JPH04170453A - Cycloolefin resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]
Cyclic olefin resin composition with excellent balance of scratch resistance.

ABS resins (acrylonitrile, butadiene, styrene resin) have been widely used as raw material resins for molded products in applications such as automatic office equipment and miscellaneous goods. ：、、ABS resin is inferior and has excellent heat resistance, rigidity, and dimensional accuracy. However, it has poor light resistance, and the resin deteriorates after long-term use. Mechanical strength decreases. There's a problem.

On the other hand, crystalline polypropylene and the like are used as resins with excellent light resistance, but there are problems in that they are inferior in heat resistance, rigidity, dimensional accuracy, etc. compared to ABS resins.

By the way, cyclic olefins having an ethylenic double bond in the ring have polymerizability, and can react with a-olefins such as ethylene to form cyclic olefins and a-
It is known that an olefin random copolymer can be obtained (see Japanese Patent Application No. 60-26024).

These cyclic olefin-based random copolymer compounds have excellent heat resistance and scratch resistance, and by taking advantage of these characteristics, they can be used as resins suitable for molding materials such as automatic equipment, tOA machine miscellaneous goods, etc. However, the impact resistance of cyclic olefin random copolymers alone is insufficient, and to improve this, compositions with rubber-like elastic bodies are already known (Japanese Patent Application Laid-Open No. -167318
). However, there is a demand for a composition with a better balance of physical properties that substantially maintains the impact resistance of such compositions and has excellent rigidity, scratch resistance, etc.

The present invention was made in view of the above problems, and provides a cyclic olefin resin composition with an excellent balance of heat resistance, impact resistance, rigidity, strength, moldability, and scratch resistance. is intended to provide.

irim Cyclic olefin resin composition storage [A] (a
) 100 parts by weight of at least one cyclic olefin polymer selected from the group consisting of the following groups (a) to (:); and (b) an elastic modulus of 0.1 kg/cm2 to 20,000 kg.
/ cm', and the glass transition point (Tg) is 0°C or lower,
Rubber-like elastic body with crystallinity of 30% or less 30.5-5
(c) crosslinking agent; a reaction product obtained by contacting 0.01 to 1 part by weight with respect to a total of 100 parts by weight of components (a) and (b).

[B1 elastic modulus is 1 y/cm2 to 30000 kg/
cm2, a glass transition point (Tg) of 0°C or less, and a crystallinity of 30% or more Polyethylene or ethylene/a-olefin polymer 1 The above reaction product [A] 1
0.00 parts by weight to 0.5 to 50 parts by weight.

(a) A copolymer of ethylene and a cyclic olefin represented by the following formula [l] or [I゛], which has an intrinsic viscosity [η] of 0.05 to 10 a/m as measured in decalin at 135°C.
(b) Ethylene/cyclic olefin copolymer having a softening temperature (TMA) of 70°C or higher; (b) the following formula [
A ring-opening polymer of a cyclic olefin represented by I] or [■°], which has an intrinsic viscosity [η] measured in decalin at 135°C in the range of 0.05 to 10 dll/H, and has a softening temperature Cyclic olefin ring-opening polymer in which (TMA) is 70°C or higher: (c) A ring-opening copolymer of a cyclic olefin represented by the following formula [I or [I°], in decalin at 135°C. A cyclic olefin ring-opening copolymer having an intrinsic viscosity [η] measured in the range of 0.05 to 10 dQ/g and a softening temperature (TMA) of 70°C or higher; (d) the above (b) or (c); ) hydrogen additives.

・[lco(in the formula, n is O or 1, m is 0 or a positive integer, R1 to RI @ 11 each independently a hydrogen atom,
Represents an atom or group selected from the group consisting of a halogen atom and a hydrocarbon group RI s −R+ @IL May be combined with each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring is a double may have a bond, and Re5 and Re6 or R17 and R1 may form an alkylidene group).

... [I°] (In formula [I'], p is an integer of 0 or 1 or more, and q
and rl is 0, 1 or 2, and R1 to Ras each independently represent an atom or 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, , R' (or R
e) and Re (or Rma) and Tane may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group. ) Also, 1 Buri U (Hasashi J) Hereinafter, the cyclic olefin resin composition according to the present invention will be specifically explained.

Cyclic olefin resin composition IL of the present invention: a cyclic olefin polymer (a), a rubber-like elastic body (b), and a crosslinking agent (
It consists of a reaction product [A] with C) and an ethylene/a-olefin polymer [B].

In addition, when referring to a polymer in the present invention, the polymer is used with a concept including both a homopolymer and a copolymer.

Hereinafter, the cyclic olefin polymer (a), the rubber-like elastic body (b), the crosslinking agent (C), and the ethylene/a-olefin polymer will be explained in order.

Polymerization of olefin (a) Examples of the cyclic olefin polymer (a) used in the present invention include the polymers or copolymers listed in (a) to (d) below.

(b) Copolymerization of ethylene and cyclic olefin, which is a copolymer of ethylene and a cyclic olefin represented by the following formula [l] or [I゛] (b) The following formula [I] or [I°] (c) Ring-opening copolymerization of a cyclic olefin represented by the following formula [I] or [I'l (:) Hydrogenation of the above (b) or (c) thing.

These polymers or copolymers may be used alone or in combination.
More than one species can be used in combination.

As for the above-mentioned cyclic olefin polymers,
The tia viscosity [vl] measured in decalin at 135'C ranges from 0.05 to 10 dl/g and the softening temperature (
A cyclic olefin polymer having a TMA) temperature of 70° C. or higher is used.

... [lco (in the formula, n is 0 or 1, m is 0 or a positive integer, and R1-R1/Koji each independently - from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group) Represents a selected atom or group RI!-RIs L may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond, Mata, R'' and R'@ may form an alkylidene group, or Ra7 and R''+!: may form an alkylidene group).

... [I'] (In the formula [I'l, p is O or an integer of 1 or more, and q
and r is 0. 1 or 2, and R1 to RIS each independently represent an atom or 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. ．． R' (or Re) and R (or R7) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group. ) However, in the above formula [I], n is O or 1, preferably O. Moreover, m is 0 or a positive integer, preferably 0-3.

