following formula [I] or [II],
A cyclic olefin polymer selected from the group consisting of hydrogenated products of ring-opening polymers of at least one cyclic olefin, which has an intrinsic viscosity [η] in decalin at 135 ° C. of 0.0.
5 to 5.0 dl / g, a glass transition temperature (Tg) measured by DSC is 70 ° C. or higher, and a refractive index n _D measured at 25 ° C. is 1.500 to 1.650. Coalescing.

[0107]

[Chemical 64]

(In the formula [I], u is 0 or 1, and v
Is 0 or a positive integer, w is 0 or 1, and R
^{61 to} R ⁷⁸ and R ^a1 and R ^b1 are each independently
A hydrogen atom, a halogen atom or a hydrocarbon group, R ⁷⁵
To R ⁷⁸ may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and R ⁷⁵ and R ⁷⁶ are each represented by Alternatively, R ⁷⁷ and R ⁷⁸ may form an alkylidene group).

[0109]

[Chemical 65]

(In the formula [II], x and d are 0 or 1
Is an integer greater than or equal to y and z is 0, 1 or 2.
R⁸¹~ R⁹⁹Are independently hydrogen atom and halogen atom
Child, aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic carbonization
A hydrogen group or an alkoxy group, R⁸⁹Or R⁹⁰Concludes
A carbon atom and a R⁸³The carbon atom to which
Or R⁹¹The carbon atom to which is bound is directly or
Even if it is bonded through an alkylene group having 1 to 3 elementary atoms
Well, when y = z = 0, R⁸⁵And R⁸²Or R ⁸⁵When
R⁹⁹And are bonded to each other to form a monocyclic or polycyclic aromatic ring.
May be made). In the above formulas [I] and [II],
The definition of each symbol is as defined in the above formulas [III] and [IV].
It can be understood concretely from the concrete examples of the symbols.

Cyclic olefin random copolymer [A-
Examples of the (i) α-olefin having 2 or more carbon atoms used in the copolymerization of 1] include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 4
-Methyl-1-pentene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene,
2 to 2 carbon atoms such as 1-octadecene and 1-eicosene
0 α-olefins. You may use these in combination of 2 or more types. Of these, ethylene is particularly preferably used.

Specific examples of the cyclic olefin represented by the above formula [I] or [II] include bicyclo-2-heptene derivative (bicyclohept-2-ene derivative), tricyclo-3-decene derivative, Tricyclo-
3-undecene derivative, tetracyclo-3-dodecene derivative, pentacyclo-4-pentadecene derivative, pentacyclopentadecadiene derivative, pentacyclo-3-pentadecene derivative, pentacyclo-4-hexadecene derivative, pentacyclo-3-hexadecene derivative, hexacyclo-4 -Heptadecene derivative, heptacyclo-5-
Eicosene derivative, heptacyclo-4-eicosene derivative, heptacyclo-5-heneicosene derivative, octacyclo-5-docosene derivative, nonacyclo-5-pentacosene derivative, nonacyclo-6-hexacosene derivative,
Cyclopentadiene-acenaphthylene adduct, 1,4-
Examples thereof include methano-1,4,4a, 9a-tetrahydrofluorene derivative and 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene derivative.

In the following, the above formula [I] or [I
Specific examples of the cyclic olefin represented by [I] are shown below.

[0114]

[Chemical formula 66]

[0115]

[Chemical formula 67]

[0116]

[Chemical 68]

[0117]

[Chemical 69]

[0118]

[Chemical 70]

[0119]

[Chemical 71]

[0120]

[Chemical 72]

[0121]

[Chemical formula 73]

[0122]

[Chemical 74]

[0123]

[Chemical 75]

[0124]

[Chemical 76]

[0125]

[Chemical 77]

[0126]

[Chemical 78]

[0127]

[Chemical 79]

[0128]

[Chemical 80]

[0129]

[Chemical 81]

[0130]

[Chemical formula 82]

[0131]

[Chemical 83]

[0132]

[Chemical 84]

[0133]

[Chemical 85]

[0134]

[Chemical 86]

General formula [I] or [II] as described above
The cyclic olefin represented by can be produced by subjecting cyclopentadiene and olefins having a corresponding structure to a Diels-Alder reaction.

The structural unit derived from the cyclic olefin represented by the above formula [I] or [II] is a cyclic olefin random copolymer having a repeating structure represented by the following formula [I '] or [II']. It is considered to form a unit.

[0137]

[Chemical 87]

(In the formula [I ′], u, v, w and R ⁶¹ to
R ⁷⁸ and R ^a1 and R ^b1 are the same as defined in the above formula [I]. )

[0139]

[Chemical 88]

(In the formula [II '], y, z, x, d and R ^{81 to} R ⁹⁹ are the same as defined in the above formula [II].) These cyclic olefins may be used alone or in the form of 2
A combination of two or more species can be used.

The cyclic olefin random copolymer [A-1] used in the present invention includes (i) at least one α-olefin having 2 or more carbon atoms, and (ii)
A catalyst (a) formed from a soluble vanadium compound and an organoaluminum compound (A) or at least one cyclic olefin represented by the above formula [I] or [II], as described below. By copolymerization in the presence of a metallocene compound of a transition metal selected from Group IVB or lanthanides and an organoaluminum oxy compound, and optionally a catalyst (b) formed with an organoaluminum compound (B). It can be manufactured.

The soluble vanadium compound forming the catalyst (a) is specifically represented by the following general formula. VO (OR) _a X _b or V (OR) _c X _d where R is a hydrocarbon group, and a, b, c, d are 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦, respectively. a + b ≦ 3,0
≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c + d ≦ 4 are satisfied. More specifically, VOCl ₃ , VO (OC ₂ H ₅ ) Cl ₂ , VO
(OC ₂ H ₅ ) ₂ Cl, VO (O-iso-C ₃ H ₇ ) Cl ₂ , V
_{O (O-n-C 4} H 9) Cl 2, VO (OC 2 H 5) 3, VOB
r ₂ , VCl ₄ , VOCl ₂ VO (O-n-C ₄ H ₉ ) ₃ , VOCl ₃ · 2OC ₈ H ₁₇ 7OH
Vanadium compounds such as

These compounds can be used alone or in combination of two or more kinds. The soluble vanadium compound can also be used as an electron donor adduct obtained by contacting an electron donor as shown below. Such electron donors include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, organic acid or inorganic acid esters, ethers, diethers, acid amides,
Examples thereof include oxygen-containing electron donors such as acid anhydrides and alkoxysilanes, and nitrogen-containing electron donors such as ammonias, amines, nitriles, pyridines and isocyanates.

More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol,
Alcohols having 1 to 18 carbon atoms such as cumyl alcohol, isopropyl alcohol, and isopropylbenzyl alcohol, and halogen-containing alcohols having 1 to 18 carbon atoms such as trichloromethanol, trichloroethanol, and trichlorohexanol;

Phenol, cresol, xylenol,
C6-C20 phenols that may have a lower alkyl group such as ethylphenol, propylphenol, nonylphenol, cumylphenol, and naphthol; carbon numbers such as acetone, methylethylketone, methylisobutylketone, acetophenone, benzophenone, and benzoquinone 3 to 15 ketones, acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, and other aldehydes having 2 to 15 carbon atoms;

Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, crotonic acid. Ethyl, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate. , Ethyl benzoate, methyl anisate,
Ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide,
Organic acid esters having 2 to 18 carbon atoms such as ethyl carbonate;

Acetyl chloride, benzoyl chloride,
2 carbon atoms such as toluyl chloride and anisyl chloride
To 15 acid halides; ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether; acids such as acetic anhydride, phthalic anhydride, benzoic anhydride Anhydride: Alkoxysilane such as ethyl silicate, diphenyldimethoxysilane; Acetic acid N, N-dimethylamide, Benzoic acid N, N
-Acid amides such as diethylamide, toluic acid N, N-dimethylamide;

Examples are amines such as trimethylamine, triethylamine, tributylamine, tribenzylamine and tetramethylethylenediamine; nitriles such as acetonitrile, benzonitrile and trinitrile; pyridines such as pyridine, methylpyridine, ethylpyridine and dimethylpyridine. can do.

When preparing an electron donor adduct of a soluble vanadium compound, these electron donors can be used alone or in combination of two or more kinds. The organoaluminum compound (A) that forms the catalyst (a) with the above-mentioned soluble vanadium compound has at least one Al-C bond in the molecule, and for example, the following (a) and (b) It is represented by a formula.

(A) General formula R ¹ _m Al (OR ² ) _n H _p X _q (In the formula, R ¹ and R ² are usually a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. And these may be the same or different, X is a halogen atom,
m is 0 ≦ m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q
Is a number 0 ≦ q <3, and m + n + p + q = 3
(B) General formula M ¹ AlR ¹ (in the formula, M ¹ is Li, Na, K, and R ¹ is the same as the above), and a complex alkyl compound of a Group 1 metal and aluminum. Specific examples of the organoaluminum compound represented by (a) include the following compounds.

(1) General formula R ¹ _m Al (OR ² ) _3-m (In the formula, R ¹ and R ² are the same as above, and m is preferably a number of 1.5 ≦ m <3. (2) General formula R ¹ _m AlX _3-m (wherein R ¹ is the same as above, X is halogen, and m is preferably a number of 0 <m <3) (3) General Formula R ¹ _m AlH _3-m (wherein R ¹ is the same as above, and m is preferably 2 ≦
m <3 is a number) (4) General formula R ¹ _m Al (OR ² ) _n X _q (wherein R ¹ and R ² are the same as defined above, X is a halogen, and 0 <m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, m
+ N + q = 3) More specifically, as the organoaluminum compound (A) represented by (a), the following compounds can be exemplified.

