JP2001031716A - Modified ethylene-based copolymer and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modified ethylene-based copolymer which can be produced from a widely used versatile raw material, has no coloration at the time of molding and is excellent in transparency and heat resistance. SOLUTION: To the modified ethylene-based copolymer and a its production process for the copolymer which comprising a polymer in which an unsaturated bond-containing ethylene-based copolymer (but, with a cyclopentadiene content of 20-70 mole %) obtained by copoluymerizing either ethylene or ethylene and α-olefin with at least one kind of a cyclic diene selected from dicyclopentadiene, methyl-substituted dicryclopentadiend and tricyclopentadiene, an epoxy group and/or a hydroxyl group by 10 mole % or more of the unsaturated bond contained in the ethylene-based copolymer are introduced, and the resultant remained unsaturated-bond in hydrogenated, is characterized in that the copolymer has properties: (a) a weight-average molecular weight of 20,000-1,000,000 (b) a glass transition temperature of 100 deg.C or above, and (c) the whole light transmission of 90% or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a modified ethylene copolymer obtained by modifying an unsaturated bond-containing ethylene copolymer. More specifically, the present invention has no coloring at the time of molding obtained by chemically modifying ethylene or an unsaturated bond-containing ethylene copolymer obtained by copolymerizing ethylene and an α-olefin with a specific cyclic diene, The present invention relates to a modified ethylene copolymer having excellent transparency and heat resistance.

[0002] The modified ethylene copolymer obtained by the method of the present invention can be easily hot-melt molded by a well-known molding method at a high temperature without causing crosslinking or thermal deterioration. The obtained molded article is excellent in hue, transparency, heat resistance and the like, and can be used in a wide range of application fields. For example, a protective film of a photoresist, an optical lens,
Optical fields such as optical disks; water tanks for electric irons, microwave oven supplies, liquid crystal display substrates, printed circuit boards, electric fields such as transparent conductive sheets and films; medical and chemical fields such as syringes and pipettes; camera bodies and various instruments Can be used in the field of housings such as covers; other fields such as films, sheets and helmets.

[0003]

2. Description of the Related Art Conventionally, α-olefin homopolymers and copolymers have been widely used because they are inexpensive but have excellent moldability and physical properties. In order to utilize these olefin-based polymers at a higher level, higher performance or functional properties are being imparted by copolymerizing with a specific comonomer or conducting a polymer reaction.

Recently, various methods for synthesizing olefin copolymers having good transparency and excellent heat resistance by copolymerizing an α-olefin such as ethylene or propylene with a cyclic olefin or a cyclic polyene have been studied and proposed. Have been.

In particular, as a copolymer of ethylene and a cyclic olefin, for example, US Pat. No. 2,883,372 discloses ethylene and 2,3-dihydrodicyclopentadiene (IUPAC name: 4,7-methano- 2,3,3a,
4,7,7a-Hexahydro-1H-indene (MHI
)) Is disclosed in JP-A-60-16.
8708 and JP-A-61-115912 disclose ethylene and 1,4,5,8-dimethano-1,2,2.
A random copolymer comprising 3,4,4a, 5,8,8a-octahydronaphthalenes (abbreviated as DMONs) or a method for producing the same is disclosed. However, the cyclic olefin used in these inventions is special and cannot be said to be a general-purpose raw material.

On the other hand, JP-A-63-243103 discloses ethylene-MHI by polymerizing ethylene and dicyclopentadiene and hydrogenating the resulting copolymer.
It is disclosed that a polymer having the same structure as the copolymer can be obtained. This method is more advantageous than the above method using MHI or DMON in that dicyclopentadiene which is a highly versatile raw material is used as a cyclic comonomer,
In the case where the hydrogenation is less than 100% and the unsaturated bond remains, there is a disadvantage that coloring is likely to occur during molding. Further, even when completely hydrogenated, there is room for improvement in that the heat resistance is lower than that of an ethylene-DMON copolymer or the like.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an unsaturated bond-containing ethylene copolymer (hereinafter referred to as "unsaturated") which is obtained mainly from ethylene and a cyclic diene which is highly versatile or easily synthesized. (Sometimes abbreviated as a copolymer)) by a simple method of chemically modifying
An object of the present invention is to provide a modified ethylene copolymer (hereinafter, sometimes abbreviated as a modified copolymer) having no coloring at the time of molding and excellent in transparency and heat resistance, and further to provide a production method thereof. .

[0008]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that ethylene or ethylene and α-olefin, dicyclopentadiene, methyl-substituted dicyclopentadiene and tricyclopentadiene. Using an unsaturated copolymer obtained by copolymerizing at least one cyclic diene selected from pentadiene, introducing an epoxy group and / or a hydroxyl group into an unsaturated bond in the copolymer, and optionally hydrogenating the copolymer. The inventor has found that the modified copolymer has no coloring at the time of molding and is excellent in transparency and heat resistance, thereby completing the present invention.

That is, the gist of the first invention is to copolymerize ethylene or ethylene and an α-olefin with at least one cyclic diene selected from dicyclopentadiene, methyl-substituted dicyclopentadiene and tricyclopentadiene. The resulting unsaturated bond-containing ethylene copolymer (provided that the content of the cyclic diene unit is from 20 to 70)
Mol%) of the unsaturated bond contained in the ethylene-based copolymer is 10 mol% or more (that is, 10 to 100 mol%).
Mole%), and the remaining unsaturated bonds (that is, 90 to 0 mole%) are hydrogenated. The physical properties of the polymer are (a) the weight average molecular weight is 2%.
(B) a glass transition temperature of 100 ° C. or higher, and (c) a total light transmittance of 90% or higher.
Further, the gist of the second invention is that an ethylene or ethylene and α-olefin is copolymerized with at least one cyclic diene selected from dicyclopentadiene, methyl-substituted dicyclopentadiene and tricyclopentadiene. Saturated bond-containing ethylene copolymer (however,
(The content of the cyclic diene unit is from 20 to 70 mol%), (1) an epoxy group and / or a hydroxyl group are introduced into part or all of the unsaturated bonds contained in the ethylene-based copolymer. After that, the remaining unsaturated bonds are hydrogenated, or (2) after partially hydrogenating some of the unsaturated bonds contained in the ethylene-based copolymer, an epoxy group and And / or a method for producing a modified ethylene copolymer, characterized in that a hydroxyl group is introduced and at least 10 mol% of unsaturated bonds contained in the ethylene copolymer contain an epoxy group and / or a hydroxyl group. Exist.