In the above formula [I°], p is an integer of 0 or 1 or more, preferably an integer of 0 to 3.

and R1-R111C formula [■]), or R1-R
15 (formula [I']) each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. Here, the halogen atom is
For example, fluorine atom, chlorine atom, bromine atom and iodine atom can be mentioned.

In addition, as a hydrocarbon group (each independently, usually an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms, specific examples of alkyl groups include methyl Groups include ethyl group, isopropyl group, isobutyl group, amyl group, and specific examples of cycloalkyl groups include cyclohexyl group, cyclopropyl group, cyclobutyl group, and cyclopentyl group.

Further, in the above formula [I'], R6 (or Re) and R
s (or R4) and mi may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group.

Sara & Mi In the above formula [I], Has~R1@ may be bonded to each other (together) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring has a double bond. You may do so. Also, with R116 and RIM, or R1"
and R111 may form an alkylidene group.

Such alkylidene groups usually have 2 to 4 carbon atoms.
Specific examples thereof include ethylidene groups, isopropylidene groups, and isobutylidene groups.

The cyclic olefin represented by the above formula [Ico or [I'] can be easily produced by condensing cyclopentadiene and the corresponding olefin or cyclic olefin by Diels-Alder reaction. can.

Specifically, the cyclic olefin represented by the above formula [I] or [r'] includes one bicyclo[2,2,11hept-2-ene derivative such as (hereinafter blank): Notetracyclo[4,4,0,1'-',1''']
-3-dodecene derivative; l!・1.01・14]-, i-hebutadecene derivative;
octacyf (7[8,8,0,1'-'', 14
．． ff, lIl, 1811″I@g!, 1.61
LIff] -]5-tococene derivative fis
-4-\Pentacyclo [6,6,1,1", 0", 0'-" such as xatecene
]-4-hexadecene derivatives; heptacyclo-5-eicosene derivatives such as heptacyclo-5-eicosene derivatives or hephtacyclo-5-heneicosene derivatives; tricyclo[4,3,0,1” ]-]3-decene derivatives such as 4,0,1" ] -] Pentacyclo[6-5,1,1"1 such as 3-undecene derivatives
．． 0'・? , OL+! ]-4-pentadecene derivatives; diene compounds such as: pentacyclo[7,4,0,1”・@, 11
11.01. Hl-3-pentadecene derivative: θth, 0th ratio Co-4-eicosene derivative; -5-bentacocene gth, 01. l11. QIH Mountain o 14.11]
−]s-bentacocene F conductor; such as heptacyclo[
Heptacyclo [8, 8, 0, 14, 7, 111,
11,11LIJL1. glLI? ]=5-heneicosene derivative; etc. Tsunonacyclo[I0,10,1,1", I"! 1
．． 111'1. OL I+.

04, @, ON, 1m. 01L! . ]-]5-hexacosene derivatives and furthermore, ! Ill 1 can be mentioned. (Left below) This cyclic olefin random copolymer (a), which is a copolymer of cyclic olefins and ethylene, has ethylene and the cyclic olefin as essential components7.
! In addition to lτ and the two essential components, other copolymerizable unsaturated monomer components may be contained as required, within a range that does not impair the terms of the present invention. Specifically, the unsaturated monomer which may be optionally copolymerized includes, for example, propylene, 1-butene, 4-methyl in an amount less than equimolar to the ethylene component unit in the random copolymer to be produced. −
a-olefins having 3 to 20 carbon atoms such as 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. can be exemplified.

Cyclic olefin random copolymer (a) as above
Then, the repeating unit (a) derived from ethylene is 40
The repeating unit (b) derived from the cyclic olefin is present in a range of 15 to 60 mol%, preferably 25 to 50 mol%.
The repeating units (a) derived from ethylene and the repeating units (b) derived from the cyclic olefin are randomly arranged substantially linearly. In addition, the ethylene composition and cyclic olefin composition are “
The fact that this cyclic olefin random copolymer is substantially linear, has a gel-like crosslinked structure, and has no v-balls, as measured by C-NMR, indicates that the copolymer is completely dissolved in decalin at 135°C. This can be confirmed by

The intrinsic viscosity [η]11 of such a cyclic olefin random copolymer (a) measured in decalin at 135°C
0.05-10.111/g, preferably 0.08
~5,111/H.

In addition, the softening temperature (T
MA) IL 70°C or less, preferably 90-250
℃, more preferably in the range of 100 to 200℃.

The softening temperature (TMA) L is Therm manufactured by DuPont.
.

The thermal deformation behavior of a sheet with a thickness of 1 crane was measured using a mechanical analyzer. That is, a quartz needle was placed on the sheet, a load of 49 g was applied, and the temperature was raised at a rate of 5°C/min. TM the temperature that entered
In addition, the glass transition temperature (Tg) of the cyclic olefin random copolymer is usually 50 to 230°C,
The temperature is preferably in the range of 70 to 210°C.

In addition, the crystallinity of this cyclic olefin random copolymer (a) measured by X-ray diffraction method is 10 to 10%,
The range is preferably from 0 to 7%, particularly preferably from 0 to 5%.

In the present invention, as the cyclic olefin polymer, other than the above-mentioned cyclic olefin random copolymer (a),
Ring-opened polymers (@, ring-opened copolymers (c)) of cyclic olefins represented by the formula [I co or [I°] or hydrogenated products (c) of these (c) can also be used. .

Cyclic olefin polymer (b) to (,1-), 135
Intrinsic viscosity [η], softening point (T) measured in decalin at ℃
MA), glass transition temperature (Tg), and crystallinity 1 are the same as for the crowned olefin random copolymer (a).

Cyclic olefin polymer used in the present invention 1 JP-A-60-168708 Publication JP-A-61-1208
16 revolution JP 61-115912 revolution JP 61-115916 revolution JP 62-252406
Revolution: JP-A-62-252407 Revolution: JP-A-61
It can be manufactured by appropriately selecting conditions according to the method proposed by the present applicant in JP-A-61-272216 and the like.