Examples of the organoaluminum compound represented by (1) include trialkylaluminums such as triethylaluminum and tributylaluminum; trialkenylaluminums such as triisopropenylaluminum; dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; Ethyl aluminum sesquiethoxide, butyl aluminum sesquibutoxide and R ¹ _2.5 Al (O
Partially alkoxylated alkylaluminum having an average composition represented by R ² ) _{0.5 and the} like can be mentioned.

Examples of the organoaluminum compound represented by (2) include dialkylaluminum halides such as diethylaluminium chloride, dibutylaluminum chloride and diethylaluminum bromide; alkylaluminum sesquichlorides, butylaluminum sesquibromide and ethylaluminum sesquibromide. Aluminum sesquihalide; partially halogenated alkyl aluminum such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide and the like can be mentioned.

Examples of the organoaluminum compound represented by (3) include dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; and partially hydrogenated alkylaluminums such as ethylaluminum dihydride and propylaluminum dihydride. Can be mentioned.

Examples of the organoaluminum compound represented by (4) include partially aluminum-alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxy chloride, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide.

Further, it may be a compound similar to the compound represented by the above general formula (a), for example, an organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ and (C _{4
H 9) 2 AlOAl (C 4} H 9) 2, (C 2 H 5) 2 AlN (C
_{6 H 5) Al (C 2} H 5) 2, and the like can be exemplified.

Further, as the compound belonging to the above (b),
_{LiAl (C 2 H 5) 4} , LiAl (C 7 H 15) 4 and the like can be exemplified. Of these, alkylaluminum halides, alkylaluminum dihalides, and mixtures thereof are particularly preferable.

Next, the catalyst (b) formed from a metallocene compound of a transition metal selected from Group IVB of the periodic table or a lanthanide and an organoaluminum oxy compound, and optionally an organoaluminum compound (B) will be described. To do.

Examples of the transition metal compound of Group IVB or lanthanide of the periodic table containing such a ligand having a cyclopentadienyl skeleton include compounds represented by the following general formula [XI]. .

ML _X ... [XI] In the above general formula [XI], M is a transition metal selected from Group IVB and lanthanides of the periodic table, and specifically, zirconium, titanium, hafnium, neodymium, samarium. Or yttrium, L is a ligand that coordinates to a transition metal, and at least one L is
L is a ligand having a cyclopentadienyl skeleton, and L other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group. Group, SO ₃ R
(However, R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen.) Or a hydrogen atom, and x is the valence of the transition metal.

Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group. Group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclo Examples thereof include an alkyl-substituted cyclopentadienyl group such as a pentadienyl group and a hexylcyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

Of these ligands which coordinate to a transition metal, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the above general formula [XI] contains two or more groups having a cyclopentadienyl skeleton, the groups having two cyclopentadienyl skeletons are
Alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene,
They may be bonded via a silylene group or a substituted silylene group such as a dimethylsilylene group, a diphenylsilylene group and a methylphenylsilylene group.

Examples of the ligand other than the ligand having a cyclopentadienyl skeleton include the following. Specifically as a hydrocarbon group having 1 to 12 carbon atoms,
Alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and neophyll group It is illustrated. Examples of the alkoxy group include methoxy group, ethoxy group, butoxy group and the like.
A phenoxy group etc. are illustrated as an aryloxy group. Examples of halogen include fluorine, chlorine, bromine, iodine and the like. The ligand represented by SO ₃ R includes a p-toluenesulfonato group, a methanesulfonato group,
Examples thereof include a trifluoromethanesulfonato group.

The compound represented by the general formula [XI] is more specifically represented by the following general formula [XI '] when the valence of the transition metal is 4, for example. R ¹ _a R ² _b R ³ _c R ⁴ _d M ... [XI ′] (In the formula [XI ′], M is zirconium, titanium, hafnium, neodymium, samarium or ytterbium, and R ¹ is a cyclopentadienyl skeleton. R ² , R ³ and R ⁴ are groups having a cyclopentadienyl skeleton, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, halogen atoms, trialkylsilyl groups. , SO ₃ R or a hydrogen atom, a is an integer of 1 or more, and a + b + c +
d = 4. )

In the present invention, a transition metal compound in which one of R ² , R ³ and R ^{4 in} the above formula [XI ′] is a group having a cyclopentadienyl skeleton, for example, R ¹ and R ² are cyclopenta A transition metal compound which is a group having a dienyl skeleton is preferably used. Groups having these cyclopentadienyl skeletons include alkylene groups such as ethylene and propylene, alkylidene groups such as isopropylidene, substituted alkylene groups such as diphenylmethylene, silylene groups or dimethylsilylene, diphenylsilylene, substituted methylphenylsilylene groups and the like. It may be bound via a silylene group or the like. Also, R ³ and R ⁴
Is a group having a cyclopentadienyl skeleton, an alkyl group,
It is a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, SO ₃ R or a hydrogen atom.

Specific examples of transition metal compounds in which M is zirconium will be shown below. Bis (indenyl) zirconium dichloride, bis (indenyl)
Zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato), bis (4,5,
6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride,
Ethylene bis (indenyl) zirconium dichloride,
Ethylene bis (indenyl) zirconium dibromide,
Ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconium bis (methanesulfonate), ethylenebis (indenyl) zirconium bis (p-toluene) Sulfonato), ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonato), ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,

Isopropylidene (cyclopentadienyl
-Fluorenyl) zirconium dichloride, isopropylidene (methylcyclopentadienyl-fluorenyl)
Zirconium dichloride, isopropylidene (cyclopentadienyl-indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl)
Dimethyl zirconium, dimethyl silylene bis (cyclopentadienyl) zirconium dichloride, dimethyl silylene bis (methyl cyclopentadienyl) zirconium dichloride, dimethyl silylene bis (dimethyl cyclopentadienyl) zirconium dichloride, dimethyl silylene bis (trimethyl cyclopentadienyl) ) Zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium bis (trifluoromethanesulfonato), dimethylsilylenebis (4,5,6,7-
Tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylsilylenebis (indenyl) zirconium dichloride,

Bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis ( Cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl) benzyl zirconium monochloride, bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclo Pentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bi (Cyclopentadienyl) dibenzyl zirconium, bis (cyclopentadienyl) zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methane sulfonato),
Bis (cyclopentadienyl) zirconium bis (p-
Toluenesulfonato), bis (cyclopentadienyl)
Zirconium bis (trifluoromethane sulfonate),

Bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethane) Sulfonato), bis (dimethylcyclopentadienyl) dimethyl zirconium, bis (ethylcyclopentadienyl) zirconium dichloride,
Bis (methylethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl)
Zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis ( Methanesulfonato), bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride , Bis (trimethylsilylcyclopentadienyl) zirconium dichloride.

In the above examples of the transition metal compounds, the disubstituted products of the cyclopentadienyl ring include 1,2- and 1,3-substituted products, and the trisubstituted products thereof are 1,2,3- and 1,3. Including 2,4-substituted compounds. The alkyl groups such as propyl and butyl include isomers such as n-, i-, sec-, and tert-.

In the present invention, in the above zirconium compound, a transition metal compound in which the zirconium metal is replaced with titanium metal, hafnium metal, neodymium metal, samarium metal or ytribium metal can also be used.

The organoaluminum oxy compound which forms the catalyst (b) together with the transition metal compound of Group IVB of the periodic table or the lanthanide containing the ligand having the cyclopentadienyl skeleton as described above is a conventionally known aluminum compound. It may be nooxane or a benzene-insoluble organoaluminum oxy compound. Such conventionally known aluminoxane is specifically represented by the following general formula.

[0173]

[Chemical 89]

(Wherein R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group or a butyl group, preferably a methyl group or an ethyl group, particularly preferably a methyl group, and m
Is an integer of 2 or more, preferably 5 to 40. ) Here, this aluminoxane is an alkyloxyaluminum unit represented by the formula (OA1 (R ¹ )) and a formula (OA
alkyloxyaluminum unit represented by l (R ² )) [wherein R ¹ and R ² can be the same hydrocarbon groups as R, and R ¹ and R ² represent different groups]
May be formed from a mixed alkyloxyaluminum unit consisting of

The conventionally known aluminoxane is prepared, for example, by the following method and is usually recovered as a solution of an aromatic hydrocarbon solvent. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to an aromatic hydrocarbon solvent in which is suspended and reacted to recover a solution of the aromatic hydrocarbon solvent. (2) A method in which water (water, ice, or steam) is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran to recover it as a solution of an aromatic hydrocarbon solvent. (3) To an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene or toluene,
A method of reacting an organic tin oxide such as dimethyltin oxide or dibutyltin oxide.

Among these methods, the method (1) is preferably adopted. Specific examples of the organoaluminum compound used when preparing the aluminoxane solution include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, and trisec-. Trialkylaluminums such as butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; dimethylaluminum chloride, diethyl. Aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum chloride Dialkylaluminum halides, such as de diethyl aluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride; dimethyl aluminum methoxide, dialkylaluminum alkoxides such as diethylaluminum ethoxide;
Examples thereof include dialkylaluminum aryloxides such as diethylaluminum phenoxide.

Of these, trialkylaluminum is particularly preferable. Further, as the organoaluminum compound, isoprenylaluminum represented by the following general formula can also be used.

[0178] _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x.) The organic aluminum such as The compounds may be used alone or in combination.

The benzene-insoluble organoaluminum oxy compound used in the present invention is, for example, a method of bringing a solution of aluminoxane into contact with water or an active hydrogen-containing compound, or an organoaluminum compound and water as described above. It can be obtained by a method of contacting.

