JPH03122157A - Production of impact-resistant cyclic olefinic resin composition - Google Patents

Abstract

PURPOSE:To obtain an impact-resistant cyclic olefinic resin composition by reacting a cyclic olefinic resin formed from a specific cyclic olefin with a soft copolymer and organic peroxide. CONSTITUTION:The objective composition obtained by reacting (A) a cyclic olefinic resin composed of a (co)polymer prepared by carrying out ring opening (co)polymerization of a cyclic olefin expressed by the formula (n is 0 or 1; m is 0 or a positive integer; R<1> to R<18> are H, halogen, hydrocarbon, etc.) or a hydrogeneted substance thereof with (B) a soft copolymer, selected from cyclic olefinic random copolymers having units composed of ethylene, an alpha-olefin and the cyclic olefin expressed by the formula, amorphous or low-crystalline alpha-olefinic copolymers, copolymers of >=2 kinds of alpha-olefins and non-conjugated dienes, etc., and having <=0 deg.C glass transition temperature and (C) an organic peroxide and preferably a radical-polymerizable compound.

Description

[Detailed description of the invention] 1. The present invention: A method for producing a resin composition with excellent impact resistance, which comprises reacting a cyclic olefin resin, a soft copolymer, and an organic peroxide. Regarding.

1 Cyclic olefin has an ethylenic double bond in its ring, and by reacting with an a-olefin such as ethylene, cyclic olefin and ethylene random can be produced. This random copolymer, which was often used as a copolymer, has excellent properties such as transparency, heat resistance, chemical resistance, electrical properties, mechanical strength, and moldability. The molded bodies produced from the same also have excellent dimensional stability.

Cyclic olefin 1 as above α
-It is already known that polymers used as copolymers with olefins, ring-opened cyclic olefins themselves, and hydrogenated products thereof can be used as optical materials with excellent rigidity, transparency, water resistance, and thermal properties. (Refer to the specification of JP-A-60-26024).

Although such cyclic olefin resin iL has transparency, water resistance, and thermal properties, as a result of further research by the present inventor, it has been found that it is possible to blend other resins into such cyclic olefin resin. The present invention has found that it is possible to obtain a resin composition with even more excellent properties that can be used for various purposes. The object of the present invention is to provide a method for producing a resin composition with dramatically improved properties, that is, a cyclic olefin resin composition with an extremely excellent balance between rigidity and impact resistance.

1 Skin A patient 1 The method for producing a cyclic olefin resin composition according to the present invention includes a ring-opening polymer or a ring-opening copolymer formed by ring-opening polymerization of a cyclic olefin represented by the following formula [1], or a ring-opening copolymer thereof. It is characterized by reacting a cyclic olefin resin made of a hydrogenated product of a polymer or copolymer, a soft polymer, and an organic peroxide.

... [■ However, in formula [I], n is O or 1, and m
is O or a positive integer, R1 to R18 each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group; RIS to R+8 are bonded to each other to form a monocyclic or A polycyclic group may be formed, and the monocyclic or polycyclic group may have a double bond, and R1' and RI6 or R17 and R1'' may form an alkylidene group. It may form a group.

The resin composition produced according to the present invention is made by reacting a cyclic olefin polymer obtained by ring-opening polymerization or copolymerization of a specific cyclic olefin with a soft copolymer and an organic peroxide. Therefore, it has an excellent balance between rigidity and impact resistance.

Next, a method for producing a cyclic olefin resin composition according to the present invention will be specifically explained.

In the method for producing a cyclic olefin resin composition according to the present invention,
A cyclic olefin resin formed by ring opening of a specific cyclic olefin represented by the following formula [I] is reacted with a specific amount of a soft copolymer and an organic peroxide.

[■] In the above formula [2], n is 0 or 1, and m
is 0 or a positive integer.

And R1 to RI8 are each independently a hydrogen atom,
Represents an atom or group selected from the group consisting of a halogen atom and a hydrocarbon group. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In addition, examples of the hydrocarbon group include, each independently, an alkyl group usually having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms. Specific examples of the alkyl group include:
Methyl toad Ethyl group Isopropyl group Inbutyl group
Amyl group, Hexyl group, Octyl group, Decyl group, Dodecyl group, Heptadecyl group, Octadecyl group, etc., and specific examples of the cycloalkyl group include Cyclopentyl group, Cyclohexyl group, and Cyclooctyl group.

Furthermore, in the above formula [I], RI5 and R116, or RI7 and R18 and force ＼ Furthermore, RI 6 ~
R11 may be bonded to each other (together) to form a monocyclic or polycyclic group, and this monocyclic or polycyclic group may have a double bond.

Also, RI6 and RI6, or RI7 and R111
and may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include a propylidene group and an impropylidene group.