Regarding the modification of the same unsaturated bond-containing copolymer as in the present invention, for example, Japanese Unexamined Patent Publication (Kokai) No. 7-82323 discloses an unsaturated copolymer of ethylene and a cyclic polyene such as dicyclopentadiene. A modified copolymer into which an epoxy group or a hydroxyl group has been introduced has been proposed. However, this modified copolymer is an unsaturated copolymer having a low polymer dicyclopentadiene content of 0.01 to 3.5 mol%. That is, the object is to improve the adhesiveness, printability, hydrophilicity, etc. while maintaining the basic performance of polyethylene, and to provide a polymer excellent in transparency and heat resistance aimed at by the present invention. It is not the purpose.
In fact, according to the findings of the present inventors, in an unsaturated copolymer having a dicyclopentadiene content of 3.5 mol% or less, even if an epoxy group or a hydroxyl group is introduced, transparency and heat resistance are almost the same as those of polyethylene. There is no big difference.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The ethylenic copolymer containing an unsaturated bond used in the present invention is selected from ethylene or ethylene and an α-olefin, and dicyclopentadiene, methyl-substituted dicyclopentadiene and tricyclopentadiene. An unsaturated copolymer obtained by copolymerizing at least one cyclic diene.

Among the cyclic dienes used, dicyclopentadiene and methyl-substituted dicyclopentadiene are represented by the following general formula (1), and tricyclopentadiene is represented by the following general formula (2).

Embedded image (In the formula, Me represents a methyl group; l, m, n, and p represent 0 or 1; l + m + n + p = 0 or 1, or 1 = p = 0 and m = n = 1.)

Embedded image

In these cyclic dienes, one unsaturated bond is incorporated into a polymer chain by copolymerization, and the other unsaturated bond remains as it is, and each of the following general formulas (3) and (4) Is an unsaturated copolymer containing a structural unit represented by

Embedded image (Wherein, the meaning of Me, l, m, n, p, and l, m, n
And p are the same as in the above equation (1). )

Embedded image

The content of the unit derived from the cyclic diene in the unsaturated copolymer is from 20 to 70 mol%, preferably from 25 to 60 mol%. When the content is 20 mol% or less, the heat resistance becomes insufficient even if the degree of modification of the unsaturated bond in the copolymer is large. On the other hand, when the content exceeds 70 mol%, it becomes difficult to obtain an unsaturated copolymer having a high molecular weight, and it is not suitable for the intended application field.

The unsaturated copolymer used in the present invention has a weight average molecular weight (Mw) of 20,000.
~ 1,000,000, preferably 30,000 ~ 50
It is 0000.

The cyclic dienes used in the present invention are readily available and versatile raw materials. For example, dicyclopentadiene can be easily obtained by dimerizing cyclopentadiene, which is the main component of the C5 fraction generated by naphtha decomposition, and purifying it by distillation. Further, tricyclopentadiene can be easily obtained by further distilling the remaining fraction obtained by distilling and separating dicyclopentadiene from the dimerized product of cyclopentadiene, followed by extraction and purification.
Furthermore, methyl-substituted dicyclopentadiene can be easily obtained by distilling and purifying a reaction product obtained by codimerization of cyclopentadiene and methylcyclopentadiene.

Further, the unsaturated copolymer of the present invention may be a copolymer obtained by co-existing an α-olefin having 3 to 20 carbon atoms in addition to ethylene and a cyclic diene. Propylene, 1-butene, 1-
Penten, 1-hexene, 1-octene, 4-methylpentene-1 and the like. The content of these α-olefins in the unsaturated copolymer is usually 5 mol% or less.

For the production of the unsaturated copolymer of the present invention, a catalyst comprising a metallocene compound [A] and an organic aluminum oxy compound [B] is used. The metallocene compound [A] is a compound represented by the following general formula (5) or (6). (R ¹ _e Cp) _m (R ² _f Cp) _n M (Y) _{4- (m + n)} (5) (where M is titanium, zirconium or hafnium,
Cp is a group having a cyclopentadienyl skeleton, R ¹ and R ² are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an alkylaryl group, an arylalkyl group or an alkylsilyl group, Y is a halogen atom, a hydrogen atom, a carbon atom A hydrogen group, a silyl group, a halogenated hydrocarbon group, a nitrogen-containing organic group, an oxygen-containing organic group or a sulfur-containing organic group;
An integer of 5, m and n each represent an integer of 0 to 3.
Where m + n is an integer of 1 to 3) R ′ (R ¹ _g Cp) (R ² _h Cp) M (Y) ₂ (6) (where M is titanium, zirconium or hafnium,
Cp is a group having a cyclopentadienyl skeleton, R ¹ and R ² are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an alkylaryl group, an arylalkyl group or an alkylsilyl group, and R ′ is (R ¹ _g Cp) And (R ² _h C
p) an alkylene group, an arylalkylene group, a dialkylsilylene group, a dialkylgermylene group,
A divalent group selected from an alkylphosphinediyl group or an alkylimino group, Y is a halogen atom, a hydrogen atom, a hydrocarbon group, a silyl group, a halogenated hydrocarbon group, a nitrogen-containing organic group, an oxygen-containing organic group, or a sulfur-containing organic group; Groups, g and h are 0
To 4).

In the general formulas (5) and (6),
The Cp group as a ligand is not particularly limited as long as it is a group having a cyclopentadienyl skeleton, and two adjacent carbon atoms of a cyclopentadienyl ring as well as a cyclopentdienyl group are replaced with other carbon atoms. Cyclopentadienyl groups bonded to form a 4-, 5- or 6-membered ring are also included.
Examples of the cyclopentadienyl group in which two adjacent carbon atoms of the cyclopentadienyl ring are bonded to another carbon atom to form a 4-, 5- or 6-membered ring include, for example, indenyl Group, tetrahydroindenyl group,
And a fluorenyl group.

In the general formulas (5) and (6), R ¹ and R ² are each other than a hydrogen atom, especially an alkyl group having 1 to 20 carbon atoms and an alkenyl group having 2 to 20 carbon atoms. , An aryl group having 6 to 20 carbon atoms, 7 to 2 carbon atoms
An alkylaryl group having 0, an arylalkyl group having 7 to 20 carbon atoms, or an alkylsilyl group having 3 to 20 carbon atoms is preferable.

