JPH06100743A - Cyclic olefinic copolymer composition and its production - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent fluorocarbon resistance and adhesiveness by blending a modified resin composition consisting of a cyclic olefinic resin, an elastomer, etc., with a polyolefin resin in a specific ratio. CONSTITUTION:(A) A modified resin composition comprising (i) a cyclic olefinic resin selected from the group consisting of a random copolymer of ethylene and a cyclic olefin of formula I ((n) is 0 or 1; (m) is 0 or more; (r) is 0 or 1; R<1> to R<18>, R<a> and R<b> are H, halogen, etc.) or formula II ((p) and (q) are 0 or more; (m) and (n) are 0-2; R<1> to R<19> are H, halogen, aliphatic hydrocarbon, etc.), a ring opening polymer or copolymer of the cyclic olefin of formula I or formula II and a hydrogenated substance of the ring opening polymer or copolymer, (ii) an elastomer having 30% or lower crystallinity and 0.1-2,000kg/cm<2> tensile modulus at 23 deg.C and (iii) a modifier such as an ethylenically unsaturated group-containing carboxylic acid is blended with (B) a polyolefin resin having 30% or lower crystallinity and 2,000kg/cm<2> or higher tensile modulus in the ratio of 1/99-99/1 to give the objective composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cycloolefin polymer composition having excellent flon resistance and adhesiveness, and a method for producing the same. More specifically, the present invention relates to a modified cyclic olefin polymer composition having excellent chlorofluorocarbon resistance and having excellent adhesion to, for example, foamed polyurethane even when an adhesive or the like is not used, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Random cyclic olefin copolymer, cyclic olefin ring-opening (co) polymer and ring-opening (co) polymer
A cyclic olefin resin, which is a hydrogenated product of a polymer, is a resin having excellent properties such as heat resistance, dimensional stability, chemical resistance, electrical properties, mechanical strength, and moldability. For example, JP-A-60
-168,708, 61-115,912, 61-115,916, 62-1
In the publications such as 20,816, the above cyclic olefin random copolymer is described in detail. Attempts have been made to use the cyclic olefin resin as an interior member for electric appliances, ornaments, automobiles, etc. by utilizing the excellent properties of the cyclic olefin resin. However, when this cyclic olefin resin is used as an interior member or the like, there is room for further improvement in mechanical properties such as impact resistance.

Attempts have been made to blend an elastic copolymer with a cyclic olefin resin in order to improve the characteristics of such a cyclic olefin resin. In this case, the phase of the cyclic olefin resin and the elastic copolymer is mixed. The solubility is not good,
Even if both are simply added, the improvement effect may not be sufficiently exhibited. For example, as a method for improving the impact resistance of a cyclic olefin random copolymer, a composition of a crystalline polyolefin containing polypropylene and a cyclic olefin random copolymer has been proposed (JP-A-1-318,054).
(See Japanese Patent Publication). Although this composition has excellent rigidity and heat resistance, it may not necessarily have sufficient impact resistance depending on the application. In addition, this composition has a problem in that the compatibility between the polypropylene and the cyclic olefin random copolymer is not sufficient, so that delamination occurs in the molded product.

By the way, as described above, the cyclic olefin-based resin itself has essentially excellent characteristics, but it has sufficient durability against specific freons such as Freon R-123 and Freon R-141b. There isn't. For example, when manufacturing the interior member and the like as described above, it is often lined with a foamed resin or the like, and the foamed resin to be lined is often foamed using CFC or the like. So, for example,
When used for the above-mentioned applications, it was necessary to improve the durability of the cyclic olefin-based resin against fluorocarbons. Furthermore, for example, when backing is performed as described above, the adhesiveness with other resins becomes a problem. Conventionally, when backing using a resin foam such as urethane foam, the adhesive force developed when the resin foams and the adhered force of the molded product to be backed are used to make an adhesive particularly A method of adhering the molded body and the resin foam without using it is often adopted. Therefore, when the cyclic olefin-based resin is used as the interior member, it is necessary to improve the adhesiveness with other resins, especially with metal.

Under these circumstances, the present applicant obtained a composition by previously contacting a cyclic olefin resin with rubber elasticity and a cross-linking agent, and then adding a propylene polymer to the composition. I have already applied for an invention (Japanese Patent Application No. 3-
171,406 specification).

Since the cyclic olefin-based resin has excellent properties as described above, when the properties of the cyclic olefin-based resin are improved, the cyclic olefin-based resin essentially has the properties. It has to be modified to add new properties to its essential properties without compromising its excellent properties.

However, in this respect, the conventional characteristic improvement is not always satisfactory.

[0008]

An object of the present invention is to improve the properties of a cyclic olefin copolymer without impairing the excellent properties inherent to the cyclic olefin copolymer. In addition, it is an object of the present invention to provide a composition having excellent CFC resistance, adhesiveness and mechanical strength. Another object of the present invention is to provide a method for producing a cyclic olefin-based copolymer composition having the above characteristics.

[0009]

SUMMARY OF THE INVENTION The cyclic olefin copolymer composition of the present invention comprises a random copolymer (a-1) of (a) ethylene and a cyclic olefin represented by the following formula [I] or [II]: ), A ring-opening polymer or ring-opening copolymer (a-2) of a cyclic olefin represented by the following formula [I] or [II], and a hydrogenated product of the ring-opening polymer or ring-opening copolymer With respect to at least one kind of cyclic olefin resin selected from the group consisting of (a-3) and 100 parts by weight of the cyclic olefin resin, (b) the crystallinity is 3
The tensile modulus at 23 ° C is 0% or less and is 0.
Elastomer in the range of 1 to 2000 Kg / cm ² ;
5 to 50 parts by weight and a total of 1 of the above-mentioned components (a) and (b)
0.1 part by weight of at least one modifier selected from the group consisting of (c) ethylenically unsaturated group-containing carboxylic acid, its anhydride and ethylenically unsaturated group-containing carboxylic acid hydroxyalkyl ester; 1 to 10 parts by weight of a modified resin composition formed by contact with [B] a polyolefin resin having a crystallinity of more than 30% and a tensile modulus at 23 ° C. of more than 2000 kg / cm ^2. It is characterized in that it is contained in a weight ratio of / 99 to 99/1.

[0010]

[Chemical 5]

[I] In the above formula [I], n is 0 or 1 and m is 0.
Or a positive integer, r is 0 or 1, and R ¹ ~
R ¹⁸ and R ^a and R ^b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are bonded to each other to form a monocyclic or polycyclic ring. A ring group may be formed, and the monocyclic or polycyclic group may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ It may form an alkylidene group.

[0012]

[Chemical 6]

[II] In the above formula [II], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ¹
To R ¹⁹ are each independently a hydrogen atom, a halogen atom,
Represents an atom or group selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, wherein the carbon atom to which R ⁹ is bonded and R ¹³ are bonded to each other. The carbon atom or the carbon atom to which R ¹⁰ is bonded and the carbon atom to which R ¹¹ is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and n = m = When it is 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring.

Further, the method for producing a cyclic olefin copolymer composition of the present invention comprises a random copolymer (A) (a) of ethylene and a cyclic olefin represented by the above formula [I] or [II] ( a-1), the above formula [I]
Or a ring-opening polymer or ring-opening copolymer (a-2) of a cyclic olefin represented by [II], and a hydrogenated product (a-3) of the ring-opening polymer or ring-opening copolymer At least one cyclic olefin resin selected from the group, and (b) the crystallinity is 30% or less, and the tensile modulus at 23 ° C. is 0.1 to 2000 kg with respect to 100 parts by weight of the cyclic olefin resin. an elastomer in the range of / cm ² ;
At least one selected from the group consisting of (c) an ethylenically unsaturated group-containing carboxylic acid, an anhydride thereof and an ethylenically unsaturated group-containing carboxylic acid hydroxyalkyl ester. The denaturing agent of the above (a) and component (b) to 100 parts by weight in total,
After preparing a modified resin composition by blending in an amount of 0.1 to 10 parts by weight and bringing them into contact with each other, the modified resin composition and [B] the crystallinity exceeds 30% and the tensile strength at 23 ° C. It is characterized in that a polyolefin resin having a modulus of more than 2000 kg / cm ² is mixed in a weight ratio of 1/99 to 99/1.