(The following is a blank space) The cyclic olefin represented by the above formula [I] can be easily produced by condensing cyclopentadiene and a corresponding olefin by a Diels-Alder reaction.

Formula [I ] As a cyclic olefin represented by in particular, Parable number f1 hmm 7-methylbicyclo[2 Bicyclo [2, 2, 11 hept-2- enticement conductor: 5.10-dimethyltetra CH.

9-Inbutyl-2,7- 9,11,12-trimethyl 2,7.9-) Remethylte CH.

Sen 9-Inbutyl-11,12 5,8,9,10-tetramethy 1＠　]-]3-Dodese -Methyl-9-ethylte 8-chlorotetrashif -3-Dodecene 8-Promotitrasif 8-Fluorotetracy +@]-3-dodecene 1a]-]3-dodece -Methyltetrashif 8-ethyltetrashif 1@]-3-dodecene 8-hexyltetracy C,,H,.

・I @]-]3-dodecene, 17 1 day]-3-dodecene+@]-3-dodecene-3-dodecene, 1@] 3-dodecene, 12. S.1? , l5l-3-)'f-1=nn8-ethylidene-9-iso-dodecene 12, s, 17. ll! ]-3-dodecene 5, 1+8 3-dodecene 8-n-propylidene-9 1-dodecene 8-isopropylidene 1-dodecene + s ]-]3-dodece-tetracyclo[4,4,0,12 such as dodecene 5,17 +el-3-dodecene derivative: (blank below) 8-n-propylidene-9 [4,4,0,12 5,17・11-3 dodecene chro[4,4,0,12 7 +a]-3 -Dodecene 8-n-propylidene-9 [4,4,0,12 5,17 +8]-dodecene 8-isopropylidene+41-4-heptadecenedecenedeceneheptadecene+8, Ql 11. Ql2 1 Co-5-tocosene derivative; +3. Q2.7. Hexacyclo[6,6,1,13,6,119+ such as Ql, +4]-4-heptadecene
3, Q2, 7, Qs +-]-4-hebutadecene derivatives; tococene 18.113 + 6, Ql 8.01 Hs sen 171-5-tococene 15-ethyl octasiph 2-lo]-5-tococene, etc. Pentacyclo[6,6,1,13,6,027,
09th] -4- and other octacyclo [8, 8, 0, 129, 14? , I+ 1 18.11 hexadecene derivatives; tricyclo[4,3,0,12.5]-3-decene derivatives such as heptacyclo[8,7,0 5-methyl-tricyclo; heptacyclo-5-icosene such as cosene Derivatives or hebutacyclo-5-heneicosene! Conductor; 10-methyltrisic CH.

tricyclo[4,4,0,12.5]-3-undecene derivatives such as 2-methyltricyclo; pentacyclo[4,7,0,12 such as 1,3-dimethyl-penta1,6-dimethylpentacene ,5,08,+
3.19. +2]-3-pentadecene derivatives; nopentacyclo[6,5,1,13,6,Q2. γ
, Qs, +3]-4-pentadecene derivative; 2, +s]-4-eicosene, etc.
11"+7,011.18.l12.15] -4-Diene compounds such as eicosene derivatives; 21.113.2@, □z.19.118, l] -5-
Bentacosen 3.29. QIJ, +9. lIs, +8]-5-bentacocene and other nonacyclo[9,10,1,147,03,s,
02. +s, 0+2.21, 113.211. QIJ,
Ifl, l15.111] -5-bentacocene derivatives.

(Left below) The ring-opening polymer or ring-opening copolymer used in the present invention can be obtained by subjecting the cyclic olefin represented by the formula [I] to ring-opening polymerization or ring-opening copolymerization using a known method. Polymers can be produced.

That is, such a ring-opening polymer or ring-opening copolymer can be produced by polymerizing or copolymerizing a cyclic olefin represented by the above formula [I] in the presence of a ring-opening polymerization catalyst.

The ring-opening polymerization catalyst used here includes ruthenium,
A catalyst consisting of a metal halide, nitrate or acetylacetone compound such as rhodium, palladium, osmium, indium or platinum, and a reducing agent such as alcohol.

Examples of the catalyst include a metal halide such as titanium, palladium, zirconium, or molybdenum, or an acetylacetone compound, and an organic aluminum.

The rAJIJ polymer or copolymer used in the present invention contains repeating units derived from the cyclic olefin represented by the above formula [y], usually at least 50 mol%, preferably at least 80 mol%, particularly preferably at least 80 mol%. It contains 90 mol% or more. The molecular weight of such a ring-opened polymer or ring-opened copolymer is usually in the range of 1,000 to 500,000, preferably 10,000 to 10,000. This molecular weight can be controlled by adjusting the reaction conditions.
For example, it can be adjusted by blending a small amount of olefin or other cycloolefin.