In such a cyclic olefin random copolymer (a), the structural unit (b) derived from the cyclic olefin represented by the above formula [I] or [I°] is represented by the following formula [n]
or [IIM] is considered to form a repeating unit of the structure.

... [n] (In formula [n], a, n and R1 to Rl 8 are the above formula [
It is the same as the definition in [I]. ) ...[n゛] (In formula [n'], ps qq r and R1-R1
5 is the same as the definition in the above formula [I'l. ) In the present invention, as mentioned above, in addition to the above-mentioned cyclic olefin random copolymer (a), a cyclic olefin ring-opened polymer obtained by ring-opening the same or different cyclic olefin monomers It is also possible to use ring-opened copolymers (c) or their hydrogenated products (:). Regarding (d), if we take the cyclic olefin represented by the above formula [I] as an example, it reacts as described below to form a ring-opened (co)polymer and a hydrogenated product thereof. Conceivable.

Examples of such polymers include ring-opening copolymers of tetracyclododecene and norbornene and their derivatives, and hydrogenated products thereof.

In addition, in the present invention, a part of the above-mentioned ring-opening polymerization, ring-opening copolymer, these hydrogenated products, and the cyclic olefin random copolymer is modified with an unsaturated carboxylic acid such as maleic anhydride. You can. Such a modified product can be produced by reacting a cyclic olefin resin as described above with an unsaturated carboxylic acid, an anhydride thereof, and a derivative such as an alkyl ester of an unsaturated carboxylic acid. In this case, the content of structural units derived from the modifier in the modified cyclic olefin resin is usually 50 to 10 mol%. 4L of such a modified cyclic olefin resin can be produced by blending a modifier with a cyclic olefin resin and graft polymerizing it to a desired modification rate, or by preparing a modified product with a high modification rate in advance. It can also be produced by subsequently mixing this modified product with an unmodified cyclic olefin resin.

In the present invention, these hydrogenated substances, cyclic olefin random copolymers, and modified products thereof can be used alone or in combination.

Furthermore, in the present invention, when producing the above-described cyclic olefin-based random copolymer, the formula [I] or [l'l] may be expressed as long as the physical properties of the resulting polymer are not impaired. Cyclic olefins other than cyclic olefins can also be polymerized. An example of such a cyclic olefin! , cyclobutene, cyclopentene, cyclohexene, 3.4-dimethylcyclohexeno, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, 2,
3.3a, ? a-metetrahytone-4,7-methano-
Examples include IH-indene, 3a, 5.6.7a-tetrahydro-4,7-methano-IH-indene, and the like. Such other cyclic olefins can be used alone or in combination, and are usually 0 to 50 mol% (7)
Quantity is used.

In addition, in the present invention, the intrinsic viscosity [η] measured in decalin at 135°C as described above is 0.05 to 10 tons/g.
In addition to a cyclic olefin polymer having a softening temperature (TMA) of 70° C. or higher, G″-135
Intrinsic viscosity measured in decalin at ℃ [η is 0.05~
Other cyclic olefin polymers having a softening temperature (TMA) of less than 70° C. and a softening temperature (TMA) of less than 70° C. may be used.

Rubber-like elastic body used in the present invention (b) has a modulus of elasticity of O,ltg/cm2 to 20000kg/cm2
and preferably 10 kg/cm2 to 15000 kg
/cm2, particularly preferably 10kg/cm2 to 1
0000 kg/cm2. For the elastic modulus, the test piece shape is based on ASTM TYPE rv, and the thickness is 2 mm.
This is a value measured with a tension speed of 50mmZ between the chucks and L chucks.

The glass transition temperature (Tg
) 44 Usually below 0°C, preferably below -10°C,
More preferably, the temperature is within the range of -20°C or lower. Intrinsic viscosity [I] of this rubbery elastic body (b) measured in decalin at 135°C If, 0.01 to 10aI
I/g, preferably 0.08 to 7 aa/g.

Crystallinity of this rubbery elastic body (b) measured by X-ray diffraction method is usually 30% or less, preferably 20% or less, and this rubbery elastic body (b) IL
It is preferable that it has low crystallinity or poor quality.

Specifically, the rubber-like elastic body (b) used in the present invention includes ethylene/a-olefin copolymer comb, propylene/
An example is a-olefin copolymer rubber. The above ethylene/a-olefin copolymer rubber and propylene/
The a-olefin copolymer rubber can be used alone or in combination.

The a-olefin constituting the above ethylene/a-olefin copolymer comb usually has 3 to 20 carbon atoms.
-Olefins, such as propylene, 1-butene, 1-
Pentene, 1-hexene, 4-methyl-1-pentene,
Mention may be made of 1-octene, 1-decene and mixtures thereof. Among these, α-olefins having 3 to 10 carbon atoms are particularly preferred.

In addition, the a-olefin constituting the propylene/a-olefin copolymer rubber is usually a-olefin having 4 to 20 carbon atoms.
-olefins, such as 1-butene, 1-pentene,
Mention may be made of 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. Among these, α-olefins having 4 to 10 carbon atoms are particularly preferred.

Note that the a-olefin copolymer 14 used in the present invention
Within the range that does not impair the properties of the a-olefin copolymer, a component such as a component unit derived from a diene compound, etc.
- May contain component units other than those derived from olefins.

For example, the component units that are allowed to be included in the a-olefin copolymer used in the present invention are: 1,
Chain nonconjugated dienes such as 4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-hebutadiene, 7-methyl-1;6-octadiene ; Cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene,
Cyclic non-conjugated dienes such as 6-chloromethyl-5-isopropenyl-2-norbornene.

2.3-diisopropylidene-5-norbornene, 2-
Examples include component units derived from diene compounds such as ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene. Such diene components can be used alone or in combination. The content of such diene components is usually 1 to 20 mol%, preferably 2 to 15 mol%.

In the ethylene/a-olefin copolymer used in the present invention, the molar ratio of ethylene to a-olefin (ethylene/me-olefin) varies depending on the type of a-olefin, but is generally 1799 to 99/1. , preferably 30/70 to 95,4-11.