The cyclic olefin-based copolymer composition of the present invention exhibits excellent flon resistance and adhesiveness as compared with conventional cyclic olefin-based resin compositions.

[0016]

DETAILED DESCRIPTION OF THE INVENTION Next, the cyclic olefin copolymer composition of the present invention will be specifically described. The cyclic olefin resin which is the component (a) used in the present invention is (a-
1) Random copolymer of ethylene and a cyclic olefin represented by the formula [I] or [II] [hereinafter, sometimes abbreviated as "cyclic olefin random copolymer"], (a-
2) A ring-opening polymer or a ring-opening copolymer of a cyclic olefin represented by the formula [I] or [II] [hereinafter sometimes abbreviated as "ring-opening (co) polymer"] and (a-3 ) Above (a-2)
A hydrogenated product of a ring-opening polymer or a ring-opening copolymer [hereinafter,
It may be abbreviated as "hydrogenated product"], and these may be used alone or in combination.

The cyclic olefin is represented by the following formula [I] or [II].

[0018]

[Chemical 7]

[I] In the above formula [I], n is 0 or 1, and m is 0.
Alternatively, it is a positive integer and r is 0 or 1. In addition,
When r is 1, R ^a and R ^b are each independently
It represents the following atom or hydrocarbon group, and when r is 0, the respective bonds bond to form a 5-membered ring.

Further, R ^{1 to} R ¹⁸ and R ^a and R
^b is each independently a hydrogen atom, a halogen atom or a hydrocarbon group. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Further, as the hydrocarbon group,
Independently, usually, an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms can be exemplified. More specifically, examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group and octadecyl group. Moreover, a cyclohexyl group can be mentioned as an example of a cycloalkyl group.

Further, in the above formula [I], R ¹⁵ and R
¹⁶ and includes a R ¹⁷ and R ¹⁸ may further have a R ^{1 5} and R ^17, R ¹⁶
And R ¹⁸ , R ¹⁵ and R ¹⁸ , or R ¹⁶ and R ¹⁷ may be bonded to each other (in cooperation with each other) to form a monocyclic or polycyclic structure, and The monocyclic or polycyclic structure thus formed may have a double bond.

Examples of monocyclic or polycyclic structures are shown below.

[0023]

[Chemical 8]

In the above-exemplified structures, carbon atoms numbered 1 and 2 are represented by the following formula [I]:
It represents a carbon atom of an alicyclic structure to which the groups represented by R ¹⁵ (R ¹⁶ ) and R ¹⁷ (R ¹⁸ ) are bonded.

R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸
And may form an alkylidene group. Such an alkylidene group can usually include an alkylidene group having 2 to 20 carbon atoms, and specific examples thereof include an ethylidene group, a propylidene group and an isopropylidene group.

Next, the cyclic olefin represented by the formula [II] will be described.

[0027]

[Chemical 9]

[II] In the above formula [II], p is 0 or a positive integer,
It is preferably 0 to 3. In the above formula [II],
m and n are 0, 1 or 2. Further, q is 0 or a positive integer, preferably 0 or 1.

R ^{1 to} R ¹⁹ are, independently of each other,
It is a hydrogen atom, a halogen atom or a hydrocarbon group. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Moreover, as a hydrocarbon group, a C1-C10 alkyl group, a C5-C15 cycloalkyl group, and a C6-C12 aromatic group can be mentioned.

Specific examples of the alkyl group include methyl group, ethyl group, isopropyl group, isobutyl group, n-amyl group, neopentyl group, n-hexyl group, n-octyl group,
Examples thereof include n-decyl group and 2-ethylhexyl group.

Specific examples of the cycloalkyl group include:
Examples thereof include cyclohexyl group, methylcyclohexyl group and ethylcyclohexyl group. Further, specific examples of the aromatic group include an aryl group and an aralkyl group, and specific examples include a phenyl group, a tolyl group, a naphthyl group, a benzyl group, a phenylethyl group and a biphenyl group. You can These groups may have a lower alkyl group.

Further, examples of the alkoxy group include methoxy group, ethoxy group and propoxy group. These groups may be substituted with a halogen atom. Further, in the above-mentioned formula [II], the carbon atom to which R ⁹ and the carbon atoms or R ¹¹ carbon atoms and R ^{1 3} are bonded to R ¹⁰ is bonded is bonded, directly or carbon 1 It may be bonded via the alkylene group of ~ 3. That is, when the above two carbon atoms are bonded via an alkylene group, R ⁹ and R ¹³ or R ¹⁰ and R ¹¹ cooperate with each other to form a methylene group (—CH
_2- ), ethylene group (-CH ₂ CH _2- ) or propylene group (-CH ₂ CH
It is preferable that any one of ₂ CH _2- ) is formed.

Further, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. Preferred examples in this case include the groups described below in which R ¹⁵ and R ¹² further form an aromatic ring when n = m = 0.

[0034]

[Chemical 10]

In the above formula, q has the same meaning as in formula [II]. The cyclic olefin represented by the above formula [I] or [II] can be produced by condensing a cyclopentadiene and a corresponding olefin or a corresponding cyclic olefin using the Diels-Alder reaction. .

Specific examples of the cyclic olefin represented by the above formula [I] or [II] used in the present invention include the compounds described below and derivatives thereof.

A bicyclo [2.2.1] hept-2-ene derivative,
Tricyclo [4.3.0.1 ^2,5 ] -3-decene derivative, tricyclo [4.3.0.1 ^2,5 ] -3-undecene derivative, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene derivative, pentacyclo ^{[6.6.1.1 3,6 .0 2,7 .0 9,14]} -4- hexadecene derivative,
Pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4- hexadecene derivative, pentacyclo ^{[7.4.0.1 2,5 .1 9,12 .0 8,13]} -3
- pentadecene derivatives, penta cyclopentadiene decadiene derivative, pentacyclo ^{[8.4.0.1 2,5 .1 9,12 .0 8,13]} -3-
Pentadecene derivatives, hexacyclo [6.6.1.1 ^3,6 .1
^10,13 .0 ^2,7 .0 ^9,14] -4-heptadecene derivatives, heptacyclo ^{[8.7.0.1 3,6 .1 10,17 .1 12,15 .0} 2,7 .0 11,16] - 4-eicosene derivatives, heptacyclo [8.7.0.1 ^3,6 .1 ^10,17 .1
^12,17 .0 ^2,7 .0 ^11,16] -5-eicosene derivatives, heptacyclo ^{[8.8.0.1 4,7 .1 11,18 .1 13,16 .0} 3,8 .0 12,17] - 5-heneicosene derivatives, heptacyclo [8.8.0.1 ^2,9 .1 ^4,7 .1
^11,18 .0 ^3,8 .0 ^12,17] -5-heneicosene derivatives, octacyclo ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .1} 13,16 .0 3,8.
0 ^12,17 ] -5-dococene derivative, nonacyclo [10.9.1.
1 ^4,7 .1 ^13,20 .1 ^15,18 .0 ^3,8 .0 ^2,10 .0 ^12,21 .0 ^14,19] -5-pentacosene derivatives, Nonashikuro [10.10.1.1 ^5,8. 1 ^14,21 .
1 ^16,19 .0 ^2,11 .0 ^4,9 .0 ^{13, 22} .0 ^15,20] -5-hexacosenoic derivatives.

1,4-methano-1,4,4a, 9a-tetrahydrofluorene derivative, 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene derivative, cyclopentadiene-acenaphthylene adduct .

Then, the above expressions [I] and [I
Specific examples of the compound of the cyclic olefin represented by [I] include the compounds described below.