By performing ring-opening polymerization or ring-opening copolymerization as described above, a cyclic olefin represented by the following formula [nl
It is thought that it has the structure shown below.

... [nl However, in the above formula [■], n and m and R
1 to R111 has the same meaning as above.

In the present invention, as the cyclic olefin resin, a hydrogenated product of the ring-opening polymer or copolymer described above can be used together with or separately from the ring-opening polymer or copolymer described above. This hydrogenated product can be produced by hydrogenating double bonds remaining in the ring-opened polymer or copolymer produced as described above.

As the hydrogenation catalyst used in this case, a heterogeneous catalyst or a homogeneous catalyst that is generally used in hydrogenating olefins can be used.

Examples of such heterogeneous catalysts include catalysts in which nickel, palladium, platinum, or these metals are supported on a carrier such as carbon, silica diatomaceous earth, alumina, or titanium oxide. Mention may be made of nickel/silica, nickel/diatomaceous earth, palladium/carbon, palladium/silica, palladium/diatomaceous earth, palladium/alumina.

In addition, examples of heterogeneous catalysts include catalysts based on metals from group Ⅰ of the periodic table; specific examples include (
A catalyst consisting of a Ni or Co compound such as nickel naphthenate/triethylamine, n-butyllithium naphthenate, nickel acetylacetonate/triethylaluminum, and an organometallic compound of a metal in Groups 1 to M of the periodic table.Additionally, Rh compounds are listed. be able to.

The hydrogenation reaction can be carried out in a homogeneous or heterogeneous system depending on the type of catalyst.

The pressure of hydrogen gas +L during such hydrogen addition is usually 1
~150 atm, reaction temperature 1 ℃, usually set within the range of 0 to 100°C, preferably 20 to 100°C.

The hydrogenation rate can be adjusted arbitrarily by changing the hydrogen pressure, reaction temperature, reaction time, catalyst concentration, etc. As the hydrogenation rate increases, the weather resistance and heat aging resistance of the resin improve. As for the hydrogenated substance used in the invention, it is preferable that 50% or more of the double bonds present in the polymer or copolymer are hydrogenated, particularly 80% or more, and more preferably 90% or more. It is preferable that

The hydrogenated product produced in this way can be expressed, for example, by the following formula [
It is thought to have a structure represented by I[I].

... [ml However, in the above formula [m], n and m and R
1 to Rla LL Same meaning as above.

In the present invention, the ring-opening polymer, the ring-opening copolymer, and the hydrogenated product can be used individually or in combination. Furthermore, these ring-opening polymerized Honma ring copolymers and hydrogenated compounds may be modified with an unsaturated carboxylic acid such as maleic anhydride. When producing a ring-opening copolymer or a hydrogenated product, it is also possible to polymerize a cyclic olefin other than the cyclic olefin represented by the above formula [I] within a range that does not impair the properties of the resulting polymer, etc. If 1 is also used as such a cyclic olefin.

Cyclobutene, cyclopentene, cyclohexene, 3.4-dimethylcyclohexene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, 2,
3.3a, 7a-tetrahydro-4,7-methano-I
Examples include H-indene, 3a, 5.6.7a-tetrahydro-4,'I-) tanoh-IH-indene, and the like. Such other cyclic olefins can be used alone or in combination, and are usually used in an amount of 0 to 20 mol%.

In the present invention, the soft polymer has a glass transition temperature (Tg) measured with a thermomechanical analyzer.
A resin having a temperature of 0°C or lower, preferably -10°C or lower, more preferably -20°C or lower is used.

Furthermore, the intrinsic viscosity of the soft polymer used in the present invention measured in decalin at 135° C.
1~10dJ/g Good tt, <Hao, 08~7d
It is within the range of Q/g.

In addition, the crystallinity of the soft polymer used in the present invention measured by X-ray diffraction is usually in the range of 0 to 10%, preferably 0 to 7%, particularly preferably 0 to 5%, Such soft polymers are copolymers with poor quality or low crystallinity.

Such soft polymers are described below (a)
It is preferable to use copolymers of -(d).

The cyclic olefin random copolymer (a) that can be used as a soft polymer in the present invention comprises a repeating unit derived from ethylene, a repeating unit derived from an a-olefin other than ethylene, and a repeating unit derived from the above formula [I A cyclic olefin random copolymer consisting of a repeating unit derived from a cyclic olefin represented by
The intrinsic viscosity measured in decalin at 135°C is usually 0.
．． 01-10di7/mi, preferably 0.08-7d1
It is a cyclic olefin random copolymer with a glass transition temperature of usually 0° C. or lower, preferably -20° C. or lower. Here, examples of a-olefins other than ethylene include a-olefins having 3 to 20 carbon atoms, and specific examples of such a-olefins include propylene, 1-butene, 4-methyl −
Mention may be made of 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