In the general formula (5), the groups R ¹ _e Cp and R ² _f Cp having a cyclopentadienyl skeleton include, for example, cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group , N-propylcyclopentadienyl group, isopropylcyclopentadienyl group, n-butylcyclopentadienyl group,
Isobutylcyclopentadienyl group, tertiarybutylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadienyl group A 1,2,3-trimethylcyclopentadienyl group,
Tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group, trimethylsilyltetramethylcyclopentadienyl group, (phenyldimethylsilyl) cyclopentadienyl group, triphenylsilylcyclopentadienyl Group, 1,3-di (trimethylsilyl) cyclopentadienyl group, cyclohexylcyclopentadienyl group, allylcyclopentadienyl group, benzylcyclopentadienyl group, phenylcyclopentadienyl group, tolylcyclopentadienyl group , Indenyl group, 1-methylindenyl group, 2-methylindenyl group, 2,4-dimethylindenyl group, 4,7-dimethoxyindenyl group, 4,
7-dichloroindenyl group, 5,6-dimethylindenyl group, 2-methyl-4-ethyl-indenyl group, 2-methyl-4,6-diisopropyl-indenyl group, naphthylindenyl group, 4,5,6 , 7-tetrahydroindenyl group, 2-methyl-tetrahydroindenyl group, fluorenyl group, 2,7-ditert-butylfluorenyl group and the like.

In the general formula (6), R 'is (R
¹ carbon number bridging ¹ _g Cp) and (R ² _h Cp)
To 20; specifically, an alkylene group such as a methylene group and an ethylene group; an alkylidene group such as an ethylidene group, a propylidene group and an isopropylidene group; a phenylmethylidene group and a diphenylmethylidene group; Arylalkylidene group: Silylene group such as dimethylsilylene group, diethylsilylene group, dipropylsilylene group, diisopropylsilylene group, methylethylsilylene group, methylisopropylsilylene group, methyltert-butylsilylene group, methylphenylsilylene group, diphenylsilylene group, etc. A dimethylgermylene group, a diethylgermylene group,
Germylene groups such as dipropylgermylene group, diisopropylgermylene group, diphenylgermylene group, methylethylgermylene group, methylisopropylgermylene group, methyltertiarybutylgermylene group, methylphenylgermylene group, diphenylgermylene group, etc. An alkylphosphinediyl group such as a methylphosphinediyl group;
An alkylimino group such as a methylimino group; an alkylboranediyl group such as a methylboranediyl group;

In the general formula (6), a group R '(R ¹ _g Cp) (R ² ) having a cyclopentadienyl skeleton
_h Cp) includes, for example, an ethylenebisindenyl group,
Diphenylmethylenebisindenyl group, dimethylsilylbisindenyl group, isopropylidenebisindenyl group, dimethylsilylbistetrahydroindenyl group, isopropylidenecyclopentadienyl-1-fluorenyl group, diphenylmethylenecyclopentadienyl-1-
Fluorenyl group, dimethylsilylcyclopentadienyl-1-fluorenyl group, dimethylsilylbis (2,3
5-trimethylcyclopentadienyl) group, dimethylsilylbis (2,4-dimethylcyclopentadienyl)
A dimethylsilylbis (3-methylcyclopentadienyl) group, an isopropylidenecyclopentadienyl-methylcyclopentadienyl group, an isopropylidenecyclopentadienyl-2,3,5-trimethylcyclopentadienyl group, diphenylmethylene cyclopentadienyl - methylcyclopentadienyl group, diphenylmethylene cyclopentadienyl-2,4-dimethyl cyclopentadienyl group, diphenylmethylene cyclopentadienyl _-2, 3,5-trimethyl cyclopentadienyl Group, dimethylsilylcyclopentadienyl-methylcyclopentadienyl group, dimethylsilylcyclopentadienyl-
2,4-dimethylcyclopentadienyl group, dimethylsilylcyclopentadienyl-2,3,5-trimethylcyclopentadienyl group, isopropylidene-2,4-dimethylcyclopentadienyl-1-fluorenyl group, diphenyl Methylene-2,4-dimethylcyclopentadienyl-1-fluorenyl group, dimethylsilyl 2,4-dimethylcyclopentadienyl-1-fluorenyl group, cyclohexylidenecyclopentadienyl-1-fluorenyl group, dimethylgermyl And a bis-1-indenyl group.

The compound according to the definition of the general formula (5) described above includes a chlorine atom, a bromine atom,
The following compounds having a hydrogen atom, a methyl group, an ethyl group, a phenyl group and the like can be exemplified. For example, bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium monobromide monohydride, bis (cyclopentadienyl) methyl zirconium hydride, bis (cyclopentadienyl) ethylzirconium hydride, bis (Cyclopentadienyl) phenyl zirconium hydride, bis (cyclopentadienyl) benzyl zirconium hydride, bis (cyclopentadienyl) neopentyl zirconium hydride, bis (methylcyclopentadienyl) zirconium monochloride monohydride, bis (indenyl) ) Zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadiene) Nil) zirconium dibromide, bis (cyclopentadienyl) methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl Zirconium monochloride, bis (cyclopentadienyl) benzylzirconium monochloride,
Bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (trimethylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) ) Zirconium dimethyl, bis (cyclopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) zirconium dibenzyl, bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (fluorenyl) zirconium dichloride, etc. Can be