[0040]

[Chemical 11]

[0041]

[Chemical 12]

[0042]

[Chemical 13]

[0043]

[Chemical 14]

[0044]

[Chemical 15]

[0045]

[Chemical 16]

[0046]

[Chemical 17]

[0047]

[Chemical 18]

[0048]

[Chemical 19]

[0049]

[Chemical 20]

[0050]

[Chemical 21]

[0051]

[Chemical formula 22]

[0052]

[Chemical formula 23]

[0053]

[Chemical formula 24]

[0054]

[Chemical 25]

[0055]

[Chemical formula 26]

[0056]

[Chemical 27]

[0057]

[Chemical 28]

[0058]

[Chemical 29]

[0059]

[Chemical 30]

[0060]

[Chemical 31]

[0061]

[Chemical 32]

The cyclic olefin random copolymer (a-1) used in the present invention is a copolymer of the above cyclic olefin and ethylene, and this copolymer is a repeating unit derived from ethylene. The amount of the repeating unit derived from a cyclic olefin is usually 10 to 48 mol%, preferably 20 to 45 mol%. Included in the amount within the range of%. The repeating units derived from the ethylene and the repeating units derived from the cyclic olefin are randomly and substantially linearly arranged.

This cyclic olefin random copolymer (a-
1) has ethylene and the cyclic olefin as essential components, but other than these essential two components, other copolymerizable unsaturated compounds, if necessary, within a range not impairing the object of the present invention. It may contain a monomer component. As the unsaturated monomer which may be optionally copolymerized, specifically, propylene, 1-butene, 4-methyl-1-pentene, 1-
Examples include α-olefins having 3 to 20 carbon atoms such as hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. Cyclic olefin random copolymer
(a-1) may contain the repeating unit derived from the other unsaturated monomer in an amount less than equimolar to the repeating unit derived from ethylene.

Further, in the present invention, when the above cyclic olefin random copolymer is produced,
A cyclic olefin other than the cyclic olefin represented by the above formula [I] or [II] can be polymerized as long as the physical properties of the obtained polymer and the like are not impaired. Examples of such a cyclic olefin include cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclohexene, 3-methylcyclohexene, and 2- (2-methylbutyl) -1-.
Cyclohexene, 2,3,3a, 7a-tetrahydro-4,7-methano-
1H-indene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-
Inden, etc. can be mentioned. Such other cyclic olefins can be used alone or in combination, and are usually used in an amount of 0 to 50 mol%.

The ethylene composition and the cyclic olefin composition in the cyclic olefin random copolymer can be measured by measuring ¹³ C-NMR for this copolymer. Further, the fact that this cyclic olefin random copolymer is substantially linear and does not have a gel-like crosslinked structure can be confirmed by completely dissolving this copolymer in decalin at 135 ° C. .

The intrinsic viscosity [η] of such cyclic olefin random copolymer (a-1) measured in decalin at 135 ° C. is usually 0.05 to 10 dl / g, preferably 0.03 to 2 dl. / g, more preferably 0.4 to 1.2 dl / g
Is within the range of.

Further, the cyclic olefin random copolymer (a
-1), the softening temperature (TMA) measured by a thermal mechanical analyzer is usually 70 ° C or higher, preferably 70 to 200 ° C, particularly preferably 100 to 180.
Within the range of ° C.

In the present invention, the softening temperature (TMA) is
It is a value measured by thermal deformation behavior of a sheet having a thickness of 1 mm using a Thermomechanical Analyser manufactured by DuPont. Specifically, a quartz needle is placed on the sheet, a load of 49 g is applied to the quartz needle, and the temperature is raised at a heating rate of 5 ° C./min. TMA.

The glass transition temperature (Tg) of the cyclic olefin random copolymer is usually in the range of 50 to 190 ° C, preferably 80 to 170 ° C. The crystallinity of the cyclic olefin random copolymer (a-1) measured by the X-ray diffraction method is usually 0 to 20%, preferably 0 to 2%.

The reaction of the above ethylene with the cyclic olefin represented by the formula [I] or [II] is usually carried out in a hydrocarbon solvent. As the hydrocarbon solvent used here, any solvent of an aliphatic hydrocarbon, an alicyclic hydrocarbon and an aromatic hydrocarbon can be used. Further, among the polymerizable unsaturated monomers that can be used when preparing the cyclic olefin random copolymer, a compound that is liquid under the reaction conditions can be used as a reaction solvent. These solvents can be used alone or in combination.

The catalyst used in the reaction of the above ethylene with the cyclic olefin represented by the formula [I] or [II] is usually a vanadium compound soluble in a reaction solvent and an organoaluminum compound. Is a catalyst.

Examples of the vanadium compound used as a catalyst in this copolymerization include compounds represented by the formula VO (OR) _a V _b or the formula V (OR) _c X _d .

However, in the above formula, R is a hydrocarbon group, and 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3,
It has a relationship of 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, and 3 ≦ c + d ≦ 4. Further, the vanadium compound used herein may be an electron donor adduct of the vanadium compound represented by the above formula. Examples of the electron donor that forms an adduct here include alcohols having 1 to 18 carbon atoms and phenols having 6 to 20 carbon atoms (the phenols may have a lower alkyl group). , C3-C15 ketones, C2-C15 aldehydes, C2-C30 organic acid esters, C2-C15
Acid halides, ethers having 2 to 20 carbon atoms, amines, and alkoxysilanes. These electron donors can be used alone or in combination.

The organoaluminum compound used in this copolymerization is a compound having at least one Al-carbon bond in the molecule. Examples of this organoaluminum compound include (i) formula R ¹ _m Al (OR ² ) _n H _p X _q
The organoaluminum compound represented by the formula (wherein R ¹ and R ² each independently have a carbon number of usually 1 to 1).
5 hydrocarbon groups, preferably 1 to 4 hydrocarbon groups, X is halogen, m is 0 ≦ m ≦ 3, n is 0 ≦ n <3, and p is 0 ≦ n.
<3, q is a number 0 ≦ q <3, and m + n + p
+ Q = 3), (ii) a complex alkylated product of a Group I metal represented by the formula M ¹ AlR ¹ ₄ and aluminum (wherein M ¹ is Li, Na or K, and R ¹ is the same as above). Meaning).

In the above reaction, the vanadium compound is used in an amount of usually 0.01 to 5 as a vanadium atom.
It is in the range of gram atom / liter, preferably 0.05 to 3 gram atom / liter. The amount of the organoaluminum compound used is usually in the range of 2 or more, preferably 2 to 50, particularly preferably 3 to 20, when expressed as the ratio of aluminum atoms to vanadium atoms in the polymerization reaction system (Al / V). It is inside.

In the cyclic olefin random copolymer (a-1), the cyclic olefin [I] or [II] forms a repeating unit represented by the following formula [Ia] or [II-a]. it is conceivable that.

[0077]

[Chemical 33]

[Ia] In the above formula [Ia], n, m, r, R ^{1 to} R ¹⁸ ,
R ^a and R ^b have the same meaning as in the above formula [I].

[0079]

[Chemical 34]

[II-a] In the above formula [II-a], p, q, m, n, R ^{1 to} R ¹⁹
Has the same meaning as in the above formula [II].

The ring-opening polymer or ring-opening copolymer (a-2) of the cyclic olefin is a ring-opening polymer or ring-opening copolymer of the cyclic olefin represented by the above formula [I] or [II]. is there.
The intrinsic viscosity [η] of such a cyclic olefin ring-opening polymer or cyclic olefin ring-opening copolymer (a-2) measured in decalin at 135 ° C. is usually 0.05 to 10 dl /
g, preferably 0.03 to 2 dl / g, more preferably 0.03.
It is in the range of 4-1.2 dl / g.

The softening temperature (TMA) of the cyclic olefin ring-opening polymer or cyclic olefin ring-opening copolymer (a-2) measured by a thermal mechanical analyzer.
Is usually 70 ° C. or higher, preferably 70 to 200 ° C., and particularly preferably 100 to 180 ° C.

Further, the glass transition temperature (T of the cyclic olefin ring-opening polymer or cyclic olefin ring-opening copolymer (a-2))
g) is usually 50 to 190 ° C., preferably 80 to 17
Within the range of 0 ° C.

The crystallinity of this cyclic olefin ring-opening polymer or cyclic olefin ring-opening copolymer (a-2) measured by X-ray diffraction is usually 0 to 20%, preferably 0 to 20%. It is in the range of 2%. The intrinsic viscosity [η] measured in decalin at 135 ° C is usually 0.05 to 10 dl /
g, preferably in the range of 0.08 to 5 dl / g.