In addition, in the propylene/α-olefin copolymer used in the present invention, the molar ratio of propylene to α-olefin (propylene/α-olefin) varies depending on the type of α-olefin, but is generally 30/ 70
It is preferable that it is 9515-9515.

In the present invention, among the a-olefin copolymers described above, ethylene/propylene random copolymers or ethylene/a-olefin random copolymers with an ethylene content of 30 to 95 mol% and a crystallinity of 10% or less are preferred. Particular preference is given to using coalescence.

Furthermore, as the rubber-like elastic body (b) used in the present invention,
A graft-modified me-olefin copolymer obtained by graft-modifying the above a-olefin copolymer with an unsaturated carboxylic acid or a derivative thereof can also be used. Graft-modified a-olefin copolymers are preferred because they are excellent in improving mechanical properties such as impact strength.

It is preferable to use an unsaturated carboxylic acid or a derivative thereof as the graft monomer used to produce the above-mentioned graft-modified α-olefin copolymer. Examples of such unsaturated carboxylic acids include (acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid (endocys-bicyclo[2,2,
1] hept-5-ene-2,3-dicarboxylic acid). Sara & Mi As derivatives of the above unsaturated carboxylic acids, there may be mentioned unsaturated carboxylic acid anhydrides, unsaturated carboxylic acid halides, unsaturated carboxylic acid amides, unsaturated carboxylic acid imides, and ester compounds of unsaturated carboxylic acids. . Specific examples of such derivatives include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate.

These graft monomers can be used alone or in combination.

Among the graft monomers mentioned above, unsaturated dicarboxylic acids or their acid anhydrides are preferred, and maleic acid, nadic acid, or their acid anhydrides are particularly preferred.

Graft-modified olefin copolymer used in the present invention (1) For example, it can be produced by modifying the above-mentioned graft monomer and a-olefin copolymer using various conventionally known methods. can. For example, there is a method of melting the a-olefin copolymer and adding a graft monomer to carry out graft polymerization, or a method of dissolving the a-olefin copolymer in a solvent and adding a graft monomer to carry out graft copolymerization. As a method for producing a graft-modified olefin copolymer, IL unmodified a-
A method of modifying an olefin copolymer by blending a graft monomer to achieve a desired graft modification rate, in which a graft-modified olefin copolymer with a high graft modification rate is prepared in advance and this a-olefin copolymer with a high graft modification rate is prepared. There is a method for producing a graft-modified a-olefin copolymer having a desired modification rate by diluting the copolymer with an unmodified a-olefin copolymer. - In the present invention, a graft-modified olefin copolymer produced by any of the IL methods can also be used. The graft modified meolefin copolymer used in the present invention has a modification rate of usually 0.01.
-5% by weight, preferably 0.1-4% by weight of the copolymer.

In order to efficiently graft copolymerize the above-mentioned graft monomer, it is preferable to carry out the reaction in the presence of a radical initiator.

The graft reaction is usually carried out at a temperature of 60 to 350°C.

The proportion of the radical initiator used is usually in the range of 0.001 to 5 parts by weight per 100 parts by weight of the unmodified a-olefin elastomeric copolymer.

As the radical initiator, organic peroxides and organic peresters are preferably used. Specific examples of the radical initiators include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2. 5-dimethyl-2,5-di(peroxidebenzoate)hexyne-al, 4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert
-butyl peracetate, 2,5-dimethyl-2,5-
Di(tert-butylperoxy)hexyne mother 2.5
-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylperbenzoate, te
rt-butyl perphenylacetate, tert-butyl perisobutyrate, tert-butylperu 5ec
-octoate, tert-butyl perbivalate, cumyl perpivalate and tert-butyl perdiethyl acetate. Further, in the present invention, an azo compound can also be used as a radical initiator, and specific examples of the azo compound include C azobisisobutyronitrile and dimethyl azoisobutyrate.

Among these, as a radical initiator, benzoyl peroxide, dicumyl peroxide, ditert
-butyl peroxide, 2,5-dimethyl-2,5-
Di(tert-butylperoxy)hexyne 2.5-
Dimethyl-2,5-di(tert-butylperoxy)
Dialkyl peroxides such as hexane and 1,4-bis(tert-butylperoxyisopropyl)benzene are preferably used.

Graft modified olefin copolymer used in the present invention Usually, the above-mentioned graft modified ethylene/a-olefin copolymer and graft modified propylene/a-olefin copolymer are used alone or in combination. The graft-modified elastic copolymer may contain other polymers or copolymers, or other graft copolymers within a range that does not impair the properties of the graft-modified olefin elastic copolymer.

In the present invention, examples of such other polymers or copolymers include IL aromatic vinyl hydrocarbon/conjugated diene copolymer or hydride thereof. Specifically, such aromatic vinyl hydrocarbon/conjugated diene copolymers or their hydrides include styrene/butadiene co-X polymer rubber, styrene/butadiene/styrene copolymer rubber, and styrene/isoprene block copolymer. Coalcomb, styrene/isoprene/styrene block copolymer rubber, hydrogenated styrene/butadiene/styrene block copolymer rubber, and hydrogenated styrene/isoprene/styrene block copolymer rubber
Mention may be made of styrene block copolymer rubber.

In the present invention, the rubber-like elastic body (b) as described above is used.
It is used in an amount of 0.5 to 50 parts by weight, preferably 1 to 40 parts by weight, per 100 parts by weight of the cyclic olefin polymer (a). In addition, the crosslinking agent (C) described later is (ω,
It is used in an amount of 0.01 to 1 part by weight or 0.05 to 0.5 part by weight per 100 parts by weight of component (b).

As the crosslinking agent (C) used in producing the reaction product [AI], organic peroxides and cationic polymerization initiator amino group-containing compounds can be preferably used.

When bringing components (a) to (C) into contact: Crosslinking agent (C)
is used in an amount of 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, per 100 parts by weight of the above components (a) and (b). As the contacting method, a known method can be applied, and for example, it is preferable to mix the components (a) and (b) with a force that allows the components to be mixed simultaneously, and then mix the component (c). In addition, the component (C) is (ω,
When mixed with component (b), it is preferable that component (C) is also sufficiently mixed.