The metallocene compound of the general formula (5) includes compounds having various phenoxy groups or substituted phenoxy groups as the Y group in the formula. Specific examples of this metallocene compound are described in International Patent Application No. PCT / JP98.
For example, dicyclopentadienyl bis (4-fluorophenoxy) zirconium, dicyclopentadienyl bis (4-
Chlorophenoxy) zirconium, dicyclopentadienyl bis (2,4-difluorophenoxy) zirconium, dicyclopentadienyl bis (2,4,6-trifluorophenoxy) zirconium, dicyclopentadienyl bis (3-fluoro Methylphenoxy) zirconium, dicyclopentadienylbis (4-fluoromethylphenoxy) zirconium, dicyclopentadienylbis (2-chloromethylphenoxy) zirconium, dicyclopentadienylbis (3-trifluoromethylphenoxy) zirconium , Dicyclopentadienyl bis (4-trichloromethylphenoxy) zirconium, dicyclopentadienyl bis (2-methylphenoxy) zirconium, dicyclopentadienyl bis (3-methylphenoxy) zircon , Dicyclopentadienyl bis (2,4-dimethylphenoxy) zirconium, dicyclopentadienyl bis (pentamethylphenoxy) zirconium, dicyclopentadienyl bis (2-ethylphenoxy) zirconium, dicyclopentadienyl Bis (4-tert-butylphenoxy) zirconium, dicyclopentadienylbis (2-methoxycarbonylphenoxy) zirconium, dicyclopentadienylbis (2-cyanophenoxy) zirconium, dicyclopentadienylbis (2-nitro Phenoxy) zirconium, bis (methylcyclopentadienyl) bis (2
-Fluorophenoxy) zirconium, bis (methylcyclopentadienyl) bis (2-trifluoromethylphenoxy) zirconium, bis (1,2,4-trimethylcyclopentadienyl) bis (4-methylphenoxy) zirconium, bis ( Pentamethylcyclopentadienyl) bis (2-fluorophenoxy) zirconium, bis (pentamethylcyclopentadienyl) bis (4-fluorophenoxy) zirconium, bis (ethylcyclopentadienyl) bis (2-ethylphenoxy) zirconium , Bis (ethylcyclopentadienyl) bis (3-ethylphenoxy) zirconium, bis (n-butylcyclopentadienyl) bis (3-trifluoromethylphenoxy) zirconium, bis (tert-butylcyclopentadienyl) Sulfonyl) bis (2-ethylphenoxy) zirconium, bis (trimethylsilyl cyclopentadienyl) bis (4-tert-butoxy-phenoxy) zirconium, bis (trimethylsilyl cyclopentadienyl) bis (2-phenylphenoxy)
Zirconium, bis (indenyl) bis (2-methylphenoxy) zirconium, bis (indenyl) bis (3
-Methylphenoxy) zirconium, bis (indenyl) bis (4-methylphenoxy) zirconium, bis (1-methylindenyl) bis (2-fluorophenoxy) zirconium, bis (1-methylindenyl) bis (3-fluorophenoxy ) Zirconium, bis (1-
Methylindenyl) bis (4-fluorophenoxy) zirconium, bis (2-methylindenyl) bis (2-
Bromophenoxy) zirconium, bis (2-methylindenyl) bis (3-bromophenoxy) zirconium, bis (2-methylindenyl) bis (4-bromophenoxy) zirconium, bis (5,6-dimethylindenyl) bis (2-isopropylphenoxy) zirconium, bis (5,6-dimethylindenyl) bis (3-
Isopropylphenoxy) zirconium, bis (5,6
-Dimethylindenyl) bis (4-isopropylphenoxy) zirconium, bis (5,6-dimethoxyindenyl) bis (2-cyanophenoxy) zirconium, bis (5,6-dimethoxyindenyl) bis (3-cyanophenoxy) Zirconium, bis (5,6-dimethoxyindenyl) bis (4-cyanophenoxy) zirconium, bis (fluorenyl) bis (2-chlorophenoxy) zirconium, bis (fluorenyl) bis (3-fluorophenoxy) zirconium, bis (4 , 5,6
7-tetrahydroindenyl) bis (4-tert-butylphenoxy) zirconium and the like.

On the other hand, as the metallocene compound represented by the general formula (6), a metallocene compound having a chlorine atom, a bromine atom, a hydrogen atom, a methyl group, an ethyl group, a benzyl group, a phenyl group, etc. as a Y group in the formula For example, ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) diethyl zirconium, ethylene bis (indenyl) diphenyl zirconium, ethylene bis (indenyl) methyl zirconium monochloride, ethylene bis (indenyl) ethyl Zirconium monochloride, ethylenebis (indenyl) methylzirconium monobromide, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, dimethylsilylenebis (cyclope Tadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) Zirconium dichloride, isopropylidene (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl fluorenyl) zirconium dichloride, and the like.

As the metallocene compound represented by the general formula (6), the following compounds having various phenoxy groups or substituted phenoxy groups as the Y group in the formula can also be used. Specific examples of this metallocene compound are described in detail in International Patent Application No. PCT / JP98 / 05621, and include, for example, ethylenebis (indenyl) bis (4-trifluoromethylphenoxy) zirconium,
Ethylenebis (indenyl) bis (4-fluorophenoxy) zirconium, ethylenebis (indenyl) bis (4-chlorophenoxy) zirconium, ethylenebis (indenyl) bis (2-fluorophenoxy) zirconium, ethylenebis (3-methylindenyl) ) Bis (4-trifluoromethylphenoxy) zirconium,
Ethylenebis (3-methylindenyl) bis (4-fluorophenoxy) zirconium, methylenebis (cyclopentadienyl) bis (2-fluorophenoxy) zirconium, methylenebis (cyclopentadienyl) bis (2-ethylphenoxy) zirconium, Methylenebis (methylcyclopentadienyl) bis (3-chlorophenoxy) zirconium, methylenebis (1,3-dimethylcyclopentadienyl) bis (2-trifluoromethylphenoxy) zirconium, methylenebis (n-butylcyclopentadienyl) Bis (4-tert-butylphenoxy) zirconium, ethylenebis (3-methylcyclopentadienyl) bis (4-trifluoromethylphenoxy) zirconium, ethylenebis (3-methylcyclopentadi Nil) bis (4-fluorophenoxy) zirconium, ethylenebis (3-isopropylcyclopentadienyl) bis (4-trifluoromethylphenoxy) zirconium, dimethylsilylenebis (indenyl) bis (4-trifluoromethylphenoxy) zirconium, Dimethylsilylenebis (indenyl) bis (4-fluorophenoxy) zirconium, dimethylsilylenebis (2-methylindenyl) bis (4-trifluoromethylphenoxy) zirconium, dimethylsilylene (cyclopentadienyl) (indenyl) bis (4
-Trifluoromethylphenoxy) zirconium and the like.

Further, in addition to the various metallocene compounds exemplified above, metallocene compounds in which M in the general formulas (5) and (6) is replaced with a titanium atom or a hafnium atom from a zirconium atom can also be used.