This cyclic olefin ring-opening polymer or cyclic olefin ring-opening copolymer (a-2) is prepared by converting the cyclic olefin represented by the above formula [I] or [II] into ruthenium, rhodium, palladium, osmium, A catalyst comprising a metal halide such as indium and platinum, a nitrate of these metals or an acetylacetone compound of these metals, and a reducing agent; a metal halide such as titanium, palladium, zirconium and molybdenum or these metals. It can be produced by (co) polymerizing in the presence of a catalyst consisting of the acetylacetone compound of 1 and organoaluminum.

In the cyclic olefin ring-opening polymer or cyclic olefin ring-opening copolymer (a-2), the cyclic olefin [I] or [II] is represented by the following formula [Ib] or [II], respectively.
-b] is considered to form the repeating unit.

[0087]

[Chemical 35]

[Ib] In the above formula [Ib], n, m, r, R ^{1 to} R ¹⁸ ,
R ^a and R ^b have the same meaning as in the above formula [I].

[0089]

[Chemical 36]

[II-b] In the above formula [II-b], p, q, m, n, R ^{1 to} R ¹⁹
Has the same meaning as in the above formula [II].

The hydrogenated product (a-3) of the above-mentioned cyclic olefin ring-opening polymer or cyclic olefin ring-opening copolymer (a-2) is a cyclic olefin ring-opening polymer or an olefin ring-opening polymer obtained as described above. It can be produced by reducing the ring copolymer (a-2) with hydrogen in the presence of a hydrogenation catalyst.

Regarding such hydrogenated products (a-3) 13
The intrinsic viscosity [η] measured in decalin at 5 ° C is usually in the range of 0.05 to 10 dl / g, preferably 0.03 to 2 dl / g, and more preferably 0.4 to 1.2 dl / g. It is in.

The softening temperature (TMA) of this hydrogenated product (a-3) measured by a thermal mechanical analyzer is usually 70 ° C. or higher, preferably 70 to 2
It is in the range of 00 ° C, particularly preferably 100 to 180 ° C.

The glass transition temperature (Tg) of the hydrogenated product (a-3) is usually 50 to 190 ° C., preferably 8
It is in the range of 0 to 170 ° C. In addition, this hydrogenated product (a
For -3), the crystallinity measured by the X-ray diffraction method is
It is usually in the range of 0 to 20%, preferably 0 to 2%.

In the hydrogenated product (a-3) of the above-mentioned cyclic olefin ring-opening polymer or ring-opening copolymer, the cyclic olefin [I] or [II] is represented by the following formula [Ic] or [II-c], respectively. It is considered that the repeating unit represented by

[0096]

[Chemical 37]

[Ic] In the above formula [Ic], n, m, r, R ^{1 to} R ¹⁸ ,
R ^a and R ^b have the same meaning as in the above formula [I].

[0098]

[Chemical 38]

[II-c] In the above formula [II-c], p, q, m, n, R ^{1 to} R ¹⁹
Has the same meaning as in the above formula [II].

The cyclic olefin polymer used in the present invention is not limited to the above-mentioned ones, and those disclosed in JP-A-60-168708, 61-120816 and 61-120816 can be used.
61-115912, 61-115916, 61-271308, 61-27
It can be produced by appropriately selecting the conditions according to the method proposed by the applicant in the publications such as 2216, 62-252406 and 62-252407.

The elastomer as the component (b) used in the present invention has a tensile modulus at 23 ° C. of 0.1 to 2
It is an elastomer in the range of 000 kg / cm ² . Further, the elastomer (b) has a glass transition temperature (Tg) of usually 0 ° C or lower, preferably 0 ° C to -150 ° C.
More preferably, it is in the range of -80 to -20 ° C. The intrinsic viscosity [η] of this elastomer measured in decalin at 135 ° C. is usually 0.2 to 10 dl / g,
It is preferably 1 to 5 dl / g. The density is usually 0.82 to 0.96 g / cm ³ , preferably 0.84 to 0.9.
It is 2 g / cm ³ . The crystallinity of this elastomer measured by X-ray diffractometry is usually 30% or less, preferably 25% or less, and the copolymer is preferably low crystalline or amorphous.

The elastomer (b) used in the present invention is α-
In the case of an olefin copolymer, such α-olefin copolymers include, specifically, (a) ethylene / α-olefin copolymer rubber and (ii) propylene / α-
An olefin copolymer rubber can be illustrated. The ethylene / α-olefin copolymer rubber (a) and propylene /
The α-olefin copolymer rubber (II) can be used alone or in combination of both.

The α-olefin constituting the above ethylene / α-olefin copolymer rubber (a) is usually an α-olefin having 3 to 20 carbon atoms, for example, propylene, 1-
Mention may be made of butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. Of these, propylene and / or 1-butene are particularly preferable.

The α-olefin constituting the propylene / α-olefin copolymer rubber (b) is usually
Α-olefins having 4 to 20 carbon atoms, such as 1-butene, 1
Mention may be made of -pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. Of these, 1-butene is particularly preferable.

The elastomer may have a repeating unit other than the repeating unit derived from α-olefin, such as a repeating unit derived from a diene compound, as long as the characteristics are not impaired.

For example, as repeating units that are allowed to be contained in the elastomer (b), 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1 Repeating units derived from linear non-conjugated dienes such as 1,5-heptadiene and 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2 -Norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene and 6
Repeating units derived from cyclic non-conjugated dienes such as -chloromethyl-5-isopropenyl-2-norbornene;
3-diisopropylidene-5-norbornene, 2-ethylidene-
There may be mentioned repeating units derived from diene compounds such as 3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene. The content of the repeating unit derived from the above-mentioned diene component in the α-olefin copolymer is usually 10 mol% or less, preferably 5 mol% or less.

In the above ethylene / α-olefin copolymer (a), the molar ratio of the repeating unit derived from ethylene and the repeating unit derived from α-olefin (ethylene / α-olefin) is α- Generally varies from 10/90 to 99 /, depending on the type of olefin
1, preferably 50/50 to 95/5. The above molar ratio is 5 when the α-olefin is propylene.
It is preferably 0/50 to 90/10, and when the α-olefin is an α-olefin having 4 or more carbon atoms, it is preferably 80/20 to 95/5.

In the propylene / α-olefin copolymer (b), the molar ratio of the repeating unit derived from propylene and the repeating unit derived from α-olefin (propylene / α-olefin) is α -Generally 50 / 50-9, depending on the type of olefin
Within the range of 5/5. Further, the above molar ratio is 50/50 to 90 when the α-olefin is 1-butene.
It is preferably / 10, and when the α-olefin has 5 or more carbon atoms, it is preferably 80/20 to 95/5.

Among these elastomers (b), an ethylene-propylene random copolymer is preferable. The elastomer (b) is used in an amount of 0.5 to 50 parts by weight based on 100 parts by weight of the cyclic olefin resin (a). The elastomer (b) is preferably used in an amount of 1 to 30 parts by weight, and more preferably 5 to 20 parts by weight.

In the present invention, the cyclic olefin resin (a) and elastomer (b) as described above, and a specific modifier (c) are used.
And are brought into contact with each other to form the modified resin composition [A]. The modifier (c) used here is at least one kind of modifier selected from the group consisting of an ethylenically unsaturated group-containing carboxylic acid, an anhydride thereof and an ethylenically unsaturated group-containing carboxylic acid hydroxyalkyl ester.

Specific examples of the ethylenically unsaturated group-containing carboxylic acid or acid anhydride thereof include (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, Norbornene dicarboxylic acid and bicyclo [2,2,1] hept-2-ene
-5,6-dicarboxylic acid and other unsaturated carboxylic acids, and
These acid anhydrides can be mentioned.

Specific examples of the ethylenically unsaturated group-containing carboxylic acid hydroxyalkyl ester include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate and 3-hydroxypropyl. Acrylate, 3-hydroxypropyl methacrylate, 3-
Mention may be made of chloro-2-hydroxyacrylate, 3-chloro-2-hydroxymethacrylate, 2-hydroxy-3-phenoxypropyl acrylate and 2-hydroxy-3-phenoxypropyl methacrylate.