Composition of components (a) and (b) A method of manufacturing components (a) and (b) separately and blending them with components (a) and (b) using an extruder, or (a), (b) Add the component to a suitable latent arc, such as heptane, hexane, decane,
Saturated hydrocarbons such as cyclohexane can be obtained by solution blending by sufficiently dissolving them in aromatic hydrocarbons such as toluene, benzene, and xylene, or by synthesizing components (8) and (b) in separate polymerization vessels. It can be manufactured by a method such as blending polymers in a separate container. To the thus obtained composition of components (a) and (b), component (C) is added and blended to obtain a reaction product [AI].

The reaction product [AI] can be obtained by reacting at a temperature at which the crosslinking agent of component (c) decomposes or reacts.

The organic peroxide and the amino group-containing compound that initiates cationic polymerization will be explained using specific examples.

(Specifically, the organic peroxides include ketone peroxides such as +L methyl ethyl ketone peroxide and cyclohexanone peroxide; 1,1-bis(t-butylperoxy)cyclohexane, 2,2- Peroxyketals such as bis(t-butylperoxy)octane; t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroxyperoxide, 1,1,3.3 -Hydroperoxides such as tetramethylbutyl hydroperoxide
-Dialkyl peroxides such as butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and 2,5-dimethyl-2,5-(t-butylperoxy)hexyne-3 diacyl peroxides such as lauroyl peroxide and benzoyl peroxide; Examples include oxyesters. Such organic peroxides are 1
One species can be used alone or two or more species can be used in combination. In addition, when using the above organic peroxide, iL
It is preferable to use a compound having two or more radically polymerizable functional groups in the molecule. Examples of compounds having two or more radically polymerizable functional groups in the molecule include divinylbenzene, vinyl acrylate, vinyl methacrylate, triaryl isocyanurate, diaryl phthalate, ethylene dimethacrylate, and trimethylolpropane trimethacrylate. I can do it.

Cationic polymerization piece j As the above cationic polymerization initiator, “Toshinobu Higashimura, Lecture on Polymerization Reaction Theory 3 View ° Cationic Polymerization °, Kagaku Doujin, 19
The starting i1L listed in Chapter 2 of 1974 includes protic acids, metal oxides, halogens, metal halides, organometallic compounds, and stable cations. Among these, protic acids and metal halides are preferred. Version as protonic acid Specific NihaH, POi, H2SO,, HCQ
Os, HCtt, HB r , CCQ z CO
2H, CHCit2COeH.

CF, CO, H, H (CFa), (o2) 1°CQS
Examples include Os', ya F S OsH-p-) luenesulfone 1CF, SO, H, CH, C0CQ 04 (A 7-h methyl chlorate). In addition, as metal halides, 4L Be, Mg, Zn, Cd
, Hg, B.

11, Ga, Ti, Zr, Sn, P, Sb
, Nb, Bi, Ta, U.

Examples include halides of metals such as Re and Fe.Among these, B, Am, Ti, Sn, and Fe are particularly suitable.
halides are preferred. Specifically, boron trifluoride (BF3), boron trifluoride/diethyl ether complex (BFsO(C2H5)2), boron trifluoride/phenol complex (BF, .HOC6Ha), -Formula R1A
9X, an organoaluminum compound represented by -□ (X is salt, odor, iodine or fluorine, n is 0≦n<'
3, R represents an alkyl group), titanium tetrachloride (TiCQ,) tin tetrachloride (SnCRa), iron trichloride (
Examples include F e CB 3).

Said R7AQX3-. As an organoaluminum compound represented by +L, for example, diethylaluminum chloride, diethylaluminium bromide, ethylaluminum sesquichloride, ethylaluminum sesquipromide,
Examples include ethylaluminum dichloride and ethylaluminum dichloride. Composition is R, AΩX3-7
Mixtures of various organoaluminum compounds may be used as long as they are compatible.

These cationic polymerization initiators can be used alone or in combination of two or more.

Amino Group As the polymerized amino group-containing compound, a compound having at least two amino groups in the molecule can be used.

Such amino group-containing compounds include, for example, ethylenethiamis propylene diamine, hexamethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, iminobispropylamine, bis(hexamethylene) triamine, 1.3
．． 6-) Aliphatic amines such as risaminomethylhexane, trimethylhexamethylenediamine, diethylene glycol, bispropylenediamine, and diethylaminopropylamine.

menzendiamine, isophoronediamine, bis(4-
Alicyclic amines such as amino-3-methylcyclohexyl)methane, N-aminoethylpiperazine, 1,3-diaminocyclohexane; Fatty aromatic amines such as metaxylylenediamine; 0-1IP, p-phenylenediamine, diaminodiphenylmethane , diaminodiphenylsulfone, 2.4
-Diaminoanisole, 2.4-) Luenediamine, 2
．． Aromatic amines such as 4-diaminodiphenylamine, 4.4'-methylene dianiline, diaminodiphenylsulfone: 3.9-bis(3-aminopropyl) -2,4,8,
Bisspiro ring diamines such as 10-tetraspiro[5,5]undecane and the like can be mentioned.

Such amino group-containing compounds can be used alone or in combination of two or more.

Polyethylene or ethylene/a-olefin 10
1. The cyclic olefin resin composition according to the present invention has the above-mentioned (a)
It consists of a reaction product [A] obtained by contacting components (c) with polyethylene or an ethylene/a-olefin copolymer [BF]. polyethylene or ethylene/α-olefin copolymer [BF is the reaction product [A31
0.5 to 50 parts by weight, preferably 1 to 50 parts by weight
It is used in an amount of 40 parts by weight.

The polyethylene or ethylene/a-olefin copolymer used in the present invention [BF has an elastic modulus of 1 kg
/cm2 to 30000kg/cm2, preferably 101qi! /cm2 to 20000kg/cm2, particularly preferably 10kg/cm2 to 15000kg/cm2
cm2.

Ethylene/a-olefin copolymer [B
Glass transition temperature (Tg) L of F is usually in the range of 0°C or lower. Furthermore, the intrinsic viscosity [η] of this ethylene/a-olefin copolymer [BF measured in decalin at 135°C is 0.01 to 10a9/g, preferably 0
．． It is desirable that it is 08-7an 7g. moreover,
The crystallinity of this polyethylene or ethylene/a-olefin copolymer [BF measured by X-ray diffraction method] is about 30% or more.