The organoaluminum oxy compound [B] used in the present invention is selected from a linear aluminoxane represented by the following general formula (7) or a cyclic aluminoxane represented by the following general formula (8).

[0030]

Embedded image (Wherein, R ³ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms, and d represents an integer of 2 to 40. However, when R ³ is a halogen atom, when all are halogen atoms, except for)

[0031]

Embedded image (Wherein, the definitions of R ³ and d are the same as in the case of general formula (7))

When R ³ in the general formulas (7) and (8) is an alkyl group having 1 to 10 carbon atoms, specific examples thereof include a methyl group, an ethyl group and an isobutyl group. When R ³ is a halogen atom, it is a chlorine atom or a bromine atom.
Further, the compounds of the general formulas (7) and (8) may have different R ³ groups in the compounds. The number d of the repeating unit is selected from the range of 2 to 40, preferably 5 to 2
It is in the range of 0. Among these compounds of formulas (7) and (8), those in which R ³ has only a methyl group, or a compound having a methyl group and another group are particularly preferable.

Various known methods can be used to synthesize the organoaluminum oxy compound [B] represented by the general formula (7) or (8). For example, a method of dissolving a trialkylaluminum in a hydrocarbon solvent and gradually adding an equivalent amount of water to the trialkylaluminum of the solvent to hydrolyze, a method of dissolving copper sulfate hydrate or aluminum sulfate hydrate in a hydrocarbon solvent Is suspended, and a trialkylaluminum is contacted with 1 to 3 equivalents of the hydrated water of crystallization in the suspension to slowly hydrolyze the trialkylaluminum, or suspended in a hydrocarbon solvent. The trialkylaluminum can be synthesized by, for example, contacting 1 to 3 equivalents of trialkylaluminum with the adsorbed water of the turbid undehydrated silica gel to gradually hydrolyze the trialkylaluminum.

In the polymerization, the amount of the catalyst used is such that the metallocene compound [A] is usually 10 ^-8 to 10 ^-4 gram atom / L, preferably 1 to 10 ^-4 atom atom / L as transition metal atom concentration in the polymerization reaction system.
It is in the range of ^0-7 to ^10-5 gram atoms / L. The amount of the organic aluminum oxy compound [B] to be used is usually 10 ^-4 to 10 as the concentration of aluminum atoms in the polymerization reaction system.
^-1 gram atom / L, preferably in the range of 10 ^{-3 to} 5 × 10 ^-2 gram atom / L. The ratio of the aluminum atom to the transition metal atom in the polymerization reaction system is usually 10 to 10 ⁶ , preferably 10 ² to 10 ⁵ .

The above metallocene compound [A] and organoaluminum oxy compound [B] can be used as they are in the polymerization reaction, but they may be supported on various conventionally proposed carrier components and used as supported catalysts. Examples of the carrier component include silica, alumina, silica / alumina, magnesium chloride, magnesium oxide, and magnesium hydroxide. When a supported catalyst obtained by supporting the metallocene compound [A] and the organoaluminum oxy compound [B] on a carrier component is used, an organoaluminum compound can be further added to the polymerization system. Examples of the compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, diethylaluminum chloride and the like.

The polymerization in the present invention can be carried out by any polymerization method such as slurry polymerization and solution polymerization. When performing solution polymerization or slurry polymerization, an inert hydrocarbon solvent or olefin itself used for the polymerization can be used as a solvent. As the inert hydrocarbon solvent, for example, aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, and octane; cyclopentane,
An alicyclic hydrocarbon such as methylcyclopentane or cyclohexane; an aromatic hydrocarbon such as benzene, toluene or xylene; a petroleum fraction such as naphtha, kerosene or light oil can be used.

The polymerization temperature for carrying out the polymerization of the present invention is usually -20 to 100 ° C, preferably 20 to 90 ° C.
It is in the range of ° C. The polymerization pressure is not particularly limited, but is usually in a range from normal pressure to 10 MPa. The molecular weight of the copolymer can be adjusted by changing the polymerization temperature or adding a chain transfer agent such as hydrogen to the polymerization system.

Next, in the present invention, the unsaturated bond-containing copolymer thus obtained is modified by an epoxidation reaction, a hydroxylation reaction, or an epoxidation and a hydroxylation reaction, so that an epoxy group, a hydroxyl group or an epoxy group and a hydroxyl group are modified. Introduce.

<Introduction of Epoxy Group> An epoxy group is introduced by a method of oxidizing an unsaturated bond in an unsaturated copolymer and converting it into an epoxy group. As the epoxidation method, conventionally known various methods can be used. For example, (i) oxidation with a peracid such as formic acid, peracetic acid, perbenzoic acid, (ii) oxidation with alkaline hydrogen peroxide, (iii) ) Neutralization of acetic acid / t-butyl hypochlorite adduct with alkali.

The amount of the epoxy group introduced is at least 10 mol% of the unsaturated bonds in the unsaturated copolymer. If the amount is less than 10 mol%, the effect on heat resistance is insufficient.

<Introduction of Hydroxyl Group> Specifically, the introduction of a hydroxyl group is carried out by a method of oxidizing an unsaturated bond in an unsaturated copolymer and then hydrolyzing to generate a hydroxyl group. As a method for introducing a hydroxyl group into an unsaturated bond, various conventionally known methods can be used, for example, (i) oxidation via hydrogen peroxide and a peracid generated by an organic acid such as formic acid, (ii) )
Oxidation with a permanganate or the like in the presence or absence of a phase transfer catalyst such as a quaternary ammonium salt, and (iii) hydrolysis of the epoxy group introduced by the epoxidation reaction.

The amount of the hydroxyl group introduced is at least 10 mol% of the unsaturated bonds in the unsaturated copolymer. 10 mol% introduced
If less, the effect on heat resistance is insufficient.

<Introduction of Epoxy Group and Hydroxyl Group> The introduction of the epoxy group and the hydroxyl group is carried out by a reaction in which an unsaturated bond in the unsaturated copolymer is oxidized and hydrolysis occurs simultaneously therewith. Examples of the method for introducing an epoxy group and a hydroxyl group include: (i) oxidation via hydrogen peroxide and a peracid generated by an organic acid such as formic acid; and (ii) epoxy group introduced by the various epoxidation reactions described above. And partial hydrolysis. When an epoxy group and a hydroxyl group are introduced, the total amount of both introduced may be at least 10 mol% of the unsaturated bonds in the unsaturated copolymer.