Of these, acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferable. Of these, ethylenically unsaturated group-containing carboxylic acid hydroxyalkyl ester is preferable, and among these, 2-hydroxyalkyl (meth) acrylate and 2-hydroxyethyl acrylate are preferably used. By using the modified resin composition [A] modified with such a modifier, the cycloolefin resistance of the cyclic olefin copolymer composition of the present invention becomes particularly good.

The modifier (c) as described above has a total weight of 100 of the cyclic olefin resin (a) and the elastomer (b).
0.1 to 10 parts by weight, preferably 0.1
Used in an amount of ~ 5 parts by weight.

A radical initiator is preferably used when the components (a), (b) and (c) are brought into contact with each other. Here, as the radical initiator, an organic peroxide or an azo compound is usually used.

Specific examples of the organic peroxide include 1,1-
Bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl
-4,4-bis (t-butylperoxy) paralate and 2,2-
Peroxyketals such as bis (t-butylperoxy) butane; di-t-butylperoxide, dicumylperoxide, t-butylcumylperoxide, α, α'-bis
(t-Butylperoxy-m-isopropyl) benzene, 2,5-
Dialkyl peroxides such as dimethyl-2,5-bis (t-butylperoxy) hexane and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3; acetyl peroxide, isobutyryl Such as ruperoxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and m-trioyl peroxide. Diacyl peroxides; t-butyl peroxyacetate, t-butyl peroxyisobutyrate,
t-butylperoxy-2-ethylhexanoate, t-butylperoxylaurylate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-
Dimethyl-2,5-di (benzoylperoxy) hexane, t-
Peroxyesters such as butyl peroxy maleic acid, t-butyl peroxy isopropyl carbonate and cumyl peroxy octate; and t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5 -Hydroperoxides such as dimethylhexane-2,5-dihydroperoxide and 1,1,3,3-tetramethylbutyl hydroperoxide can be mentioned.

Among these, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, di-t-butylperoxide, dicumyl peroxide, 2,5-dimethyl-2, 5-bis (t-butylperoxy) hexane and 2,5
-Dimethyl-2,5-bis (t-butylperoxy) hexyne-3 is preferred.

Specific examples of the azo compound used as a radical initiator include azoisobutyronitrile. Such radical initiators can be used alone or in combination. When modifying the cyclic olefin resin (a) and the elastomer (b) using the modifier (c), the radical initiator is a total weight of the cyclic olefin resin (a) and the elastomer (b) of 100. It is generally used in an amount within the range of 0.005 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on parts by weight.

Further, in this modification, a crosslinked structure can be formed between the cyclic olefin resin (a) and the elastomer (b). By forming a crosslinked structure,
Mechanical properties such as impact resistance are improved.

The crosslinked structure can be formed by using the above radical initiator. Examples of the radical initiator used for forming the crosslinked structure include the compounds exemplified when the above-mentioned modifier is reacted.

In the above reaction, the radical initiator is
It is preferably used in an amount of 0.005 to 10 parts by weight, and further in an amount of 0.05 to 5 parts by weight, based on 100 parts by weight of the total weight of the cyclic olefin resin (a) and the elastomer (b). It is particularly preferred to use.

Further, in the present invention, it is preferable to use a crosslinking aid together when forming a crosslinked structure. The crosslinking assistant that can be used here is a compound having two or more radically polymerizable functional groups in the molecule. Examples of the crosslinking aid used here include divinylbenzene and vinyl (meth) acrylate. When such a cross-linking auxiliary agent is used in combination, the cross-linking agent is usually 0.005 to 1 with respect to 100 parts by weight of the total weight of the cyclic olefin resin (a) and the elastomer (b).
It is preferably used in an amount of 0 parts by weight, more preferably 0.0
It is particularly preferred to use in an amount of 5 to 5 parts by weight.

The method for producing the component [A] of the present invention is as follows:
For example, a mixture of a cyclic olefin resin which is the component (a) and an elastomer which is the component (b) is melt-kneaded, and a modifier (c), a radical initiator and a cross-linking aid are further added to the kneaded product. Method of kneading, melt-kneading a mixture of a cyclic olefin resin as the component (a) and an elastomer as the component (b), and further kneading the mixture with a modifier (c) and a radical initiator. Further, a radical initiator to the kneaded product, a method of kneading with a crosslinking aid, a cyclic olefin resin as the component (a), an elastomer as the component (b), a modifier (c) and a radical initiator. A method of melt-kneading in a batch, and further kneading the kneaded product with a radical initiator and a cross-linking aid, and melt-kneading a mixture of a cyclic olefin resin as the component (a) and an elastomer as the component (b). Then, radicals are added to this kneaded product. A method of melt-kneading an initiator and a cross-linking aid, and further adding a modifier (c) and a radical initiator to the kneaded product and melt-kneading.
And a cyclic olefin resin which is the component (a), (b)
There is a method of melt-kneading the components such as an elastomer, a modifier (c), a radical initiator and a crosslinking aid all together. In the present invention, any of the above methods can be adopted,
The mixture of the cyclic olefin resin which is the component (a) and the elastomer which is the component (b) is melt-kneaded, and the kneaded product is further mixed with a modifier (c), a radical initiator and a cross-linking auxiliary agent, and kneaded. The method is most preferred.

The amount of the modifying agent grafted in the modified resin composition [A] containing the modified product of the cyclic olefin resin (a) and the elastomer (b) produced as described above is
It is usually 0.1 to 10% by weight, preferably 0.3 to 8% by weight, particularly preferably 0.3 to 4% by weight.

In the modified resin composition [A], the amount of the modifying agent (c) is adjusted so that the graft amount is within the above range, and the cyclic olefin resin (a) and the elastomer (b) are prepared. It can also be prepared by mixing it with
Further, for example, a modified resin composition having a high grafting amount is prepared by increasing the compounding amount of the modifier, and then the unmodified cyclic olefin resin (a) and / or the elastomer ( It can also be prepared by diluting with b).

The cyclic olefin copolymer composition of the present invention is a modified resin composition [A] formed as described above.
And a specific polyolefin resin [B]. The polyolefin resin [B] used in the present invention needs to be a polyolefin having a crystallinity of more than 30% as measured by an X-ray diffraction method, and this crystallinity is 40%.
It is preferably at least 50%, more preferably at least 50%. Further, this polyolefin resin [B] has the crystallinity as described above and
It is necessary for the polyolefin to have a tensile modulus at 2000C of more than 2000 kg / cm ² , and particularly, this tensile modulus is preferably more than 2000 kg / cm ² and not more than 30000 kg / cm ² , and more preferably 3000 to 20000.
It is particularly preferable that it is in the range of Kg / cm ² .

Polyethylene or polypropylene is preferably used as the crystalline polyolefin resin [B]. The polyethylene used here is preferably polyethylene containing 50 mol% or more, preferably 90 mol% or more, of repeating units derived from ethylene, and the polypropylene is usually 70% of repeating units derived from propylene. Polypropylene containing at least mol%, preferably at least 80 mol% is used. The polyethylene may be a homopolymer of ethylene or a copolymer with a small amount of other α-olefin. Other α-copolymers with ethylene
Examples of the olefin include α-olefins having 3 to 20 carbon atoms such as propylene, butene-1, pentene-1, 4-methylpentene-1, 3-methylbutene-1 and hexene-1. Specific examples of the crystalline polyethylene that can be used in the present invention include high-density polyethylene, low-density polyethylene, linear low-density polyethylene (LLDPE) and ultra-low-density linear polyethylene (VL).
DPE). Such crystalline polyethylene usually has a density of about 0.82 to 0.96 g / cm ³ , and the intrinsic viscosity [η] measured in decalin at 135 ° C. is usually 1 to 5 dl / It is in the range of g.

When polypropylene is used as the crystalline polyolefin resin [B], a homopolymer of propylene and a copolymer of propylene and another α-olefin can be used. Examples of other α-olefins copolymerized with propylene include ethylene, butene-1, pentene-1, 4-methylpentene-1, 3-methylbutene-1 and hexene-1 having 2 to 20 carbon atoms.
.Alpha.-olefins (excluding propylene) can be mentioned. Such crystalline polypropylene is usually less than 0.0
It has a density of 88 to 0.92 g / cm ³ and 1
The intrinsic viscosity [η] measured in decalin at 35 ° C is usually in the range of 1 to 10 dl / g.