[0180] In benzene-insoluble organoaluminum oxy-compound used in the present invention, the compound was analyzed by infrared spectroscopy (IR), the absorbance at around 1220 cm ^-1 and (D _1220), the absorbance at around 1260 cm ^-1 (D ₁₂₆₀₎ and the ratio of (D _{12 60} / D ₁₂₂₀₎ is 0.09
Or less, preferably 0.08 or less, particularly preferably 0.4 to
It is desirable that the range is 0.07.

The above benzene-insoluble organoaluminum oxy compound is presumed to have an alkyloxy aluminum unit represented by the following formula.

[0182]

[Chemical 90]

In the formula, R ³ is a hydrocarbon group having 1 to 12 carbon atoms. As such a hydrocarbon group, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
Examples thereof include n-butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, cyclohexyl group and cyclooctyl group. Of these, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.

The benzene-insoluble organoaluminum oxy compound may contain an oxyaluminum unit represented by the following formula in addition to the alkyloxyaluminum unit represented by the above formula.

[0185]

[Chemical Formula 91]

In the formula, R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, a halogen or a hydrogen atom. Further, R ⁴ and R ³ in the above formula represent different groups from each other.

When the benzene-insoluble organoaluminum oxy compound contains an oxyaluminum unit,
An organoaluminumoxy compound having an alkyloxyaluminum unit containing an alkyloxyaluminum unit in a proportion of 30 mol% or more, preferably 50 mol% or more, particularly preferably 70 mol% or more is desirable.

Such a benzene-insoluble organoaluminum oxy compound is an Al that dissolves in benzene at 60 ° C.
The component is 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, and is insoluble or hardly soluble in benzene.

The organoaluminum oxy compound used in the production of the component [A-1] of the present invention may contain a small amount of an organic compound component of a metal other than aluminum. Examples of the organoaluminum compound (B) used as necessary in the catalyst (b) include the organoaluminum compound represented by the following general formula [XII].

R ⁵ _n AlX _3-n ... [XII] (In the formula [XII], R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 1). 3) In the above general formula [XII], R ⁵
Is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, a pentyl group and a hexyl group. Group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

As such an organoaluminum compound, the following compounds are specifically used. Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutyl. Dialkyl aluminum halides such as aluminum chloride and dimethyl aluminum bromide; alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; methyl Aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide; diethylaluminum hydride, and alkyl aluminum hydride such as diisobutyl aluminum hydride.

As the organoaluminum compound (B), a compound represented by the following general formula [XIII] can also be used. During ^{_{R 5 n AlY 3-n ...}} [XIII] ( wherein [XIII], R ⁵ are as defined above, Y is -
OR ₆ group, -OSiR ⁷ ₃ group, -OAlR ⁸ ₂ group, -NR
⁹ ₂ group, —SiR ¹⁰ ₃ group or —N (R ¹¹ ) AlR ¹² ₂ group, n is 1 to 2, and R ⁶ , R ⁷ , R ⁸ and R ¹² are methyl group, ethyl group and isopropyl group. Group, isobutyl group, cyclohexyl group, phenyl group, etc., R ⁹ is hydrogen atom, methyl group, ethyl group, isopropyl group, phenyl group, trimethylsilyl group, etc., R ¹⁰ and R ¹¹ are methyl group, ethyl group, etc. Is. )

As such an organoaluminum compound, the following compounds are specifically used. (I) a compound represented by R ⁵ _n Al (OR ⁶ ) _3-n , such as dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide; and (ii) R ⁵ _n Al (OSiR ⁷ ₃ ) _3- a compound represented by _n ,
For example, Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OS
iMe ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), and the like, (iii) compounds represented by R ⁵ _n Al (OAlR ⁸ ₂ ) _3-n , for example, Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOA.
l (iso-Bu) _{2 and} other compounds represented by (iv) R ⁵ _n Al (NR ⁹ ₂ ) _3-n , such as Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ AlN.
HEtEt ₂ AlN (SiMe ₃ ) ₂ , (iso-Bu) ₂ AlN (SiM
e ₃ ) _{2 and the} like, (v) R ⁵ _n Al (SiR ¹⁰ ₃ ) _3-n , for example, (iso-Bu) ₂ AlSiMe _{3 and the} like, (vi) R ⁵ _n Al (N (R ¹¹ ) A compound represented by AlR ¹² ₂ ) _3-n , such as Et ₂ AlN (Me) AlEt ₂ , (iso
-Bu) ₂ AlN (Et) Al (iso-Bu) _{2 and the} like.

The above general formulas [XII] and [XIII]
Among the organic aluminum compound represented in the general formula ^{_{R 5 3 Al, R 5 n}} Al (OR 6) 3-n, R 5 n Al (OAlR 8 2)
_A preferred example is an organoaluminum compound represented by _3-n , wherein R ⁵ is an isoalkyl group,
Particularly preferably, n = 2. Two or more kinds of these organoaluminum compounds can be mixed and used.

The cyclic olefin ring-opening polymer [A-2] used in the present invention is at least one cyclic olefin ring-opening polymer represented by the above formula [I] or [II].

Such a ring-opening polymer of a cyclic olefin can be prepared by ring-opening polymerization of the cyclic olefin represented by the above formula [I] or [II] alone or in combination. That is, a ring-opening polymer is prepared by subjecting at least one cyclic olefin represented by the above formula [I] or [II] to ring-opening polymerization in the presence of a ring-opening polymerization catalyst.

As the ring-opening polymerization catalyst used here,
For example, a catalyst comprising a halide of a metal such as ruthenium, rhodium, osmium, indium, platinum, molybdenum and tungsten, a nitrate of these metals and an acetylacetone compound of these metals, and a reducing agent such as an alcohol or a tin compound, In addition, a halogen compound of a metal such as titanium, vanadium, zirconium, tungsten and morbutene, a catalyst composed of an acetylacetone compound of these metals and a metal aluminum compound can be mentioned.

When preparing the above ring-opening polymer, other cyclic olefins other than at least one cyclic olefin represented by the above formula [I] or [II] may be used. Other cyclic olefins include cyclobutene, cyclopentene, cyclooctene,
Cyclononene, methylcyclopentene, methylcycloheptene, methylcyclooctene, methylcyclononene,
4 carbon atoms such as methylcyclodecene, ethylcyclopentene, ethylcycloheptene, ethylcyclooctene, ethylcyclononene, dimethylcycloheptene, dimethylcyclooctene, dimethylcyclononene, dimethylcyclodecene, cyclooctadiene, cyclodecadiene
The above monocyclic olefins and 2,3,3a, 7a-
Tetrahydro-4,7-methano-1H-indene, 3a,
5,6,7a-tetrahydro-4,7-methano-1H-indene and the like can be mentioned.

Further, as a molecular weight regulator, propylene,
Alkenes such as 1-butene, 1-pentene, 1-hexene can be used as a copolymerization component. In such a ring-opening polymer, at least a part of the cyclic olefin represented by the above formula [I] is considered to have a structure represented by the following formula [Ia], and the above formula [II] ] It is considered that at least a part of the cyclic olefin represented by the formula has a structure represented by the following formula [II-a].

[0200]

[Chemical Formula 92]

(In the formula [Ia], u, v, w, R ^{61 to} R
⁷⁸ and R ^a1 and R ^b1 have the same meaning as in formula [I].

[0202]

[Chemical formula 93]

(In the formula [II-a], x, y, z, d, R
^{81 to} R ⁹⁹ have the same meanings as in formula [II]) The hydrogenated products [A-3] of the ring-opening polymer of cyclic olefin used in the present invention are all of the above formula [I] or [II].
Is a hydrogenated product of a ring-opening polymer of at least one cyclic olefin represented by:

The hydrogenated product of the ring-opening polymer of cyclic olefin can be obtained by hydrogenating the ring-opening polymer of cyclic olefin prepared as described above. For hydrogenation of the ring-opening polymer, a usual hydrogenation method performed in the presence of a hydrogenation catalyst can be adopted.

As the hydrogenation catalyst used here,
A hydrogenation catalyst such as a heterogeneous catalyst or a homogeneous catalyst generally used for hydrogenating an olefin compound can be used. Specific examples of heterogeneous catalysts include metals such as nickel, palladium and platinum,
And a solid catalyst in which these metals are supported on a carrier such as carbon, silica, diatomaceous earth, alumina and titanium oxide (eg nickel / silica, nickel /
Diatomaceous earth, palladium / carbon, palladium / silica,
Palladium / diatomaceous earth, palladium / alumina, etc.). Examples of homogeneous catalysts are catalysts based on metals of Group VIII of the Periodic Table, and examples of such catalysts include cobalt naphthenate, triethylaluminum, cobalt octenoate / n-butyllithium, An organometallic compound formed from a nickel compound such as nickel acetylacetonate / triethylaluminum or a cobalt compound and a metal of Group I to III of the periodic table can be mentioned, and an Rh compound can also be used.

The hydrogenation reaction using the hydrogenation catalyst as described above can be carried out in either a heterogeneous system or a homogeneous system, depending on the type of the catalyst. The reaction conditions in such a system are usually 0 to 180 ° C., preferably 20 to 100 ° C. under a hydrogen atmosphere at 1 to 150 atm.
Set to a temperature of ℃. The hydrogenation rate under such conditions can be adjusted by appropriately setting conditions such as hydrogen pressure, reaction temperature, reaction time, and catalyst concentration, but the double bond present in the main chain of the polymer Of these,
50% or more, preferably 80% or more, more preferably 90% or more is hydrogenated.

In such a hydrogenated cyclic polymer,
At least a part of the cyclic olefin represented by the above formula [I] is considered to have a structure represented by the following formula [I] -b, and at least a part of the cyclic olefin represented by the above formula [II]. Is considered to have a structure represented by the following formula [II] -b.