The above-described reaction of introducing an epoxy group and / or a hydroxyl group is carried out in a state where the unsaturated copolymer is swollen or dissolved by a solvent or in a molten state. Among them, a reaction in a state of being dissolved by a solvent is preferable.
The solvent to be used should be appropriately selected depending on the type of the reaction and the raw materials used as described above, but may be aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; benzene And aromatic hydrocarbons such as toluene and xylene; or halides of the above hydrocarbons. Of course, a mixed solvent of two or more selected from these solvents can also be used.

<Method of Hydrogenation> In the present invention, the polymer is subjected to a hydrogenation reaction before or after the epoxy group and / or hydroxyl group is introduced into the unsaturated bond in the unsaturated copolymer. . The hydrogenation method is not particularly limited as long as it is a method generally used for hydrogenating a low-molecular unsaturated compound. For example, (i) nickel, palladium, platinum or these metals may be carbon, silica, Hydrogenation using a heterogeneous catalyst such as a supported catalyst supported on a carrier such as earth, alumina, and titanium oxide, a Raney nickel catalyst, a platinum oxide catalyst, and platinum black; or (ii) an organometallic compound belonging to Group VIII of the peri-discipline table (Eg, cobalt naphthenate / triethylaluminum, cobalt octenoate / n-butyllithium, nickel acetylacetonate / triethylaluminum, etc.) or a rhodium compound catalyst (For example, chlorotris (triphenylphosphine) rhodium (1), bromotris (tri E sulfonyl phosphine) rhodium (1), etc.) hydrogenation with homogeneous catalysts, and the like.

The hydrogenation reaction is carried out in a state where the unsaturated copolymer is swollen or dissolved by a solvent or in a state where it is melted. Among them, a reaction in a state of being dissolved by a solvent is preferable. As the solvent at that time, the solvent used in the above-described reaction for introducing the epoxy group and / or the hydroxyl group is similarly applied.

The reaction of introducing an epoxy group and / or a hydroxyl group and the reaction of introducing a hydrogen atom are performed for 100% of the unsaturated bonds in the unsaturated copolymer so that substantially no unsaturated bonds remain. I do. If unsaturated bonds remain in the modified copolymer, it is not preferable because the molded product is colored at the time of molding and the transparency is deteriorated. Here, "substantially no unsaturated bond remains" means that the integrated value of the absorption peak attributed to the unsaturated bond is zero in the spectrum obtained by the ¹³ C-NMR measurement shown in Examples described later. Means that

<Modified Ethylene Copolymer> The modified copolymer according to the present invention is obtained by using an unsaturated bond-containing ethylene copolymer obtained by using a highly versatile monomer as a raw material.
It is a modified ethylene copolymer into which an epoxy group and / or a hydroxyl group has been introduced by a general reaction called an oxidation reaction. The introduction of the epoxy group and / or the hydroxyl group into the unsaturated bond was confirmed by an infrared absorption spectrum method (IR method) and a nuclear magnetic resonance spectrum method ( ¹³ C-NMR method). In addition, it was confirmed by gel permeation chromatography (GPC) that the molecular weight and molecular weight distribution of the modified ethylene copolymer were almost the same as those of the unsaturated copolymer before modification.

The modified ethylene copolymer according to the present invention comprises:
It has the following features. (1) Since it has no unsaturated bond, hot-melt molding can be easily performed without causing crosslinking or thermal deterioration at high temperatures. (2) The resulting molded article shows good hue and transparency. That is, the total light transmittance is 90% or more, and the appearance is colorless and transparent. (3) By the introduced epoxy group and / or hydroxyl group,
The glass transition temperature is remarkably improved as compared with an unsaturated copolymer or a polymer obtained by hydrogenating an unsaturated copolymer, and shows excellent heat resistance.

Further, since this modified copolymer has an epoxy group and / or a hydroxyl group, it exhibits other characteristic properties. For example, the adhesiveness of various printing inks and paints is excellent, and the dyeability is imparted. It also has excellent adhesion to copper and other metals and other resins, and is useful as a compatibilizer when blending a polyolefin resin with a resin having a functional group reactive with an epoxy group. Further, by utilizing the reactivity of an epoxy group and / or a hydroxyl group, a compound having a functional group such as an antioxidant property, an ultraviolet absorbing property, an antifogging property, a photosensitivity and a chelating property is introduced to thereby provide an antioxidant. , An ultraviolet absorber, an antifogging agent, a photosensitive material, a chelating agent and the like.

[0051]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

In Examples, Comparative Examples and Reference Examples,
The analysis of the unsaturated copolymer or the modified copolymer and the measurement of the physical properties were performed according to the following methods. (1) Molecular weight: GPC method was used. It was measured at a temperature of 135 ° C. using trichlorobenzene as a solvent, converted into the molecular weight of standard polystyrene, and obtained as a weight average molecular weight (M
w) and number average molecular weight (Mn) were determined. (2) Dicyclopentadiene content: determined by ¹³ C-NMR method. 25 ° C using deuterated chloroform as solvent
Measured with (3) Conversion rate to epoxy group: Same as above (4) Conversion rate to hydroxyl group: Same as above (5) Hydrogenation rate: Same as above (6) Glass transition temperature (Tg): Differential scanning calorimeter (manufactured by Seiko Instruments Inc.) And was measured by the DSC method. (7) Total light transmittance: Press molded thickness 3.2 m
A test piece of m, width 50 mm and length 100 mm was cut and measured using a color computer (manufactured by Suga Test Instruments) in accordance with JIS K7105 measurement method A. The obtained numerical value is used as an index of transparency, and the larger the numerical value, the better the transparency. (8) Hue: The test piece press-molded in the above (7) was visually judged.