Among the above, α-olefins constituting the ethylene/α-olefin copolymer are usually a-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1
-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. Among these, especially a- having 3 to 10 carbon atoms
Olefins are preferred.

The polyethylene or ethylene/a-olefin copolymer [B] used in the present invention may be derived from a diene compound within a range that does not impair the properties of the polyethylene or ethylene/a-olefin copolymer [B]. It may also contain component units other than those derived from a-olefins, such as component units derived from a-olefins.

For example, the component units allowed to be included in the polyethylene or ethylene/a-olefin copolymer [B] used in the present invention include ζk 1.4-hexadiene, 1.6-octadiene, 2-methyl-1 , 5-hexadiene, 6-methyl-1,5-hexadiene, linear non-conjugated dienes such as 7-methyl-1,6-octadiene: cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5 -ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-impropylidene-2-norbornene,
Cyclic non-conjugated dienes such as 6-chloromethyl-5-isopropenyl-2-norbornene.

2.3-diisopropylidene-5-norbornene, 2-
Examples include component units derived from diene compounds such as ethylidene-3-inpropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene. Such diene components can be used alone or in combination. The content IL of such diene components
It is usually 1 to 20 mol%, preferably 2 to 15 mol%.

In the ethylene/α-olefin copolymer [B] used in the present invention, the molar ratio of ethylene and a-olefin (ethylene/molefin) varies depending on the type of a-olefin, and is generally 1. /99~99
/1, preferably 50/50 to 9515.

The above molar ratio is preferably from 50,150 to 90/10 when the a-olefin is propylene, and from 80/20 to 9,515 when the a-olefin is an α-olefin having 4 or more carbon atoms. It is preferable that there be.

Furthermore, as the polyethylene or ethylene/a-olefin copolymer [B] used in the present invention, the above polyethylene or a-olefin copolymer,
Graft-modified polyethylene or graft-modified ethylene/a-olefin copolymer graft-modified with an unsaturated carboxylic acid or a derivative thereof can also be used.

Graft-modified polyethylene or graft-modified ethylene/a-olefin copolymer is preferred because it is excellent in improving mechanical properties such as impact strength.

As the graft monomer used to produce the above-mentioned graft-modified polyethylene or graft-modified meolefin copolymer, it is preferable to use the above-mentioned unsaturated carboxylic acid or its derivative.

And 1 piece of graft modified polyethylene or graft modified ethylene/a-olefin copolymer preferably used in the present invention Modification ratio usually 0.01
-5% by weight, preferably 0.1-4% by weight of the copolymer.

Such a reaction is preferably carried out in the presence of a radical initiator in order to efficiently graft copolymerize the graft monomer.

The graft reaction is usually carried out at a temperature of 60 to 350 t.

The proportion of the radical initiator used is usually in the range of 0.001 to 5 parts by weight per 100 parts by weight of unmodified polyethylene or unmodified ethylene/a-olefin copolymer.

As the radical initiator, organic peroxides and organic esters are preferably used.These are specific examples of radical initiators. I can give an example.

The above-mentioned graft-modified elastic copolymer may contain other polymers within the range (without impairing its properties) to the graft-modified polyethylene or graft-modified ethylene/a-olefin copolymer used in the present invention. It may also contain polymers or other graft copolymers.

In the present invention, examples of such other polymers or copolymers include jL aromatic vinyl hydrocarbon/conjugated diene copolymer or a hydride thereof. Specifically, an aromatic vinyl hydrocarbon/conjugated diene copolymer or a hydride thereof that can be added to the above-mentioned rubber-like elastic body can be exemplified.

In the cyclic olefin resin composition according to the present invention, the polyethylene or ethylene/a-olefin copolymer [B]jL as described above and the reaction product [A1100 obtained by contacting the components (a) to (C) above] It is used in an amount of 0.5 to 50 parts by weight, preferably 1 to 40 parts by weight.

In addition, the cyclic olefin resin composition 1 according to the present invention may be blended with a rubber component to improve impact strength, heat-resistant stabilization, weather-resistant stabilization, anti-static shelving, anti-slip shelving, anti-blocking shelving, anti-fog shelving, slipping shelving, dyes, pigments, Natural sources Synthetic methods Wax etc. can be blended, and the blending ratio is appropriate. For example, as a stabilizer that may be added as an optional ingredient, tetrakis[methylene-3
(3゜5-di-t-butyl-4-hydroxyphenyl)
Propionate comethane, β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid alkyl ester, 2.2°-oxamidobis[ethyl-3<3
．． Phenolic antioxidants such as 5-di-t-butyl-4-hydroxyphenyl) copropionate, fatty acid metal salts such as zinc stearate, calcium stearate, and calcium 12-hydroxystearate, glycerin monostearate, glycerin monolaurate, and glycerin Examples include fatty acid esters of polyhydric alcohols such as distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. These may be blended alone or in combination;
Examples include a combination of t-butyl-4-hydroxyphenyl)propionate comethane, zinc stearate, and glycerin monostearate.

In the present invention, it is preferable to use a combination of a phenolic antioxidant and a fatty acid ester of a polyhydric alcohol.
It is preferable to use a polyhydric alcohol fatty acid ester in which a part of the alcoholic hydroxyl groups of a polyhydric alcohol having a higher valence or higher are esterified.

As a fatty acid ester of such polyhydric alcohol, GL
Specifically, glycerin fatty acid esters such as glycerin monostearate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate, and glycerin dilaurate, pentaerythritol monostearate, pentaerythritol monolaurate, and pentaerythritol monolaurate. Fatty acid esters of pentaerythritol such as erythritol dilaurate, pentaerythritol distearate, and pentaerythritol tristearate are used.

Such a phenolic antioxidant is used in an amount of 0 to 10 parts by weight, preferably 0 to 5 parts by weight, and more preferably 0 to 2 parts by weight, based on 100 parts by weight of the cyclic olefin resin composition. The amount of fatty acid ester of polyhydric alcohol is 0 based on 100 parts by weight of the cyclic olefin resin composition.
~10 parts by weight Preferably used in an amount of 0 to 5 parts by weight.