Further, as the crystalline polyolefin resin [B], at least one kind selected from the group consisting of an ethylenically unsaturated group-containing carboxylic acid, an anhydride thereof and an ethylenically unsaturated group-containing carboxylic acid hydroxyalkyl ester is used. It is also possible to use a crystalline polyolefin resin modified with a modifier.

The crystalline polyolefin resin [B] has a repeating unit derived from a chain non-conjugated diene and / or a repeating unit derived from a cyclic non-conjugated diene within a range that does not impair the crystallinity. You may have. The content of the repeating unit derived from such a non-conjugated diene in the crystalline polyolefin resin [B] of the present invention is usually 20 mol% or less, preferably 10 mol% or less.

Particularly in the present invention, it is preferable that the polyolefin resin [B] is any of low density polyethylene, linear low density polyethylene, polypropylene and maleates thereof.

The cyclic olefin copolymer composition of the present invention contains the modified resin composition [A] and the polyolefin resin [B] in a weight ratio of 1/99 to 99/1. By blending both in such an amount, the CFC resistance is excellent and the adhesiveness is good. Here, if the proportion of the component [B] becomes large, the CFC resistance and fluidity increase, but the adhesiveness decreases. And both 9/9
It is preferably contained in a weight ratio of 0 to 99/1, and more preferably contained in a weight ratio of 30/70 to 99/1.

The cyclic olefin copolymer composition of the present invention can be produced by mixing the modified resin composition [A] and the polyolefin resin [B] as described above in the above-mentioned mixing ratio.

Various methods can be adopted for this mixing, and for example, at least one of the modified resin composition [A] and the polyolefin resin [B], preferably both are melted by heating to a temperature at which they melt. And a modified resin composition [A] and a polyolefin resin [B] are dissolved in an organic solvent in which at least a part thereof is dissolved and mixed in a solution state or a dispersion state, and then an organic solvent is added. Can be mentioned.

When the modified resin composition [A] and the polyolefin resin [B] are compounded, in addition to the above components, an inorganic filler, an organic filler, a heat stabilizer, a weather resistance stabilizer and an antistatic agent. Additives such as anti-slip agents, anti-blocking agents, anti-fog agents, lubricants, pigments, dyes, natural oils, synthetic oils and waxes may be added.

The cyclic olefin polymer composition of the present invention has excellent chlorofluorocarbon resistance and good adhesion to other resins, metals and the like. That is, the cyclic olefin polymer composition of the present invention exhibits excellent resistance to fluorocarbons that may be used in the production of resin foams, particularly urethane foams. For example, when producing a heat insulating structure using urethane foam as a heat insulating agent, first, a molded article (forming a surface layer or an intermediate layer) having a desired shape is produced using the cycloolefin polymer composition of the present invention. Then, the molded body is loaded into a fixed mold, and then a urethane foam precursor is filled in the mold to foam, whereby a heat insulating structure lined with urethane foam can be manufactured. . And, even when the fluorine-based hydrocarbon used in this foaming and the cyclic olefin-based polymer composition of the present invention are in direct contact, the layer formed from the composition of the present invention is It is not easily attacked by hydrocarbons. Furthermore, the cyclic olefin-based copolymer composition of the present invention shows very good adhesiveness with the above urethane foam and the like, and does not require the use of an adhesive composed of other components when producing the urethane foam. The molded product produced from the cyclic olefin polymer composition of the present invention and urethane foam can be adhered to each other.

Further, the cyclic olefin polymer composition of the present invention is not limited to the above-mentioned urethane foam, and exhibits good adhesion to various resins such as resin, metal, ceramics, paper, cloth and nonwoven fabric. . In particular, the modified cyclic olefin polymer composition of the present invention has good adhesiveness with a resin or a metal. For example, when a metal is used as the adherend, it exhibits particularly excellent adhesion to iron, aluminum, stainless steel and the like.

When a resin is used as the adherend, the cyclic olefin polymer composition of the present invention is an acrylic resin, urethane resin, epoxy resin, polyolefin, polyvinyl chloride resin, polyester resin, polycarbonate resin, polyamide. Resin, polyacetal resin,
Good adhesion to polyphenylene oxide resin, polystyrene resin, acrylonitrile-styrene resin and ABS resin.

[0139]

The cyclic olefin polymer composition of the present invention is a modified resin composition [A] obtained by modifying the cyclic olefin resin (a) and the elastomer (b) with a specific modifier (c). And a specific crystalline polyolefin resin [B], cracks, crazing, etc. are unlikely to occur even when they come into contact with fluorocarbons. Moreover, this composition has excellent adhesiveness, and exhibits good adhesiveness not only to resins but also to metals and the like.

The cyclic olefin-based copolymer composition of the present invention has essentially the properties of the cyclic olefin-based copolymer, although it has excellent properties such as CFC resistance and adhesiveness as described above. The mechanical strength, transparency and other properties are not impaired.

The composition of the present invention having the above-mentioned excellent properties can be easily produced by preparing the modified resin composition [A] in advance and mixing it with the specific crystalline polyolefin resin [B]. can do.

[0142]

EXAMPLES Next, the present invention will be described with reference to examples, but the present invention should not be construed in a limited manner by these examples.

Method for measuring physical properties (1) Preparation of test piece Using an injection molding machine IS-55EPN manufactured by Toshiba Machine Co., Ltd. and a predetermined test piece or square plate mold, molding was performed under the following molding conditions.

Molding conditions: Cylinder temperature 250 ° C., mold temperature 50 ° C., injection pressure primary / secondary = 1000/800 Kg
/ cm ² , injection speed is medium speed. The square plate for the CFC resistance test was produced by press molding at a molding temperature of 250 ° C. (2) Melt flow index (MFR at 260 ° C.) According to ASTM D1238, temperature 260 ° C., load 2.1
It was measured at 6 kg. (3) Intrinsic viscosity [η] Decalin solution was measured at 135 ° C. (4) Softening temperature (TMA) The softening temperature (TMA) was measured by the thermal deformation behavior of a 1 mm thick sheet using a Thermo Mechanical Analyzer manufactured by DuPont. That is, place a quartz needle on the sheet, apply a load of 49 g, and
The temperature rises at a rate of ° C / min, and the quartz needles are attached to the sheet.
The temperature that penetrated 635 mm was defined as TMA. (5) Bending test The bending test was performed according to ASTM D790.

Test piece shape: 5 × 1/2 × 1/8 ^t inch, span distance: 51 mm Test speed: 20 mm / min, test temperature: 23 ° C. (6) Izod impact test The test was performed according to ASTM D256.

Test piece shape: 5/2 × 1/2 × 1/8 ^t inch (with notch) Test temperature: 23 ° C. (7) Measurement of gloss It was measured by a gloss checker IG-320 manufactured by Horiba Ltd. (8) Freon resistance test A 150 × 150 × 2 ^t _mm square plate press-formed with 145
It was cut to × 50 × 2 ^t _mm , set on a stress jig having a constant radius of curvature, left in a chlorofluorocarbon (fluorocarbon 123) atmosphere (24 hours), and then taken out of the sample to check for cracks. The test was conducted on a stress jig having a radius of curvature R of 65 mm. In the evaluation of the test, one in which no crack was generated was evaluated as ◯, and one in which crack was generated was evaluated as x.

(9) Urethane Adhesion Test Specimen A was placed at the bottom of a tapered container having a depth of 50 mm (120 mm × 130 mm). Separately, the first and second liquids of urethane foam raw materials (resin premix (R), isocyanate (I): manufactured by Mitsui Toatsu Chemicals, Inc.) are mixed and stirred (mixing ratio (R) /
(I) = 1.156, mixing; 1000 rpm, stirring time; 3-4 sec), this mixed solution was immediately added to the above container, sealed and left for 10 minutes to complete the urethane foaming.