Reference Example 1 <Production of Unsaturated Copolymer A> A 1 L stainless steel autoclave equipped with a stirrer and having an inner volume of 1 L was sufficiently dried under reduced pressure, and was replaced with dry nitrogen. 500 ml of purified toluene and dicyclopentadiene (DCP
D) was placed in an autoclave under a nitrogen stream, and methylaluminoxane (MMAO-3A manufactured by Tosoh Akzo Co.) was added in an amount of 30 moles in terms of aluminum atoms.
An amount corresponding to milligram atoms and ethylene bis (indenyl) zirconium dichloride (manufactured by Witco) in an amount corresponding to 5.0 × 10 ⁻³ milligram atoms in terms of zirconium atoms were added to the autoclave at room temperature.
Pressurized to 0.6 MPa with ethylene gas, and 0.5
Time copolymerization was performed. After the polymerization, the residual gas was released, and the polymer solution was poured into a large amount of methanol to precipitate the polymer. The obtained polymer was dissolved again in toluene, centrifuged, and then filtered to remove the catalyst residue. After the filtrate was poured into a large amount of methanol and precipitated again, the recovered polymer was dried under reduced pressure at 60 ° C. 28 g of the copolymer was obtained and the activity per unit zirconium was 65 kg polymer / gram atom Zr. DCPD in this polymer
The content is 40 mol%, Mw is 104,000, Mn
Was 41,000 and Mw / Mn was 2.5. This is designated as unsaturated copolymer A.

Reference Example 2 <Production of Unsaturated Copolymer B> Copolymerization was carried out in the same manner as in Reference Example 1, except that 0.3 mol of DCPD was used in the polymerization of Reference Example 1.
As a result, 45 g of a copolymer was obtained, and the polymerization activity was 10
It was 0 kg polymer / gram atom Zr. The DCPD content of this copolymer was 27 mol%, and Mw was 150,000. This is designated as unsaturated copolymer B.

Reference Example 3 <Production of Unsaturated Copolymer C> Copolymerization was carried out in the same manner as in Reference Example 1, except that 0.15 mol of DCPD was used in the polymerization of Reference Example 1. As a result, 45 g of a copolymer was obtained, and the polymerization activity was 100 k.
g polymer / gram atom Zr. The DCPD content of the obtained polymer was 16 mol%, and the Mw was 110,000. This is referred to as unsaturated copolymer C.

Reference Example 4 <Production of Unsaturated Copolymer D> The procedure of Reference Example 1 was repeated except that 1.0 mol of tricyclopentadiene (abbreviated as TCPD) was used instead of DCPD in the polymerization of Reference Example 1. Copolymerization was performed in the same manner. 1.0 g of copolymer was obtained and 2.0 kg of polymer /
The polymerization activity was gram atom Zr. The TCPD content of the obtained polymer was 33 mol%, and Mw was 66,000. This is designated as unsaturated copolymer D. Table 1 summarizes the physical property data of the unsaturated copolymers A to D obtained in the above Reference Examples.

[Table 1]

Next, the modified copolymers of the present invention were synthesized using these unsaturated copolymers A to D. Example 1 5.0 g of the unsaturated copolymer A obtained in Reference Example 1 was dissolved in 300 ml of toluene at room temperature. For this solution, 9
6. 15% of 0% by weight formic acid and 30% by weight of aqueous hydrogen peroxide
What had previously been mixed with 5 g was added dropwise over about 1 hour while stirring vigorously at room temperature, and stirring was further continued at 30 ° C. for 2 hours. The polymer solution was poured into a large amount of methanol to precipitate a polymer, which was separated by filtration and washed with acetone. When the collected solid product was dried under reduced pressure, 4.7 g of a modified copolymer was obtained.

This modified copolymer was obtained by the IR method and ¹³ C--N
It was confirmed by the MR method that an epoxy group was introduced into the copolymer. According to ¹³ C-NMR, the conversion of unsaturated bonds in the copolymer to epoxy groups was 100 mol%. Also, the glass transition temperature Tg of this modified copolymer
Was 178 ° C. and the total light transmittance was 91%. The molecular weight of the modified copolymer was not different from that before the epoxy group introduction reaction.

Therefore, as can be seen from the comparison with Comparative Example 1 shown below, the modified copolymer of this example is a hydrogenated modified copolymer using a raw material (unsaturated copolymer A) having the same Tg. 45 ° C. higher than Tg. Further, the total light transmittance is greatly improved as compared with the raw material unsaturated copolymer A used in this example.

Comparative Example 1 The unsaturated copolymer A 5.0 obtained in Reference Example 1 was placed in a stainless steel autoclave having an internal volume of 1 L and equipped with a stirrer.
g, 300 ml of cyclohexane and 1.0 g of palladium-supported carbon (supporting 5% by weight of palladium) were successively added at room temperature, and sufficiently replaced with hydrogen gas. Next, the pressure was increased to 6.9 MPa with hydrogen gas, and the reaction was performed at 140 ° C. After reacting for 5 hours while replenishing the consumed hydrogen gas, the remaining gas was released. After removing the catalyst from the reaction solution by filtration, the filtrate was poured into a large amount of 2-propanol to precipitate a polymer. Subsequently, the solid product was separated by filtration, washed and dried.

The obtained solid product was analyzed by IR method and ¹³ C--N
The measurement by the MR method confirmed that the unsaturated bonds in the copolymer were hydrogenated. The modified copolymer, hydrogenation rate of unsaturated bonds by ¹³ C-NMR method is 10
It was 0 mol%. Further, Tg was 133 ° C. and total light transmittance was 90%. The molecular weight was not different from that before hydrogenation.

Example 2 A polymer was modified in the same manner as in Example 1 except that the unsaturated copolymer A was changed to the unsaturated copolymer B. 4.3 g of the modified copolymer was obtained, and the conversion of unsaturated bonds in the copolymer to epoxy groups was 100 mol%. Also,
Tg was 112 ° C. and total light transmittance was 90%.

Comparative Example 2 Hydrogenation was carried out in the same manner as in Comparative Example 1, except that the unsaturated copolymer A was changed to the unsaturated copolymer B, to obtain a modified copolymer. This modified copolymer had a hydrogenation ratio of unsaturated bonds in the copolymer of 100 mol% and a Tg of 83 ° C. The total light transmittance was 90%.

Comparative Example 3 An epoxidation reaction was carried out in the same manner as in Example 1 except that the unsaturated copolymer A in Example 1 was changed to the unsaturated copolymer C, and 3.8 g of the epoxidized modified copolymer was obtained. I got The conversion of unsaturated bonds into epoxy groups in the copolymer is 100 mol%
And the Tg was 56 ° C. The total light transmittance was 90%. As in this comparative example, DCP was used as a raw material.
When an unsaturated copolymer having a low D content is used, Tg is low,
100 ° C. or less.