[0208]

[Chemical 94]

(Formula [Ib], u, v, w, R ^{61 to} R ⁷⁸
And R ^a1 and R ^b1 have the same meaning as in formula [I].

[0210]

[Chemical 95]

(In the formula [II-b], x, y, z, d, R
^{81 to} R ⁹⁹ have the same meaning as in formula [II])

Next, the cyclic olefin polymer will be described more specifically. The [A-1] cyclic olefin-based random copolymer is α-
The repeating unit derived from the olefin component is usually 35 to
It is desirable to be present in an amount in the range of 90 mol%, preferably 40 to 85 mol%, and the formula [I] or [II]
The repeating unit derived from the cyclic olefin represented by is usually present in an amount in the range of 10 to 65 mol%, preferably 15 to 60 mol%.

The intrinsic viscosity [η] in decalin at 135 ° C. is 0.05 to 5.0 dl / g, preferably 0.15 to 4.5 d.
It is preferably in the range of 1 / g. The glass transition temperature (Tg) measured by DSC is 70 ° C. or higher, and preferably 70 to 250 ° C. 25 ° C
The refractive index n _D measured in _1. is usually 1.500 to 1.650,
It is preferably in the range of 1.510 to 1.600. In the present invention, the refractive index is measured at 25 ° C. using an Abbe refractometer (D line, 589 nm).

The iodine value is preferably 30 or less. [A-2] Ring-opening polymer of cyclic olefin, and [A-
3] The intrinsic viscosity [η] of the hydrogenated product of the ring-opening polymer of cyclic olefin in decalin at 135 ° C. is 0.05 to 5.0 dl /
g, preferably 0.15 to 4.5 dl / g.

Glass transition temperature (T
g) is 70 ° C. or higher, preferably 70 to 250 ° C.
It is desirable that the range is. The refractive index n _D measured at 25 ° C. is usually 1.500 to 1.650, preferably 1.510.
It is preferably in the range of 1.600. Further, the iodine value is preferably 30 or less.

The compounding of such a cyclic olefin polymer with the core / shell elastomer can be carried out, for example, by the following method. (1) A method of melt blending a cyclic olefin polymer and a core / shell elastomer by using an extruder, a kneader, or the like. (2) Cyclic olefin polymer and core / shell elastomer in a suitable solvent (eg, saturated hydrocarbon such as heptane, hexane, decane, cyclohexane; aromatic hydrocarbon such as toluene, benzene, xylene)
Method of dissolving or dispersing in and blending. The compounding ratio of the cyclic olefin polymer [A] and the core / shell elastomer [B] (weight ratio of the former to the latter) is 4
It is desirable that it is 0/60 to 95/5 (the total of both is 100), preferably 60/40 to 90/10.

The cyclic olefin polymer composition of the present invention thus obtained comprises a cyclic olefin polymer and
Since it has a small difference in refractive index from the core / shell elastomer, it is excellent in transparency and has a good balance of transparency, heat resistance and impact strength. Further, a composition is obtained by radically reacting the above cyclic olefin polymer and a core / shell elastomer in the presence of an organic peroxide and, if necessary, a radically polymerizable polyfunctional monomer. May be.

Such a radical reaction is carried out by radically reacting the cyclic olefin polymer and the core / shell elastomer in the presence of an organic peroxide and, if necessary, a radically polymerizable polyfunctional monomer. .

As the organic peroxide used here, ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; 1,1-
Bis (tert-butylperoxy) cyclohexane,
Peroxyketals such as 2,2-bis (tert-butylperoxy) octane; tert-butylhydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroxyperoxide,
Hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide; di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-
Butyl peroxy) hexane, 2,5-diethyl-2,5
-Dialkyl peroxides such as di (tert-butylperoxy) hexyne-3, diacyl peroxides such as lauroyl peroxide and benzoyl peroxide; tert-butyl peroxyacetate, ter
Peroxyesters such as t-butylperoxybenzoate and 2,5-dimethyl-2,5-di (benzoylperoxy) hexane can be mentioned.

Examples of the radical-polymerizable polyfunctional monomer used as necessary include, for example, divinylbenzene, vinyl acrylate, vinyl methacrylate, triaryl isocyanurate, diaryl phthalate, ethylene dimethacrylate trimethylolpropane trimeta. An acrylate etc. can be mentioned.

When a composition is prepared by radically reacting a cyclic olefin polymer and a core / shell elastomer in the presence of an organic peroxide and, if necessary, a radically polymerizable polyfunctional monomer. The composition may be prepared by using one reactor, or a plurality of reactors may be used, in which the cyclic olefin polymer and the core / shell elastomer are reacted in one reactor and the other is reacted. The final composition may be obtained by reacting both in the same manner in a vessel and then blending the both.

In such a radical reaction, the amount of the organic peroxide is usually 0.0 based on 100 parts by weight of the total of the cyclic olefin polymer and the core / shell elastomer.
The radical-polymerizable polyfunctional monomer used in an amount of 1 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and optionally used, is a cyclic olefin-based polymer, a core-shell elastomer. It is usually used in an amount of 0.01 to 15 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight.

When radically reacting the cyclic olefin polymer with the core / shell elastomer, it is desirable to react at a temperature at which the organic peroxide decomposes. In the reaction, each raw material can be mixed and reacted at the same time, but a method of mixing both and then reacting by mixing an organic peroxide and, if necessary, a radically polymerizable polyfunctional monomer is preferable. . The organic peroxide is preferably added in a state where the cyclic olefin polymer and the core / shell elastomer are sufficiently mixed.

To mix the cyclic olefin polymer and the core / shell elastomer, the separately prepared cyclic olefin polymer and core / shell elastomer are melt blended by an extruder or the like. The coalesced and core / shell elastomers are combined with a suitable solvent (eg, saturated hydrocarbon such as heptane, hexane, decane, cyclohexane; toluene, benzene,
A method of sufficiently dissolving or dispersing in aromatic hydrocarbon such as xylene and blending can be employed.

An organic peroxide and, if necessary, a radically polymerizable polyfunctional monomer are added to the mixture of the thus obtained cyclic olefin polymer and the core / shell elastomer, and the mixture is blended. React at the temperature at which the substance decomposes.

Such a radical reaction can be carried out in a state where the mixture of raw materials is melted, or in a state where the mixture of raw materials is dissolved or dispersed in a solvent. When performing a radical reaction in the molten state, a mixing roll, a Banbury mixer, an extruder, a kneader,
Using a kneading device such as a continuous mixer, the mixture of raw materials is melt-mixed and reacted. The radical reaction is carried out at a temperature not lower than the one-minute half-life of the organic peroxide, usually 150 to 300 ° C.
Preferably at a temperature of 170 to 270 ° C., usually 10 seconds to 3
It is desirable to carry out for 0 minutes, preferably for 3 to 10 minutes.

As the solvent used when carrying out the radical reaction in the state of being dissolved or dispersed in the solvent, the same solvent as the solvent used in the solution blending method can be used. The radical reaction is preferably carried out at a temperature not lower than the 10-minute half-life of the organic peroxide, usually at a temperature of 50 to 300 ° C., usually for 10 seconds to 2 hours.

From the reaction product obtained as described above, a composition is obtained by removing the solvent by a method such as distillation. This composition can be used alone or in a blend with another transparent resin.

The cyclic olefin polymer composition thus provided is molded and processed by a known method. For example, single-screw extruder, vented extruder, twin-screw extruder, conical twin-screw extruder, co-kneader, plastifier, mixer, twin-screw conical screw extruder, planetary screw extruder, gear-type extruder. Machine, screwless extruder, etc., extrusion molding, injection molding, blow molding, rotational molding.

A rubber component is added to such a cyclic olefin polymer composition in order to further improve the impact strength of the composition, and a heat stabilizer, a weather stabilizer, an antistatic agent and a slip agent are added. , An antiblocking agent, an antifogging agent, a lubricant, a dye, a pigment, a natural oil, a synthetic oil, a wax and the like can be appropriately added.

For example, as the stabilizer to be added as an optional component, specifically, phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, fatty acid metal salts and fatty acid esters of polyhydric alcohols are preferable. Used. Examples of the phenol-based antioxidant include the following formula A
n-1

[0232]

[Chemical 96]

(Here, R ₁ and R ₂ are each 1 to 1 carbon atoms.
4 is an alkyl group having a straight chain or a side chain, R ₃ is an alkyl group having a straight chain or a side chain having 8 to 20 carbon atoms, or —CH ₂ —CH ₂ —COOX where X is a straight chain having 8 to 20 carbon atoms. An alkyl group having a chain or a side chain. ), A compound represented by the following formula An-2

[0234]

[Chemical 97]

(Here, the definition of R ₁ and R ₂ is defined by the above formula A
n-1 is the same, R ₄ and R ₅ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or

[0236]

[Chemical 98]

The group represented by can be mentioned. )
The compound represented by the above formula An-1 is 2,6-
Di-t-butyl-4-nonylphenol, 2,6-di-t-
Butyl-4-dodecylphenol, 2,6-di-t-butyl-4-hexadecylphenol, 2,6-di-t-butyl-4-octadecylphenol, 2-t-butyl-6
-Isopropyl-4-octadecylphenol, 2,6
-Diisopropyl-4-octadecylphenol, 3-
(4'hydroxy-3 ', 5'-di-t-butylphenyl) -n-dodecyl propionate, 3- (4'-hydroxy-
3 ', 5'-Dit-butylphenyl) propionic acid-hexadecyl, 3- (4'-hydroxy-3', 5'-dit-butylphenyl) -propionic acid-n octadecyl, 3-
(4′-Hydroxy-3′-t-butyl-5′-isopropylphenyl) propionate-n octadecyl, 3-
(4′-hydroxy-3′-t-butyl-3′-methylphenyl) propionic acid-n octadecyl and the like.