In the present invention, 11 silica, diatomaceous earth,
Alumina, titanium oxide, magnesium oxide, pumice grains, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, Contains fillers such as glass fiber, glass flakes, glass peas, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, and polyamide fiber. You can.

The cyclic olefin resin composition as described above is a polymer that exhibits excellent properties as described above. I can do it. Examples of polymers that can be blended into the cyclic olefin resin composition include the following (1) to (17).

(1) Polymers derived from hydrocarbons having one or two unsaturated bonds, specifically? L For example, polyethylene, polypropylene, polymethylbutene-1, poly4-methylpentene-1
, polyolefins such as polybutene-1 and polystyrene. Note that these polyolefins may have a crosslinked structure.

(2) Halogen-containing vinyl polymers, specifically polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene, chlorinated rubber, etc. (3) Polymers derived from ff, β-unsaturated acids and their derivatives For example, acrylonitrile-butadiene-styrene copolymerization image. Styrene/acrylic acid ester copolymer, etc.
(4) Polymerization derived from unsaturated alcohols and amines or their acyl derivatives or acetals, specifically polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, (5) Polymerization derived from epoxide, specifically polyethylene oxide or bis Polymers derived from glycidyl ethers, etc. (6) Polyacetals, specifically polyoxymethylene, polyoxyethylene,
such as polyoxymethylene containing ethylene oxide as a comonomer, (7) polyphenylene oxide, (8) polycarbonate, (9) polysulfone, (10) polyurethane and urea resin, (11)
Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or aminocarboxylic acids or corresponding lactams, in particular nylon 6, nylon 66, nylon 11, nylon 12, etc. (12) dicarboxylic acids and dialcohols and/or
or polyesters derived from oxycarboxylic acids or corresponding lactones, in particular polyester terephthalate, polybutylene terephthalate, poly1,4-dimethylol cyclohexane terephthalate, etc. (13) derived from aldehydes and phenols, urea or melamine. Polymerization with a crosslinked structure Specifically, phenol/formaldehyde resin, urea/formaldehyde resin, melamine/formaldehyde resin, etc. (14) Alkyd resin, specifically glycerin/phthalate resin, etc. (15) Saturated and Unsaturated polyester resins derived from copolyesters of unsaturated dicarboxylic acids and polyhydric alcohols and halogen-containing modified resins obtained by using vinyl compounds as crosslinking agents, (16) natural type composites, specifically cellulose , rubber, protein, or derivatives thereof such as cellulose acetate, cellulose propionate, cellulose ether, etc. (17) A soft polymer or copolymer consisting of inbutylene or inbutylene/conjugated diene, specifically ζ-based polyisobutylene rubber, These include polyisoprene rubber, polybutadiene rubber, and isobutylene/isoprene copolymer rubber.

As a method for producing the cyclic olefin resin composition according to the present invention, known methods can be applied, and the reaction product [A] obtained by contacting the components (a) to (C) with polyethylene or ethylene a- Olefin copolymer [B]
, as well as other components added as desired, using an extruder, kneader, etc., or blend each component in a suitable latent arc, such as hexane, heptane, decane, etc.
Examples include a method of simultaneously dissolving in a hydrocarbon solvent such as cyclohexane, benzene, toluene, xylene, etc., or a method of dissolving each separately and then mixing and removing the solvent, and a method of combining these two methods.

According to the present invention, it is possible to provide a cyclic olefin resin composition that has excellent heat resistance, impact resistance, rigidity, strength, moldability, and scratch resistance. In addition, the cyclic olefin resin composition 1 according to the present invention not only has excellent properties as described above, but also has remarkable thermal adhesion to different materials such as various resins and metals, so it can be used in lamination with various resins. Wood Can be suitably used for applications such as metal coating. Specifically, the following examples (1) to (3) include automobile parts and machine housings, machine parts, gaskets for other building materials, waterproof sheets for civil engineering and construction, industrial hoses and tubes, housings for home appliances, etc. For sports &
It can be widely used for office supplies and other purposes.

(1) Automotive parts Instrument panels, console boxes, door trims, pillars, meter clusters, column covers, grill door mirrors, fenders, bonnets, radiator grills, side protection moldings, bumpers, soft fascias, mudguards, glass run channels,
windshield gasket.

(2) Machine housing tools (power tools), office equipment (word processors, personal computers, copiers, printers, FDD, CRT), precision equipment (cameras), home appliances (microwave ovens, electric kettles, refrigerated pots, cleaning machine).・(3) Sirocco fan for mechanical parts air conditioners.

[Examples] The present invention will be explained below with reference to Examples. The present invention is not limited to these Examples. In addition, the measuring method and evaluation method of various physical property values in this invention are shown next.

(1) Preparation of test piece The test piece was molded under the following molding conditions using an injection molding machine 15-55 manufactured by Toshiba Machine Co., Ltd. and a specified mold for test pieces.The test piece was left at room temperature for 48 hours after molding and was then subjected to measurement immediately. Molding conditions: Cylinder temperature 270°C, mold temperature 70°C, injection pressure primary/secondary = 1000/600 kg/cm, injection speed (-) 30 m/s, screw rotation speed 150 r, 4 cycles ([injection + maintenance]). (Pressure]/cooling) = 77155ec (2) Bending test Performed according to ASTM D790.9 Test piece shape: 5 x 1/2 x 1/8' inches, distance between spans 51° Test speed: 20 m, 7 minutes Test temperature = 23°C ( 3) Izotsu impact test Test conducted in accordance with ASTM D256 Test piece shape: 5/2 x 1/2 went.

Test piece shape: 5X1/4X1/2' inch Load: 264psi (5) Softening temperature (TMA) Thermo Mechanical A manufactured by DuPont
Using a nalyzer, the thickness is 1. In other words, a quartz needle was placed on the sheet, a load of 49 g was applied, the temperature was increased at a rate of 5°C/min, and the temperature at which the needle penetrated 0.635 m was measured by TMA binding. (6)
Melt Flow Index (MFR2ae'C) ASTM D123
(7) Rockwell hardness (R scale) ASTM D7 measured at a temperature of 260°C and a load of 2.16-
85 was followed.