Example 3 1.0 g of the resin D obtained in Reference Example 4 was dissolved in toluene 60 at room temperature.
Dissolved in ml. To this solution was added 3 g of 90% by weight formic acid.
And 1.7 g of 30% by weight aqueous hydrogen peroxide were added dropwise at room temperature over about 1 hour. Then
Stirring was continued at 30 ° C. for a further 2 hours. The product was poured into a large amount of methanol to precipitate a polymer, which was separated by filtration, washed, and dried under reduced pressure to obtain 0.9 g of a modified copolymer. This modified copolymer had a conversion of unsaturated bonds in the copolymer to epoxy groups of 100 mol%. Also,
Tg was 204 ° C. and total light transmittance was 90%.

Example 4 5.0 g of unsaturated copolymer A was added at room temperature to 300 ml of toluene.
dissolved in l. Under reflux with heating, 15 g of 90% by weight formic acid and 7.5 g of 30% by weight aqueous hydrogen peroxide were previously added to this solution at room temperature. The mixture was added dropwise with stirring for about 1 hour. Reflux was continued for another 1 hour.
After neutralizing the reaction solution with alcoholic NaOH, it was poured into a large amount of methanol to precipitate a polymer. The solid product was treated in the same manner as in Example 1 to obtain 4.8 g of a modified copolymer.
It was confirmed by IR method and ¹³ C-NMR method that a hydroxyl group was introduced into the copolymer. Further, the conversion to the unsaturated bonds of the hydroxyl group in the copolymer by ¹³ C-NMR method 10
It was 0 mol%. The Tg of this modified copolymer is 175 ° C.
The total light transmittance was 90%. The molecular weight was not different from before the introduction of the hydroxyl group.

Example 5 5.0 g of unsaturated copolymer A was added at room temperature to 300 ml of toluene.
Dissolved in 1. While stirring this solution, 90% by weight
A mixture of 15 g of formic acid and 7.5 g of 30% by weight aqueous hydrogen peroxide was added dropwise at room temperature over about 1 hour. The reaction solution was poured into a large amount of methanol to precipitate a polymer, which was treated in the same manner as in Example 1 to obtain a modified copolymer. The conversion of unsaturated bonds into epoxy groups in the modified copolymer was 42 mol%.

Next, 300 ml of this modified copolymer, 300 ml of toluene and 1.0 g of palladium-supported carbon (supporting 5% by weight of palladium) were placed in the autoclave used in Comparative Example 1.
Were sequentially added at room temperature, and after sufficiently replacing with hydrogen gas, the pressure was increased to 6.9 MPa with hydrogen gas, and the mixture was heated at 140 ° C. After reacting for 3 hours while replenishing the hydrogen gas consumed by the reaction, the remaining gas was released. The resulting reaction solution was post-treated in the same manner as in Comparative Example 1 to obtain a modified copolymer.

The unsaturated bonds in the modified copolymer remaining after the epoxidation reaction were all hydrogenated. This modified copolymer had a Tg of 152 ° C. and a total light transmittance of 91%. That is, Tg is higher than that of Comparative Example 1 in which only the hydrogenation modification was performed using the same unsaturated copolymer.

Example 6 The procedure of Example 5 was repeated, except that the mixture of formic acid and hydrogen peroxide was added dropwise, and stirring was continued for another hour, followed by epoxidation in the same manner as in Example 5, followed by hydrogenation.

The resulting modified copolymer had a conversion of unsaturated bonds in the copolymer to epoxy groups of 82 mol%,
All unsaturated bonds remaining after the epoxidation reaction were hydrogenated. This modified copolymer has a Tg of 166.
At ℃, the total light transmittance was 91%.

Table 2 summarizes the results of the above examples. As is clear from Tables 1 and 2, the epoxy group and / or hydroxyl group-containing copolymer according to the present invention has excellent hue, transparency and heat resistance as compared with the unsaturated copolymer of Reference Example. In addition, it shows superior heat resistance as compared with the hydrogenation-modified copolymer shown in Comparative Examples.

[Table 2]

[0073]

The modified ethylene copolymer according to the present invention is obtained by using an unsaturated copolymer obtained from a highly versatile monomer as a raw material, into which an epoxy group and / or a hydroxyl group are introduced and hydrogenated. By denaturation. As a result, a molded article obtained from the modified ethylene copolymer exhibits excellent hue and transparency, and also exhibits excellent heat resistance.

Continued on the front page F term (reference) 4J100 AA02P AA03R AA04R AA07R AA16R AA17R AA19R AR22Q BA03H BC28Q BC54H CA05 CA31 HA03 HA61

Claims (2)

[Claims] 1. An unsaturated bond-containing ethylene copolymer obtained by copolymerizing ethylene or ethylene and an α-olefin with at least one cyclic diene selected from dicyclopentadiene, methyl-substituted dicyclopentadiene and tricyclopentadiene. 10 mol% of unsaturated bonds contained in the ethylene-based copolymer with respect to the polymer (however, the content of the cyclic diene unit is 20 to 70 mol%)
An epoxy group and / or a hydroxyl group is introduced as described above, and the remaining unsaturated bond is a hydrogenated polymer having physical properties (a) having a weight average molecular weight of 20,000 to 1,000,000.
00, (b) a modified ethylene copolymer having a glass transition temperature of 100 ° C. or higher and (c) a total light transmittance of 90% or higher. 2. An unsaturated bond-containing ethylene copolymer obtained by copolymerizing ethylene or ethylene and an α-olefin with at least one cyclic diene selected from dicyclopentadiene, methyl-substituted dicyclopentadiene and tricyclopentadiene. For the polymer (however, the content of the cyclic diene unit is 20 to 70 mol%)
(1) After introducing an epoxy group and / or a hydroxyl group into a part or all of the unsaturated bonds contained in the ethylene-based copolymer, hydrogenating the remaining unsaturated bonds, or (2) After hydrogenating some of the unsaturated bonds contained in the copolymer, an epoxy group and / or a hydroxyl group are introduced into all of the remaining unsaturated bonds, and the unsaturated polymer contained in the ethylene copolymer is introduced. A method for producing a modified ethylene copolymer, characterized in that an epoxy group and / or a hydroxyl group is contained in 10 mol% or more of the bond.