As an example of the compound represented by the above formula An-2, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane (registered trademark "Topanol CA") is used. Commercially available) and 4,4′-butylidene bis (6-t-butyl-m-cresol) (registered trademark “Sant
(commercially available as “owhite Powder”).
anol CA "is preferred. Other phenolic antioxidants include tetrakis [methylene-3 (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate]
Methane, β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2′-
Oxamide bis [ethyl-3 (3,5-di-t-butyl-4-hydroxyphenyl)] propionate and the like can be mentioned. As the sulfur-based antioxidant, the following formula An-3

[0239]

[Chemical 99]

(Here, m and n are integers of 1 to 4, and R ₆
And R ₇ is an alkyl group having a straight chain or a side chain having 8 to 20 carbon atoms. ).

Examples of the compound represented by the above formula An-3 include dicaprylthiodipropionate, dilaurylthiodipropionate, dipalmitylthiodipropionate and distearylthiodipropionate. Other sulfur-based antioxidants include 4,4'-thiobis (6
-T-butyl) -3-methylphenol, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5
-Di-t-butylanilino) -1,3,5-triazine and the like can be mentioned. Further, as the phosphorus-based antioxidant, the following formula An-4 is used.

[0242]

[Chemical 100]

(Where X is an oxygen atom or a lone pair of electrons, R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom,
The compound represented by a C1-C20 alkyl group or a mono- or di (C1-C20 alkyl) substituted phenyl can be mentioned.

Examples of the phosphorus compound represented by the above formula An-4 include phosphoric acid and tris (nonylphenyl) phosphite. As fatty acid metal salt,
For example, zinc stearate, calcium stearate, 1
2-hydroxystearate calcium etc. can be mentioned. Examples of fatty acid esters of polyhydric alcohols include glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate and the like. .

These may be blended alone or may be blended in combination, for example, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and stearin. Examples thereof include a combination with zinc acid and glycerin monostearate.

In particular, it is preferable to use a phenolic antioxidant and a fatty acid ester of a polyhydric alcohol in combination, and the fatty acid ester of the polyhydric alcohol is 3
It is preferable that the polyhydric alcohol fatty acid in which a part of the alcoholic hydroxyl groups of the polyhydric alcohol having a valency or higher is esterified is used. As such fatty acid ester of polyhydric alcohol, specifically, glycerin monostearate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate, glycerin fatty acid ester such as glycerin dilaurate, Fatty acid esters of pentaerythritol such as pentaerythritol monostearate, pentaerythritol monolaurate, pentaerythritol dilaurate, pentaerythritol distearate, pentaerythritol tristearate are used. Such a phenolic antioxidant is used in an amount of 0 to 5 parts by weight, preferably 0 to 2 parts by weight, and more preferably 0 to 1 part by weight, based on 100 parts by weight of the cyclic olefin polymer composition. . The sulfur antioxidant is used in an amount of 0 to 5 parts by weight, preferably 0 to 2 parts by weight, more preferably 0 to 1 part by weight, based on 100 parts by weight of the cyclic olefin polymer composition. The phosphorus-based antioxidant is used in an amount of 0 to 5 parts by weight, preferably 0.01 to 2 parts by weight, and more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the cyclic olefin polymer composition.

The fatty acid metal salt is 0 to 5 parts by weight, preferably 0 to 100 parts by weight of the cyclic olefin polymer composition.
˜2 parts by weight, more preferably 0 to 1 part by weight. The fatty acid ester of polyhydric alcohol is used in an amount of 0 to 5 parts by weight, preferably 0 to 2 parts by weight, based on 100 parts by weight of the cyclic olefin polymer composition.

If necessary, silica, diatomaceous earth, alumina, titanium oxide, cycloolefin copolymer composition,
Magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate,
Barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, polycarbon number 2 Fillers such as the above α-olefin fibers, polypropylene fibers, polyester fibers, and polyamide fibers can also be blended.

[0249]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples. In the present invention, various physical property values were measured and evaluated as follows.

Various physical properties of core / shell elastomer (1) Copolymerization component constituting core / shell elastomer
The amount was calculated from the charged amount and the yield. (2) Refractive index Abbe's refractometer (D line, 589 nm) is used at 25 ° C.
It was measured at. (3) Average particle size of primary particles of core / shell elastomato Laser diffractometry particle size distribution measuring device (manufactured by Shimadzu Corporation, SA
LD-2000).

Various Physical Properties of Cyclic Olefin Copolymer (1) Intrinsic Viscosity ([η]) It was measured at 135 ° C. in a decalin solution using an Ubbelohde viscometer. (2) Glass transition point (Tg) Using a DSC-220C manufactured by Seiko Instruments Inc., the glass transition point was measured at a temperature rising rate of 10 ° C./min in an N ₂ atmosphere. (3) Monomer composition ratio in polymer Measured by ¹³ C-NMR. (4) Iodine value Measured by the iodine monochloride method according to JIS K3331.

Core / shell elastomer / cyclic olef
Measurement and evaluation methods of various physical properties of the vinyl copolymer composition (1) Preparation method of the composition A predetermined amount of the core / shell elastomer and the cyclic olefin copolymer were mixed well in a plastic bag under a nitrogen atmosphere, The atmosphere was replaced with nitrogen for 2 hours. The mixture is twin-screw extruder
(W100 type), melt-blended at a cylinder maximum temperature of 230 ° C. and a residence time of 1 minute, and pelletized with a pelletizer. (2) Preparation of test piece Using an injection molding machine IS50EPN manufactured by Toshiba Machine Co., Ltd. and a predetermined test piece mold, molding was performed under the following molding conditions.
The test piece was subjected to measurement after being left at room temperature for 48 hours after molding. Molding conditions: Cylinder temperature: 260 ° C, mold temperature: 60 ° C, injection pressure primary / secondary = 1000 / 800kg / cm ²

(3) Haze value According to ASTM D-1003, using a digital turbidity (cloudiness) meter NDH-20D manufactured by Nippon Denshoku Industries Co., Ltd., a thickness of 2
mm press sheet was measured as a sample.
(4) Izod impact strength Measured according to ASTM D256. Test piece shape: 5/2 × 1/8 × 1/2 ^t inch (with notch) Test temperature: 23 ° C. (5) Heat distortion temperature (HDT) It was performed according to ASTM D648. Test piece shape: 5 x 1/4 x 1/2 ^t inch Load: 264 psi

Production Example The core-shell elastomer can be remarkably improved in impact strength by being added to the above-mentioned cyclic olefin copolymer without significantly impairing the excellent transparency of the cyclic olefin copolymer. it can.

[Synthesis Example of Cyclic Olefin Copolymer I (hereinafter referred to as Copolymer I)] A 1 liter-stainless steel autoclave charged with 258 ml of cyclohexane was used.
Norbornene (hereinafter sometimes abbreviated as [NB]) (118 g) was added at room temperature under a nitrogen stream, and the mixture was stirred for 5 minutes. Furthermore, triisobutylaluminum was added so that the concentration in the system would be 1.0 mmol / liter. Subsequently, ethylene was circulated at normal pressure while stirring to create an ethylene atmosphere in the system. The internal temperature of the autoclave was maintained at 70 ° C., and ethylene was applied so that the internal pressure was 6 kg / cm ^{2 as a} gauge pressure. After stirring for 10 minutes, 5.0 ml of a toluene solution containing isopropylidene (cyclopentadienyl) (indenyl) zirconium dichloride and methylalumoxane prepared in advance was added to the system to carry out the copolymerization reaction of ethylene and NB. Let it start.
The catalyst concentration at this time was 0.015 mmol / liter for isopropylidene (cyclopentadienyl) (indenyl) zirconium dichloride and 7.5 mmol / liter for methylalumoxane, based on the total system.

During polymerization, ethylene was continuously fed into the system so that the temperature was 70 ° C. and the internal pressure was 6 kg / gauge pressure.
It was held at cm ² . After 60 minutes, the polymerization reaction was stopped by adding isopropyl alcohol. After depressurization, the polymer solution was taken out and concentrated hydrochloric acid 5m to 1 liter of water
The mixture was brought into contact with the aqueous solution containing 1 at a ratio of 1: 1 using a homomixer under vigorous stirring to transfer the catalyst residue to the aqueous phase.
After the contact mixed solution was allowed to stand, the aqueous phase was separated and removed, and further washed twice with distilled water to purify and separate the polymerization liquid phase.

Next, the purified and separated polymerization liquid is contacted with 3 times amount of acetone under strong stirring to precipitate a copolymer, and then a solid portion (copolymer) is collected by filtration and washed sufficiently with acetone. did. Further, in order to extract unreacted NB existing in the polymer, this solid part was put into acetone at 40 g / liter, and then extraction operation was performed at 60 ° C. for 2 hours. After the extraction treatment, the solid part is collected by filtration, and under nitrogen flow, 130 ° C., 350 mmHg
And dried for 12 hours. The polymer yield was 36 g.

The ethylene-norbornene copolymer (copolymer I) thus obtained has an intrinsic viscosity [η]; 0.60 dl / g, Tg; 148 ° C.
The B content was 49.0 mol%. Furthermore, the iodine value of the obtained copolymer was 0.2. The refractive index (n _D ) of the copolymer I was 1.532.

[0259] using a vanadium catalyst [cyclic olefin copolymer II (hereinafter referred to as copolymer II) Synthesis example], and ethylene, tetracyclo [4.4.0.1 ^{2, 5} .1 ^{7
, 10} ] -3-Dodecene (hereinafter sometimes abbreviated as “TCD”) was continuously copolymerized by the following method.