Thickness of urethane layer 25 mm, adhesion area 25 mm ×
The test piece prepared as described above is cut out so that 12.5 mm = 3.125 cm ^2, and the tensile shear strength is measured (test speed: 50 mm / min, test temperature: 23 ° C.), and the base metal is visually observed. Either destruction or interfacial peeling was confirmed. (10) Measurement of graft amount It was measured by IR absorption analysis (infrared absorption analysis).

[0149]

Example 1 As a cyclic olefin random copolymer,
A random copolymer of ethylene and 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene (DMON) (ethylene content: 73 mol%) Using. The intrinsic viscosity [η] measured for this copolymer was 0.6 dl / g, the MFR ° C. measured at 260 ° C. was 25 g / min, and the softening temperature was 115.
℃.

The above cyclic olefin random copolymer 5.
After thoroughly mixing 4 kg and an elastomer (low crystalline α-olefin copolymer) 0.6 kg, using a twin-screw extruder,
Melt blending at a cylinder temperature of 250 ° C., and to the obtained pellets 4 kg, 2-hydroxyethyl acrylate
0 g, Perhexin 25B (manufactured by NOF CORPORATION) and 4 g of divinylbenzene were added at a ratio of 5 and well mixed.
Melt blend this mixture again under the same conditions as above,
A modified resin composition was prepared by pelletizing using a pelletizer. The modification rate of the pellets with 2-hydroxyethyl acrylate was 0.8% by weight. 3.8 kg of this pellet was prepared.

Separately, as a crystalline polyolefin resin,
Homopolypropylene modified with maleic acid was used. This maleic acid-modified polypropylene was produced as follows.

To 2 kg of homopolypropylene having an MFR of 0.5 g / min at 230 ° C., 23 g of maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) and 1 g of Perhexin 25B were added and mixed well. This mixture was melt-blended by a twin-screw extruder at a cylinder temperature of 200 ° C., and pelletized by using a pelletizer. MFR of maleated polypropylene produced in this way at 230 ° C
Is 14 g / min and the grafted amount of maleic acid is 0.14% by weight. 0.2 Kg of this pellet was prepared. After thoroughly mixing the above-mentioned two types of pellets, they were melt-blended at a cylinder temperature of 250 ° C. by a twin-screw extruder and pelletized using a pelletizer to produce a cyclic olefin-based copolymer composition. Using a test piece formed from this composition, bending elastic modulus, Izod impact strength, transparency, CFC resistance and adhesive strength were tested to evaluate its characteristics. The results are shown in Table 1.

[0153]

Example 2 7.1 Kg of cyclic olefin random copolymer pellets was prepared. This copolymer contains ethylene, 1,4,
Random copolymer with 5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene (DMON) (Ethylene content:
73 mol%), and the intrinsic viscosity [η] measured for this copolymer was 0.6 dl / g, MFR ° C measured at 260 ° C.
Is 25 g / min and the softening temperature is 115 ° C.

Separately, an ethylene / propylene random copolymer pellet having an ethylene content of 80 mol% as an elastomer (low crystalline α-olefin copolymer) 0.9K
I prepared g. Intrinsic viscosity measured for this copolymer
[η] is 2.55 dl / g, glass transition temperature is -54 ° C, 2
The MFR measured at 30 ° C is 0.4 g / min.

After thoroughly mixing the above two types of pellets,
Cylinder temperature of 25 with a twin-screw extruder (TEM-35)
Melt blended at 0 ° C. and pelletized using a pelletizer.

To 6 kg of the obtained pellets, 60 g of 2-hydroxyethyl acrylate and 25B of perhexin
6 g (manufactured by Nippon Oil & Fats Co., Ltd.) and 6 g of divinylbenzene were added and mixed well.

This mixture was melt-blended again under the same conditions as above and pelletized using a pelletizer to prepare a modified resin composition. The modification rate of the pellets with 2-hydroxyethyl acrylate was 0.8% by weight. 3.6 Kg of this pellet was prepared.

Separately, as a crystalline polyolefin resin,
Homopolypropylene modified with maleic acid was used. This maleic acid-modified polypropylene was produced as follows.

To 2 kg of homopolypropylene having an MFR of 0.5 g / min at 230 ° C., 23 g of maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) and 1 g of perhexin 25B were added and mixed well. This mixture was melt-blended by a twin-screw extruder at a cylinder temperature of 200 ° C., and pelletized by using a pelletizer. MFR of maleated polypropylene produced in this way at 230 ° C
Is 14 g / min and the grafted amount of maleic acid is 0.14% by weight. 0.4 Kg of this pellet was prepared. After thoroughly mixing the above-mentioned two types of pellets, they were melt-blended at a cylinder temperature of 250 ° C. by a twin-screw extruder and pelletized using a pelletizer to produce a cyclic olefin-based copolymer composition. Using a test piece formed from this composition, bending elastic modulus, Izod impact strength, transparency, CFC resistance and adhesive strength were tested to evaluate its characteristics. The results are shown in Table 1.

[0160]

Example 3 7.0 kg of the cyclic olefin random copolymer used in Example 1 and 1.0 kg of the elastomer (low crystalline α-olefin copolymer) were thoroughly mixed, and then a cylinder was produced by a twin-screw extruder. Melt blending at a temperature of 250 ° C., 6 g of pellets obtained, 60 g of 2-hydroxyethyl acrylate, 25 g of Perhexin (manufactured by NOF Corporation)
6 g and 6 g of divinylbenzene were added and mixed well. This mixture was melt-blended again under the same conditions as above and pelletized using a pelletizer to prepare a modified resin composition. The modification rate of the pellets with 2-hydroxyethyl acrylate was 0.8% by weight. 3.2 kg of this pellet was prepared.

Separately, as a crystalline polyolefin resin,
0.8 kg of maleated polypropylene pellets used in Example 1 was prepared. After thoroughly mixing the above-mentioned two types of pellets, they were melt-blended at a cylinder temperature of 250 ° C. by a twin-screw extruder and pelletized using a pelletizer to produce a cyclic olefin-based copolymer composition. Using a test piece formed from this composition, bending elastic modulus, Izod impact strength, transparency, CFC resistance and adhesive strength were tested to evaluate its characteristics. The results are shown in Table 1.

[0162]

Example 4 6.86 kg of the cyclic olefin random copolymer used in Example 1 and 1.14 kg of an elastomer (low crystalline α-olefin copolymer) were thoroughly mixed, and then a cylinder was formed by a twin-screw extruder. Melt blend at a temperature of 250 ° C,
60 g of 2-hydroxyethyl acrylate, Perhexin 25B (Nippon Oil & Fats Co., Ltd.) per 6 kg of the obtained pellets
6 g) and 6 g of divinylbenzene were added and mixed well. This mixture was melt-blended again under the same conditions as above and pelletized using a pelletizer to prepare a modified resin composition. The modification rate of the pellets with 2-hydroxyethyl acrylate was 0.8% by weight. 2.8 kg of this pellet was prepared.

Separately, as a crystalline polyolefin resin,
1.2 kg of maleated polypropylene pellets used in Example 1 were prepared. After thoroughly mixing the above two types of pellets, use a twin-screw extruder to set the cylinder temperature to 250 ° C.
Was melt-blended with and pelletized using a pelletizer to produce a cyclic olefin-based copolymer composition. Using a test piece formed from this composition, bending elastic modulus, Izod impact strength, transparency, CFC resistance and adhesive strength were tested to evaluate its characteristics. The results are shown in Table 1.

[0164]

Example 5 In the same manner as in Example 2, except that homopolypropylene (MFR at 230 ° C., 230 ° C. was 7.0 g / min) was used as the crystalline polyolefin resin in place of maleated polypropylene. To produce a cyclic olefin-based copolymer composition.
Flexural modulus using a test piece formed from this composition,
Izod impact strength, transparency, freon resistance and adhesive strength were tested and their characteristics were evaluated. The results are shown in Table 1.
Shown in.