Component (a) contains ethylene content of 62 mol% as measured by C-NMR, MF Ra5s'C7.8 g/10 minutes, and intrinsic viscosity [η of 0.6 as measured in decalin at 135°C.
1dlm Softening temperature (TMA) 147℃, 7g136
Ethylene and 1.4.5.8-dimethano-1,2,3 at °C
゜4, 4a, 5.8.8a-octahydronaphthalene (structural formula: pellet 4m, (b) component: ethylene/
Propylene random copolymer Ethylene content 80 mol χ
, Tg~54℃, MFR23++'C0,7g 71
0 minutes, [lco2.2dl/g) per)0
．． After sufficiently mixing 7 kg, the mixture was melt-blended using a twin-screw extruder (PCM 45 manufactured by Ikegai Iron Works) at a cylinder temperature of 230°C, and pelletized using a pelletizer. To 1 kg of pellets, add 1 g of Perhexin 25B (trademark) manufactured by Nippon Oil & Fats and 3 g of divinylbenzene as component (C), mix thoroughly, and transfer this mixture to the twin screw extruder described above (cylinder temperature 230°C). The reaction product [A] obtained as above was reacted in a molten state using a pelletizer and pelletized using a pelletizer.
[B] 0.47 kg of pellets of ethylene/4-methylpentene-1 copolymer (MFR2s s°C = 18g 710 minutes, crystallinity = 50%, density = 092, modulus of elasticity = 3000kg/C) as the acid component After mixing thoroughly, the pellets were pelletized using the above-mentioned twin-screw extruder (cylinder temperature = 230°C) and a melt mixer pelletizer. Using the obtained pellets, test pieces were prepared by the above-mentioned method, and the physical properties were determined. The measured results are shown in Table 1.

Ethylene content measured by 13cm NMR as component (a) 62 mol%, MFR26B'C35g/l 0 minutes, 1
Intrinsic viscosity measured in decalin at 35°C [η 0.47 d
Pellet 4 of a random copolymer of ethylene and DMON with a softening temperature (TMA) of 148°C and a Tg of 137°C.
kg, ethylene/propylene random copolymer as component (b) (ethylene content 80 mol χ, Tg - 54°C
, MFR23g℃0.7g/10min, [ηko 2
．． After thoroughly mixing 0.7 kg of 2 dl/g), the resulting component (a) was melted and blended using a twin screw extruder (PCM 45 manufactured by Ikegai Iron Works) at a cylinder temperature of 230°C, and then pelletized using a pelletizer. per 1 kg of pellets consisting of component (B), 1 g of Perhexin 25B (trademark) manufactured by NOF Corporation as component (C)
Add divinylbenzene at a rate of 3 g, mix thoroughly, and transfer this mixture to the twin-screw extruder (cylinder temperature 2
The reaction product [A'3 obtained above was pelletized using a pelletizer in a molten state using a polyethylene resin (MFR2a @
'C=13g710min, density=0.97, elastic modulus=15
After thoroughly mixing 0.47 kg/crr of pellets, the twin screw extruder described above (cylinder temperature = 230 ° C.
) and pelletized with a pelletizer. Using the resulting pellets, test specimens were prepared according to the method of Kimimi Mae, and the physical properties were measured. The results are shown in Table 1.

The same procedure was carried out as in Example 2 except that component (C) was not used.Bending elasticity measurement of the obtained composition Izot impact strength, HDT, Rockwell hardness (R scale) and MFR1f+i ('i22400 kg/cnf,
Table 1 shows the results of 106.72 at 16 kgcm/CX120°C.

Claims (1)

[Claims] (1) [A] (a) At least one cyclic olefin polymer selected from the group consisting of the following groups (a) to (d); 100 parts by weight, and (b) an elastic modulus of 0.1 kg/ cm^2~20000kg
/cm^2, and the glass transition point (Tg) is 0°C or lower,
Rubber-like elastic body with crystallinity of 30% or less; 0.5 to 5
and (c) a crosslinking agent; a reaction product obtained by contacting 0.01 to 1 part by weight with respect to a total of 100 parts by weight of components (a) and (b); [B] Elastic modulus is 1kg/cm^2~30000kg/c
m^2, a glass transition point (Tg) of 0°C or less, and a crystallinity of 30% or more; polyethylene or ethylene/α-olefin polymer; the above reaction product [A]
A cyclic olefin resin composition characterized by comprising 0.5 to 50 parts by weight per 100 parts by weight; (a) a combination of ethylene and a cyclic olefin represented by the following formula [I] or [I']; A copolymer with an intrinsic viscosity [η] of 0.05 to 10 d measured in decalin at 135°C
1/g range and has a softening temperature (TMA) of 70°C or higher; (b) Ring-opening of a cyclic olefin represented by the following formula [I] or [I'] A cyclic olefin ring-opening polymer having an intrinsic viscosity [η] measured in decalin at 135°C in the range of 0.05 to 10 dl/g and a softening temperature (TMA) of 70°C or higher; (c) A ring-opened copolymer of a cyclic olefin represented by the following formula [I] or [I'], which has an intrinsic viscosity [η] of 0.05 to 10 dl/g as measured in decalin at 135°C. A cyclic olefin ring-opened copolymer having a softening temperature (TMA) of 70° C. or higher; (d) the hydrogenated product of (b) or (c) above; ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (In the formula, n is 0 or 1, m is 0 or a positive integer, and R^1 to R^1^8 are Each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R^1^5 to R^1^8 combine with each other to form a monocyclic or polycyclic ring. and the monocyclic or polycyclic ring may have a double bond, and R^1^5 and R^1^6, or R^1^7
and R^1^8 may form an alkylidene group). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I ′] (In the formula [I ′], p is an integer of 0 or 1 or more,
q and r are 0, 1 or 2, R^1~R^1
^5 each independently represents an atom or 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^5 (
Alternatively, R^6) and R^9 (or R^7) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group. good. )