A cyclohexane solution of TCD was continuously supplied from the upper portion of a 1-liter glass-made polymerization vessel equipped with a stirring blade so that the concentration of TCD supplied in the polymerization vessel was 40 g / liter. In addition, a cyclohexane solution of VO (O.ethyl) Cl ₂ 'as a catalyst was added from the upper part of the polymerization vessel so as to adjust the vanadium concentration in the polymerization vessel to 0.5 mmol / liter of ethyl aluminum sesquichloride (Al (C ₂ A cyclohexane solution of H ₅ ) _1,5 Cl _1,5 ) was continuously fed into each of the polymerization reactors so that the aluminum concentration in the polymerization reactor was 4.0 mmol / liter. In addition, ethylene was added to the polymerization system by using a bubbling tube.
6.0 liters / hour, nitrogen 35.0 liters / hour,
Hydrogen was supplied in an amount of 1.0 liter / hour.

A copolymerization reaction was carried out while maintaining the polymerization system in which a heating medium was circulated in a jacket attached outside the polymerization vessel at 10 ° C. The polymerization solution of the copolymer produced by the above-mentioned copolymerization reaction is continuously conducted from the upper part of the polymerization vessel so that the polymerization solution in the polymerization vessel is always 1 liter (that is, the average residence time is 0.5 hours). I pulled it out. A cyclohexane / isopropyl alcohol (1: 1) mixed solution was added to the extracted polymerization solution to stop the polymerization reaction. Then, an aqueous solution prepared by adding 5 ml of concentrated hydrochloric acid to 1 liter of water was mixed with the polymerization solution at a ratio of 1 :. The catalyst residue was brought into contact with the homomixer at a ratio of 1 under strong stirring to transfer the catalyst residue to the aqueous phase.
After leaving this contact mixture still, after separating and removing the aqueous phase,
Further, it was washed twice with distilled water to purify and separate the polymerization liquid phase.

Then, the purified and separated polymerization liquid was contacted with 3 times amount of acetone under strong stirring to precipitate a copolymer,
The solid portion was collected by filtration and thoroughly washed with acetone. Furthermore, in order to extract the unreacted TCD existing in the copolymer, this solid part was put into acetone so that the concentration became 40 g / liter, and then extraction operation was performed at 60 ° C. for 2 hours. After the extraction treatment, the solid part was collected by filtration and dried at 130 ° C. and 350 mmHg for 12 hours under a nitrogen flow.

Ethylene.T obtained as described above
The CD copolymer (hereinafter referred to as copolymer II) has an intrinsic viscosity [η]; 0.65 dl / g, Tg; 82 ° C., T
CD content is 28.1 mol% and iodine value is 0.1 g
It was iodine / 100 g. The refractive index (n _D ) of the copolymer II was 1.538.

Example 1 First, an example in which the core / shell elastomer which is the component [B] of the present invention is synthesized by the first production method will be described. (1) Raw materials were charged into an autoclave equipped with a stirrer, which had been sufficiently replaced with nitrogen, so as to have the following composition, and reacted at 50 ° C. for 15 hours while stirring. Butadiene 75 parts Styrene 25 parts Polyethylene glycol dimethacrylate 1.0 parts Diisopropylbenzene hydroperoxide 0.2 parts Sodium formaldehyde sulfoxylate 0.2 parts Ethylenediaminetetraacetic acid (EDTA) disodium salt 0.006 parts Ferrous sulfate heptahydrate 0.002 parts Sodium pyrophosphate 0.3 parts Sodium oleate 2.0 parts Ion-exchanged water 200 parts Conversion of rubber 98%, average particle diameter 80nm (hereinafter referred to as latex A) )was gotten.

(2) The obtained latex was charged into an autoclave with a stirrer, which was sufficiently nitrogen-substituted as described above, so as to have the following composition, and polymerized at 50 ° C. for 50 hours. Latex A (as solid content) 8 parts Styrene 23 parts Butadiene 69 parts Diisopropylbenzene hydroperoxide 0.1 parts Sodium formaldehyde sulfoxylate 0.1 parts EDTA ・ 2 sodium salt 0.004 parts Ferrous sulfate ・ 7 water Salt 0.001 part Sodium pyrophosphate 0.3 part Sodium oleate 0.5 part Ion-exchanged water 150 parts

Every 10 hours after the start of the reaction, 0.1 part of diisopropylbenzene hydroperoxide and 0.1 part of sodium formaldehyde sulfoxylate were added. On the other hand, 1.5 parts of sodium oleate was made into a 1% aqueous solution and continuously added over 40 hours. The final conversion was about 95%, and the obtained rubber latex (hereinafter referred to as latex B) had an average particle diameter of 170 nm. When latex B was observed with an electron microscope,
There were no latex particles with a particle size below 100 nm and above 300 nm. As described above, styrene-butadiene rubber latex (= 25% by weight of styrene and 75% by weight of butadiene)
The core component) was synthesized (latex B).

(3) While displacing nitrogen, raw materials were charged into a glass container so as to have the following composition and stirred at 70 ° C. Latex B (as solid content) 70 parts EDTA. Disodium salt 0.008 part ferrous sulfate heptahydrate 0.002 part sodium formaldehyde sulfoxylate 0.2 part ion-exchanged water 250 parts To the mixture, The composition was continuously added over 2 hours. Tetracyclododecyl acrylate (TD-A) 15 parts

[0268]

[Chemical 101]

Polyethylene glycol dimethacrylate 1.0 part Diisopropylbenzene hydroperoxide 0.1 part When the stirring was continued for another 1 hour after the addition was completed, the conversion was 98%. Furthermore, the following composition was continuously added over 2 hours. Tetracyclododecyl acrylate (TD-A) 15 parts Diisopropylbenzene hydroperoxide 0.2 part After the addition was completed, diisopropylbenzene hydroperoxide 0.1 part was added, and the mixture was further stirred for 3 hours. The conversion was 98%. The average particle size of the obtained latex (hereinafter referred to as latex C) was 180 nm. As a result of observing the latex C with an electron microscope, 1
There were no latex particles with particle sizes below 00 nm and above 300 nm. On the other hand, it was confirmed by the following method whether or not the aggregation and enlargement occurred during the polymerization. That is, when the number of particles in the latex does not change, the diameter (d) of the latex particles after the grout polymerization is expressed by the following formula with respect to the diameter (d ₀ ) of the rubber particles:

[0270]

[Equation 1]

(In the formula, M ₀ is the number of charged rubber parts, and M is the number of charged rubber parts + the number of graft monomer parts (= 100 parts)). When a rubber latex having an average particle diameter of 170 nm is used, the calculated average particle diameter of the latex is 190 nm. From the results of the average particle size obtained and the average particle size calculated from the formula, except that the graft phase covers the periphery of the rubber particles and the particles naturally grow, aggregation during graft polymerization hardly occurs. I understand. The resulting latex C contains 2,6- as a stabilizer.
1 part of ditertiarybutyl-p-cresol (BHT),
Dilauryl thiodipropionate (0.5 part) was added, and the mixture was thoroughly stirred and then an aqueous hydrochloric acid solution was added to coagulate, dehydrate and dry. The composition of the core / shell elastomer thus obtained is shown in Table 1. Further, Table 1 also shows the physical property values of the composition obtained by adding 20 wt% of the core-shell elastomer to the cyclic olefin copolymer (Copolymer I).

Examples 2 and 3 Using the latex B (= the core component) shown in Example 1, the core-shell elastomers shown in Table 1 were synthesized in the same manner as in Example 1. In addition, in Example 2, styrene and methyl methacrylate (MMA) were added in addition to TD-A when the shell portion was formed. The results are shown in Table 1.

Example 4 Using the latex B shown in Example 1, norbornene acrylate was used when forming the shell part.

[0274]

[Chemical 102]

The core-shell elastomers shown in Table 1 were synthesized in the same manner as in Example 1 by adding and styrene. The results are shown in Table 1.

Example 5 Using the latex B shown in Example 1, cyclohexylmethacrylate was used when forming the shell part.

[0277]

[Chemical 103]

The core-shell blastomer shown in Table 1 was synthesized in the same manner as in Example 1 by adding styrene and styrene. The results are shown in Table 1.

Comparative Example 1 Using the latex B synthesized in Example 1, a core / shell elastomer was synthesized by the following method. While substituting nitrogen, raw materials were charged into a glass container so as to have the following composition and stirred at 70 ° C. Latex B (as solid content) 70 parts EDTA. Disodium salt 0.008 part ferrous sulfate heptahydrate 0.002 part sodium formaldehyde sulfoxylate 0.2 part ion-exchanged water 250 parts To the mixture, The composition was continuously added over 2 hours. Methyl methacrylate (MMA) 17 parts Polyethylene glycol dimethacrylate 1.0 part Diisopropylbenzene hydroperoxide 0.1 part

When the stirring was continued for another hour after the addition was completed, the conversion was 98%. Furthermore, the following composition was continuously added over 2 hours. Styrene 13 parts Diisopropylbenzene hydroperoxide 0.2 parts

After the completion of the addition, 0.1 part of diisopropylbenzene hydroperoxide was added, and stirring was continued for further 3 hours. As a result, the conversion rate was 98%, and the average particle diameter of the obtained latex (hereinafter referred to as latex D). Is 18
It was 0 nm. As a result of observing the latex D with an electron microscope, latex particles having a particle diameter of 100 nm or less and 300 nm or more were not present.