[0165]

Example 6 4.5 kg of the cyclic olefin random copolymer used in Example 1 and 1.5 kg of the elastomer (low crystalline α-olefin copolymer) were thoroughly mixed, and then a cylinder was formed by a twin-screw extruder. Melt blending at a temperature of 250 ° C., 4 kg of pellets obtained, 40 g of 2-hydroxyethyl acrylate, Perhexin 25B (manufactured by NOF Corporation)
4 g and divinylbenzene 4 g were added and mixed well. This mixture was melt-blended again under the same conditions as above and pelletized using a pelletizer to prepare a modified resin composition. The modification rate of the pellets with 2-hydroxyethyl acrylate was 0.8% by weight. 1.6 kg of this pellet was prepared.

Separately, as a crystalline polyolefin resin,
Homopolypropylene (MFR 230 ° C is 3.0 g / min)
2.4 kg of the above pellet was prepared. After thoroughly mixing the above two types of pellets, use a twin-screw extruder to set the cylinder temperature to 2
The mixture was melt-blended at 50 ° C. and pelletized using a pelletizer to prepare a cycloolefin copolymer composition.
Flexural modulus using a test piece formed from this composition,
Izod impact strength, transparency, freon resistance and adhesive strength were tested and their characteristics were evaluated. The results are shown in Table 1.
Shown in.

[0167]

Comparative Example 1 5.4 kg of the cyclic olefin random copolymer used in Example 1 and 0.6 kg of an elastomer (low crystalline α-olefin copolymer) were thoroughly mixed and then mixed with a twin-screw extruder. Melt blend at a cylinder temperature of 250 ° C,
40 kg of 2-hydroxyethyl acrylate, Perhexin 25B (Nippon Yushi Co., Ltd.) per 4 kg of the obtained pellets
4 g) and 4 g of divinylbenzene were added and mixed well. This mixture was melt-blended again under the same conditions as above and pelletized using a pelletizer to prepare a composition. Using a test piece formed from this composition, bending elastic modulus, Izod impact strength, transparency, CFC resistance and adhesive strength were tested to evaluate its characteristics. The results are shown in Table 1.

[0168]

Comparative Example 2 Comparative Example 1 is the same as Comparative Example 1 except that 2-hydroxyethyl acrylate was not added.
A composition was produced in the same manner as in. Bending elastic modulus, Izod impact strength, using a test piece formed from this composition,
The transparency, freon resistance and adhesive strength were tested to evaluate their properties. The results are shown in Table 1.

[0169]

Comparative Example 3 3.6 kg of the homopolypropylene pellets used in Example 4 and a low crystalline α-olefin copolymer.
After thoroughly mixing with 4 kg, the mixture was melt-blended by a twin-screw extruder at a cylinder temperature of 230 ° C., and pelletized using a pelletizer to prepare a composition. Using a test piece formed from this composition, bending elastic modulus, Izod impact strength, transparency, CFC resistance and adhesive strength were tested to evaluate its characteristics. The results are shown in Table 1.

[0170]

[Table 1]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshio Kimura 6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industry Co., Ltd. (72) Takashi Nakagawa Wa 6-2 Waki Kimachi, Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Takemi Yoshida 6-12 1-2 Waki, Wakimachi, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industry Co., Ltd.

Claims (10)

[Claims] 1. A random copolymer (a-1) of [A] (a) ethylene and a cyclic olefin represented by the following formula [I] or [II], represented by the following formula [I] or [II]: At least one selected from the group consisting of ring-opening polymers or ring-opening copolymers (a-2) of cyclic olefins, and hydrogenated products (a-3) of the ring-opening polymers or ring-opening copolymers (B) the crystallinity is 3 with respect to 100 parts by weight of the cyclic olefin resin.
The tensile modulus at 23 ° C is 0% or less and is 0.
Elastomer in the range of 1 to 2000 Kg / cm ² ;
5 to 50 parts by weight and a total of 1 of the above-mentioned components (a) and (b)
0.1 part by weight of at least one modifier selected from the group consisting of (c) ethylenically unsaturated group-containing carboxylic acid, its anhydride and ethylenically unsaturated group-containing carboxylic acid hydroxyalkyl ester; 1 to 10 parts by weight of a modified resin composition formed by contact with [B] a polyolefin resin having a crystallinity of more than 30% and a tensile modulus at 23 ° C. of more than 2000 kg / cm ^2. / 99 to 99/1 weight ratio of the cyclic olefin copolymer composition; [I] [In the formula [I], n is 0 or 1, m is 0 or a positive integer, r is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a and R ^b are Each independently,
Represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ may combine with each other to form a monocyclic or polycyclic group, and The cyclic or polycyclic group may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group]; ] [II] [In the formula [II], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ^{1 to} R ^1
19 independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, and R ⁹ is a bond. The carbon atom to which R ^{1 3} is bonded or the carbon atom to which R ¹⁰ is bonded and R
^The carbon atom to which ¹¹ is bonded is directly or has 1 to 1 carbon atoms.
3 may be bonded via an alkylene group, and
When n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring]. 2. The polyolefin resin [B] is at least one polyolefin selected from the group consisting of high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene and maleates thereof. The cyclic olefin-based copolymer composition according to claim 1. 3. The cyclic olefin resin (a) has a softening temperature of 70 ° C. or higher and an intrinsic viscosity [η] measured in decalin of 130 ° C. within a range of 0.05 to 10 dl / g. The cyclic olefin-based copolymer composition according to claim 1, which is characterized in that. 4. The cyclic olefin copolymer composition according to claim 1, wherein the elastomer (b) is an ethylene-propylene random copolymer. 5. The cyclic olefin-based copolymer composition according to claim 1, wherein the modifier (c) is an ethylenically unsaturated group-containing carboxylic acid hydroxyalkyl ester. 6. A random copolymer (a-1) of [A] (a) ethylene and a cyclic olefin represented by the following formula [I] or [II], represented by the following formula [I] or [II]: At least one selected from the group consisting of ring-opening polymers or ring-opening copolymers (a-2) of cyclic olefins, and hydrogenated products (a-3) of the ring-opening polymers or ring-opening copolymers (B) the crystallinity is 3 with respect to 100 parts by weight of the cyclic olefin resin.
The tensile modulus at 23 ° C is 0% or less and is 0.
Elastomer in the range of 1 to 2000 Kg / cm ² ;
5 to 50 parts by weight of a composition containing (c) at least one modification selected from the group consisting of carboxylic acids containing ethylenically unsaturated groups, their anhydrides and hydroxyalkyl esters of ethylenically unsaturated groups containing carboxylic acid. Agent
For 100 parts by weight of the total of the components (a) and (b),
After preparing a modified resin composition by blending in an amount of 0.1 to 10 parts by weight and bringing them into contact with each other, the modified resin composition and [B] the crystallinity exceeds 30% and the tensile strength at 23 ° C. A method for producing a cyclic olefin-based copolymer composition, which comprises mixing a polyolefin resin having a modulus of more than 2000 kg / cm ² with a weight ratio of 1/99 to 99/1; [I] [In the formula [I], n is 0 or 1, m is 0 or a positive integer, r is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a and R ^b are Each independently,
Represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ may combine with each other to form a monocyclic or polycyclic group, and The ring or polycyclic group may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group]; ] [II] [In the formula [II], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ^{1 to} R ^1
19 independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, and R ⁹ is a bond. The carbon atom to which R ^{1 3} is bonded or the carbon atom to which R ¹⁰ is bonded and R
^The carbon atom to which ¹¹ is bonded is directly or has 1 to 1 carbon atoms.
3 may be bonded via an alkylene group, and
When n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring]. 7. The polyolefin resin [B] is at least one polyolefin selected from the group consisting of high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene and maleates thereof. A method for producing the cyclic olefin-based copolymer composition according to claim 6. 8. The cyclic olefin resin (a) has a softening temperature of 70 ° C. or higher and an intrinsic viscosity [η] measured in decalin of 135 ° C. within a range of 0.05 to 10 dl / g. 7. The method for producing a cyclic olefin-based copolymer composition according to claim 6. 9. The method for producing a cyclic olefin copolymer composition according to claim 6, wherein the elastomer (b) is an ethylene-propylene random copolymer. 10. The method for producing a cyclic olefin copolymer composition according to claim 6, wherein the modifier (c) is a carboxylic acid hydroxyalkyl ester containing an ethylenically unsaturated group.