In the same manner as in Example 1, 1 part of 2,6-ditertiarybutyl-p-cresol (BHT) and 0.5 part of dilaurylthiodipropionate as stabilizers were added to the obtained latex D, and the mixture was thoroughly stirred. After that, add aqueous hydrochloric acid,
Coagulation, dehydration and drying were performed. The results are shown in Table 1. Since the core / shell elastomer obtained in Comparative Example 1 does not have the acrylate or methacrylate component containing the alicyclic skeleton, which is the feature of the present invention, as a constituent component in the shell phase, Since the compatibility was not good, the results were inferior in transparency and Izod impact strength as compared with Examples 1-5.

Comparative Example 2 When synthesizing the latexes A and B of Example 1, the supply weight ratio of styrene and butadiene was 25:75 to 60: 4.
The core-shell elastomers shown in Table 1 were synthesized in the same manner as in Example 1 except that the content was changed to 0. The results are shown in Table 1. In Comparative Example 2, since the styrene / butadiene ratio of the core component deviates from the preferable range, it can be seen that the transparency and impact strength of the composition with the cyclic olefin copolymer are lowered.

Comparative Examples 3 and 4 The core-shell elastomers shown in Table 1 were synthesized in the same manner as in Example 1 by changing the kinds and supply amounts of the monomers constituting the core part and the shell part. The obtained results are shown in Table 1. In Comparative Example 3, the impact strength of the composition was not improved because the weight of the rubber portion of the core was as small as 30 parts. Further, in Comparative Example 4, the average particle size of the primary particles of the core / shell elastomer is larger than the range of the present invention, so the impact strength of the composition is improved, but the transparency is lowered (H
A large aze value).

In Examples 6 and 7 below, a method (second production method) for modifying a normal MBS resin with a (meth) acrylate having an alicyclic skeleton will be described. Example 6 An attempt was made to further modify the latex D (MBS-based resin) obtained in Comparative Example 1 with TD-A. That is, 10 parts by weight of TD-A and 0.3 part of diisopropyl hydroperoxide were continuously added to an aqueous latex solution containing 100 parts by weight of the solid content of latex D for 3 hours and reacted at 70 ° C. When stirring was continued for further 3 hours, the conversion rate of TD-A was 99%. The obtained results are shown in Table 1.

Example 7 The same operation as in Example 6 was carried out except that 10 parts by weight of TD-A in Example 6 was used and 9 parts by weight of NB-A was used. The obtained results are shown in Table 1.

Example 8 and Comparative Examples 5 and 6 Comparative Examples 5 and 6 are plain physical properties of the cyclic olefin copolymers (Copolymers I and II) when the core / shell elastomer was not added. Further, Example 8 is an example in which the core-shell elastomer of Example 1 was added to the copolymer II.

[0288]

[Table 1]

[0289]

Industrial Applicability The present invention provides a composition having improved impact resistance and a core-shell elastomer used for the composition without significantly impairing the original transparency of the cyclic olefin polymer.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 45/00 LKB 51/04 LKY (72) Inventor Masayuki Okabe Waki Roku, Waki-cho, Yamaguchi Prefecture Chome 1-2 Mitsui Petrochemical Industry Co., Ltd. (72) Masahiro Kishine 6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Co., Ltd.

Claims (8)

[Claims] 1. [A], [A-1] (i) at least one kind of an α-olefin having 2 or more carbon atoms
And (ii) the following formula [I] or [II](In the formula [I], u is 0 or 1, and v is 0 or positive.
Is an integer, w is 0 or 1, and R⁶¹~ R⁷⁸Nara
Bini R^a1And R^b1Are each independently a hydrogen atom,
Rogen atom or hydrocarbon group, R⁷⁵~ R⁷⁸Are mutual
May be bonded to each other to form a monocycle or polycycle, or
The monocycle or polycycle may have a double bond,
R⁷⁵And R⁷⁶Or with or R⁷⁷And R⁷⁸And Alkylidene
May form a group). [Chemical 2](In the formula [II], x and d are 0 or an integer of 1 or more.
And y and z are 0, 1 or 2, R⁸¹~ R⁹⁹
Are independently hydrogen atom, halogen atom, and aliphatic carbon
Hydrogen group, alicyclic hydrocarbon group, aromatic hydrocarbon group or
Rukoxy group, R⁸⁹And R⁹⁰Carbon to which is bound
Atom and R⁸³The carbon atom to which is bound or R⁹¹Is joined
The carbon atoms used are either directly or having 1 to 3 carbon atoms.
May be bonded via an alkylene group of
When z = 0, R⁸⁵And R⁸²Or R ⁸⁵And R⁹⁹And each other
May combine to form a monocyclic or polycyclic aromatic ring
I). At least one cyclic olefin represented by
Random Copolymer of Cyclic Olefin Obtained by Copolymerizing
Combined [A-2] represented by the above formula [I] or [II],
A ring-opening polymer of at least one cyclic olefin [A-3] represented by the above formula [I] or [II],
It is a cyclic olefin polymer selected from the group consisting of hydrogenated products of at least one ring-opening polymer of cyclic olefin.
And the intrinsic viscosity [η] in decalin at 135 ° C is 0.0
5 to 5.0 dl / g, measured by DSC
The transition temperature (Tg) is 70 ℃ or higher, measured at 25 ℃
Refractive index n_DA cyclic ole with 1.500 to 1.650
Fin-based polymer and [B], [B-1] Styrene unit of 50% by weight or less
Core component 40-85 composed of a ethylene-butadiene rubber
Parts by weight and [B-2] (b-1) the following general formula [III](In the formula [III], n is 0 or 1, m is 0 or
Is a positive integer, q is 0 or 1, and R is¹~ R¹⁸
And R^aAnd R^bAre each independently a hydrogen atom,
A halogen atom or a hydrocarbon group, R¹⁵~ R¹⁸Are mutual
May be bonded to each other to form a monocycle or polycycle, or
The monocycle or polycycle may have a double bond,
R¹⁵And R¹⁶Or with or R¹⁷And R¹⁸And Alkylidene
May form a group, X¹And X²One of
Is an acryloyloxy group represented by the following formula [X]:
Is a methacryloyloxy group and the other is a hydrogen atom
Alternatively, it is an alkyl group. );(Wherein R is a hydrogen atom or a methyl group)
Compound represented by the following general formula [IV](In the formula [IV], p and l are 0 or 1 or more.
Is an integer, r and s are 0, 1 or 2, and R^{twenty one}
~ R³⁹Are each independently hydrogen atom, halogen atom, fat
Group hydrocarbon groups, aromatic hydrocarbon groups and alkoxy groups
Represents an atom or group selected from the group consisting of²⁹And
And R³⁰The carbon atom to which is bound and R³³Charcoal bound by
Elementary atom or R³¹Is directly with the carbon atom to which is bound
Or bonded through an alkylene group having 1 to 3 carbon atoms
May be present, and when r = s = 0, R³⁵And R³²Or
R³⁵And R³⁹And are bonded to each other to form a monocyclic or polycyclic aromatic
May form a ring, X³And X^FourOne of
Is an acryloyloxy group represented by the above formula [X].
Is a methacryloyloxy group and the other is a hydrogen atom
Alternatively, it is an alkyl group. );
And the following formula [V](In the formula [V], t is 4 or 5, and R is⁴¹~ R⁴³Haso
Each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group.
X^FiveIs an acryloyloxy group represented by the above formula [X]
Si group or methacryloyloxy group)
An alicyclic skeleton selected from the group consisting of
At least one acrylate or methacrylate monomer
20 to 100% by weight, (b-2) 0 to 70% by weight of a monovinyl aromatic monomer (b-3) 0 to 70% by weight of another monovinyl type monomer copolymerizable therewith and (b- 4) Polyfunctional monomer: A monomer or monomer mixture consisting of 0 to 3% by weight is used as a constituent component.
Shell component consisting of (co) polymer 15 to 60 parts by weight
The core component [B-1] and the shell component [B-
2] is 100 parts by weight, and the average primary particle
Since the average diameter is in the range of 100 to 300 nm,
Core and shell elastomers characterized by
And the weight ratio of the component [A] to the component [B] is 40 /
Cyclic ole in the range of 60 to 95/5
Fin-based polymer composition. 2. The [B-2 ′] (b-1) relative to 40 to 85 parts by weight of a latex of a styrene-butadiene rubber in which the [B] component is a [B-1 ′] styrene unit of 50% by weight or less. ) The following general formula [III] (In the formula [III], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸
And R ^a and R ^b are each independently a hydrogen atom,
It is a halogen atom or a carbon-hydrogen group, and R ^{15 to} R ¹⁸ may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond. , R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group, and ^one of X ¹ and X ² is an acryloyloxy group represented by the following formula [X]: Alternatively, it is a methacryloyloxy group, and the other is a hydrogen atom or an alkyl group. ); A compound represented by the formula (wherein R is a hydrogen atom or a methyl group), and is represented by the following general formula [IV]: (In the formula [IV], p and l are 0 or an integer of 1 or more, r and s are 0, 1 or 2, and R ²¹
To R ³⁹ each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, and the carbon to which R ²⁹ and R ³⁰ are bonded. The atom and the carbon atom to which R ³³ is bonded or the carbon atom to which R ³¹ is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and r = s = When 0, R ³⁵ and R ³² or R ³⁵ and R ³⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring, and one of X ³ and X ⁴ is the above formula. It is an acryloyloxy group or a methacryloyloxy group represented by [X], and the other is a hydrogen atom or an alkyl group. ); And a compound represented by the following formula [V]: (In the formula [V], t is 4 or 5, R ^{41 to} R ⁴³ are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, and X ⁵ is an acryloyloxy group represented by the above formula [X]. Or at least 1 of an acrylate or methacrylate monomer having an alicyclic skeleton selected from the group consisting of compounds represented by (methacryloyloxy group)
Species 20 to 100% by weight, (b-2) Monovinyl aromatic monomer 0 to 70% by weight (b-3) Other monovinyl type monomer copolymerizable therewith 0 to 70% by weight and (b -4) Polyfunctional monomer Obtained by graft-polymerizing 15 to 60 parts by weight of a monomer or monomer mixture consisting of 0 to 3% by weight, provided that latex [B-
1 '] and the monomer or monomer mixture [B-2'] is 100 parts by weight, and the average diameter of the primary particles is 10 parts.
The cyclic olefin polymer composition according to claim 1, which is a core-shell elastomer characterized by having a range of 0 to 300 nm. 3. The component [B] comprises 40 to 85 parts by weight of a core component [B-1], which is a styrene-butanediene rubber having a styrene unit content of 50% by weight or less, and [B-
2 ″] (b-2) Monovinyl aromatic monomer 2
0 to 80% by weight (b-3) Monomer consisting of 20 to 80% by weight of other monovinyl-based monomer copolymerizable therewith and (b-4) 0 to 3% by weight of polyfunctional monomer A core composed of 15 to 60 parts by weight of a shell component composed of a copolymer having a mixture as a constituent component.
With respect to 100 parts by weight of the shell elastomer, the total of the core component [B-1] and the shell component [B-2 ″] is 10
0 parts by weight, [B-2 ′ ″] (b-1) the following general formula [III] (In the formula [III], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸
And R ^a and R ^b are each independently a hydrogen atom,
It is a halogen atom or a hydrocarbon group, R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond. , R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group, and ^one of X ¹ and X ² is an acryloyloxy group represented by the following formula [X]: Alternatively, it is a methacryloyloxy group, and the other is a hydrogen atom or an alkyl group. ); A compound represented by the formula (wherein R is a hydrogen atom or a methyl group), and is represented by the following general formula [IV]: (In the formula [IV], p and l are 0 or an integer of 1 or more, r and s are 0, 1 or 2, and R ²¹
To R ³⁹ each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, and the carbon to which R ²⁹ and R ³⁰ are bonded. The atom and the carbon atom to which R ³³ is bonded or the carbon atom to which R ³¹ is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and r = s = When 0, R ³⁵ and R ³² or R ³⁵ and R ³⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring, and one of X ³ and X ⁴ is the above formula. It is an acryloyloxy group or a methacryloyloxy group represented by [X], and the other is a hydrogen atom or an alkyl group. ); And a compound represented by the following formula [V]: (In the formula [V], t is 4 or 5, R ^{41 to} R ⁴³ are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group, and X ⁵ is an acryloyloxy group represented by the following formula [X]. Or a methacryloyloxy group) is obtained by graft-polymerizing at least one acrylate or methacrylate monomer having an alicyclic skeleton selected from the group consisting of compounds represented by 5-100 parts by weight,
The cyclic olefin polymer composition according to claim 1, which is a core-shell elastomer characterized by having an average diameter of primary particles in the range of 100 to 300 nm. 4. The refractive index n _D of the [B] component is 1.52 to 1.
The cyclic olefin polymer composition according to any one of claims 1 to 3, which is in the range of 56. 5. A core component 40 comprising [B-1] a styrene-butadiene rubber having a styrene unit content of 50% by weight or less.
~ 85 parts by weight and [B-2] (b-1) the following general formula [III] (In the formula [III], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸
And R ^a and R ^b are each independently a hydrogen atom,
It is a halogen atom or a hydrocarbon group, R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond. , R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group, and ^one of X ¹ and X ² is an acryloyloxy group represented by the following formula [X]: Alternatively, it is a methacryloyloxy group, and the other is a hydrogen atom or an alkyl group. ); A compound represented by the following general formula [IV]: wherein R is a hydrogen atom or a methyl group. (In the formula [IV], p and l are 0 or an integer of 1 or more, r and s are 0, 1 or 2, and R ²¹
To R ³⁹ each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, and the carbon to which R ²⁹ and R ³⁰ are bonded. The atom and the carbon atom to which R ³³ is bonded or the carbon atom to which R ³¹ is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and r = s = When 0, R ³⁵ and R ³² or R ³⁵ and R ³⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring, and one of X ³ and X ⁴ is the above formula. It is an acryloyloxy group or a methacryloyloxy group represented by [X], and the other is a hydrogen atom or an alkyl group. ); And a compound represented by the following formula [V]: (In the formula [V], t is 4 or 5, R ^{41 to} R ⁴³ are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, and X ⁵ is an acryloyloxy group represented by the above formula [X]. Or at least one kind of acrylate or methacrylate monomer having an alicyclic skeleton selected from the group consisting of compounds represented by (methacryloyloxy group), (b-2) monovinyl aromatic Monomer 0 to 70% by weight (b-3) Other copolymerizable monovinyl monomer 0 to 70% by weight and (b-4) Polyfunctional monomer 0 to 3% by weight 15 to 60 parts by weight of a shell component composed of a (co) polymer having a monomer or a mixture of monomers as a constituent, provided that the core component [B-1] and the shell component [B-
2] is 100 parts by weight, and (C) the average diameter of the primary particles is in the range of 100 to 300 nm. 6. The [B-1 ′] styrene unit is 50% by weight.
The following styrene-butadiene rubber latex 40
˜85 parts by weight, [B-2 ′] (b-1) represented by the following general formula [III] (In the formula [III], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸
And R ^a and R ^b are each independently a hydrogen atom,
It is a halogen atom or a carbon-hydrogen group, and R ^{15 to} R ¹⁸ may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond. , R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group, and ^one of X ¹ and X ² is an acryloyloxy group represented by the following formula [X]: Alternatively, it is a methacryloyloxy group, and the other is a hydrogen atom or an alkyl group. ); A compound represented by the formula (wherein R is a hydrogen atom or a methyl group), represented by the following general formula [IV]: (In the formula [IV], p and l are 0 or an integer of 1 or more, r and s are 0, 1 or 2, and R ²¹
To R ³⁹ each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, and the carbon to which R ²⁹ and R ³⁰ are bonded. The atom and the carbon atom to which R ³³ is bonded or the carbon atom to which R ³¹ is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and r = s = When 0, R ³⁵ and R ³² or R ³⁵ and R ³⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring, and one of X ³ and X ⁴ is the above formula. It is an acryloyloxy group or a methacryloyloxy group represented by [X], and the other is a hydrogen atom or an alkyl group. ); And a compound represented by the following formula [V]: (In the formula [V], t is 4 or 5, R ^{41 to} R ⁴³ are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, and X ⁵ is an acryloyloxy group represented by the above formula [X]. Or at least 1 of an acrylate or methacrylate monomer having an alicyclic skeleton selected from the group consisting of compounds represented by (methacryloyloxy group)
Species 20 to 100% by weight, (b-2) Monovinyl aromatic monomer 0 to 70% by weight (b-3) Other monovinyl type monomer copolymerizable therewith 0 to 70% by weight and (b -4) Polyfunctional monomer Obtained by graft-polymerizing 15 to 60 parts by weight of a monomer or monomer mixture consisting of 0 to 3% by weight, provided that latex [B-
1 '] and the monomer or monomer mixture [B-2'] is 100 parts by weight, and (C) the average diameter of the primary particles is in the range of 100 to 300 nm. Core / shell elastomer 7. [B-1] A core component comprising a styrene-butanediene rubber having a styrene unit content of 50% by weight or less.
40 to 85 parts by weight, and [B-2 ″] (b-2) Monovinyl aromatic monomer 20 to 80% by weight (b-3) Other monovinyl monomer copolymerizable therewith 20 To 80% by weight and (b-4) a polyfunctional monomer 0 to 3% by weight, a core component comprising 15 to 60 parts by weight of a shell component made of a copolymer having a monomer mixture as a constituent.
With respect to 100 parts by weight of the shell elastomer, the total of the core component [B-1] and the shell component [B-2 ″] is 10
0 parts by weight of [B-2 ′ ″] (b-1) the following general formula [III] (In the formula [III], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸
And R ^a and R ^b are each independently a hydrogen atom,
It is a halogen atom or a hydrocarbon group, R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond. , R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group, and ^one of X ¹ and X ² is an acryloyloxy group represented by the following formula [X]: Alternatively, it is a methacryloyloxy group, and the other is a hydrogen atom or an alkyl group. ); A compound represented by the formula (wherein R is a hydrogen atom or a methyl group), represented by the following general formula [IV] (In the formula [IV], p and l are 0 or an integer of 1 or more, r and s are 0, 1 or 2, and R ²¹
To R ³⁹ each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, and the carbon to which R ²⁹ and R ³⁰ are bonded. The atom and the carbon atom to which R ³³ is bonded or the carbon atom to which R ³¹ is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and r = s = When 0, R ³⁵ and R ³² or R ³⁵ and R ³⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring, and one of X ³ and X ⁴ is the above formula. It is an acryloyloxy group or a methacryloyloxy group represented by [X], and the other is a hydrogen atom or an alkyl group. ); And a compound represented by the following formula [V]: (In the formula [V], t is 4 or 5, R ^{41 to} R ⁴³ are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, and X ⁵ is an acryloyloxy group represented by the above formula [X]. Or at least 1 of an acrylate or methacrylate monomer having an alicyclic skeleton selected from the group consisting of compounds represented by (methacryloyloxy group)
A core-shell elastomer, obtained by graft-polymerizing 5 to 100 parts by weight of a seed, and (C) having an average primary particle diameter in the range of 100 to 300 nm. 8. The core-shell elastomer according to claim 5, which has a refractive index n _D in the range of 1.52 to 1.56.