In such a cyclic olefin random copolymer,
The amount of repeating units derived from ethylene is usually 4
0 to 98 mol%, preferably 50 to 90 mol%,
The amount of repeating units derived from a-olefins other than ethylene is usually 2 to 50 mol%, preferably 5 to 4 mol%.
0 mol%, and the amount of repeating units derived from cyclic olefin is usually 2 to 20 mol%, preferably 2 to 20 mol%.
It is within the range of 15 mol%. In this cyclic olefin random copolymer, the repeating units derived from ethylene, the repeating units derived from α-olefins other than ethylene, and the repeating units derived from cyclic olefins are arranged substantially linearly. ing. That is, this cyclic olefin random copolymer does not substantially have a gel-like crosslinked structure.

Such a cyclic olefin random copolymer is produced by combining ethylene, a cyclic olefin, and optionally another a-olefin in a hydrocarbon solvent with a catalyst formed from a hydrocarbon-soluble vanadium compound and a halogen-containing organoaluminum compound. It can be produced by polymerizing in the presence of.

As the hydrocarbon solvent used here, for example, aliphatic hydrocarbon fish, alicyclic hydrocarbons, aromatic hydrocarbons, and the like can be used. Furthermore, among the monomers used in preparing the cyclic olefin resin, compounds that are liquid at the reaction temperature can also be used as the reaction solvent.

These solvents can be used alone or in combination.

The vanadium compound used as a catalyst in this reaction has the formula VO (OR), V, or the formula V (OR). Examples include compounds represented by X.

In the above formula, R is a hydrocarbon group, and 0≦a≦3
．． 0≦b≦3.2≦a+b≦3.0≦C≦4.0≦d≦
4.3≦c10d≦4.

As these vanadium compounds (specifically vOC
! 3, VO(QC2H6)C52, VO(OC2H8) 2c&2, VO(0-is o-C,H,) C(j,,
VO(0-n-C,He)C(22, VO(○C2H3)3, VOB r2, vCJ2 voc, 52, VO(On-C4H*)3% V Cfl 3 ・20 CsH+70 H etc. These vanadium compounds can be used alone or in combination.

Such a vanadium compound may be an adduct of a vanadium compound represented by the above formula and an electron donor.

Examples of electron donors that form adducts with the above vanadium compounds include alcohols, phenolic ketones, aldehydes, carboxylic acids, organic acid esters, inorganic acid esters, ethers, acid amides, acid anhydrides, and alkoxysilanes. Oxygen electron donors: Mention may be made of nitrogen-containing electron donors such as ammonia, amines, nitriles and isocyanates.

As the organoaluminum compound used as a catalyst together with the vanadium compound as described above, a compound having at least one A° C.-carbon bond in the molecule can be used.

Examples of organoaluminum compounds that can be used in the present invention include R+, Afl (OR2) nH,X.

(In the formula, R1 and R2131 to 15, preferably 1 to
Hydrocarbon groups containing 4 carbon atoms may be the same or different from each other. X is a halogen, m is 0≦m≦3, n is O≦n<3, p is 0≦n<3, q is O≦q<3, and m+n+p+q;3) Aluminum compound formula M+AIR+.

(In the formula, Ml is Li, Na or K, and R1 has the same meaning as above.) A complex alkylated product of a Group 1 metal and aluminum, etc., can be mentioned.

The concentration of the above-mentioned vanadium compound in the reaction system is usually 0.
01-5 gram atoms/liter, preferably OO5-3
It is used in amounts of gram atoms/liter. Further, it is used in an amount such that the ratio of aluminum atoms to vanadium atoms (11!/V) in the organoaluminum compound A polymerization reaction system is 2 or more, preferably 2 to 50, particularly preferably 3 to 20.

By reacting as described above, the formula [T
It is thought that the cyclic olefin represented by co is copolymerized with an a-olefin in a form represented by the following formula [n] to form a cyclic olefin random copolymer.

... [nl Just beast In the above formula [■], n, m and R
1-RIIfL Same meaning as above.

Note that the cyclic olefins used in the present invention may be used alone or in combination.

Example If, 1,4,5.8-dimethanol 1.2
．． 4.4a, 5.8.8-Octahydronaphthalenes polymerized together, and the above naphthalenes and norbornene (e.g. bicyclo[2,2,1]hept-2
-ene) can be copolymerized.

Methods for producing such cyclic olefin random copolymers include, for example, JP-A-60-168708 and JP-A-61-12.
No. 0816, No. 61-115912, No. 61-
No. 225916, No. 61-271308, No. 61
It is described in publications such as No. -272206 and No. 62-252406.

In the present invention, the α-olefin copolymer (b) used as the soft polymer is a copolymer formed from at least two types of α-olefins, and usually the glass transition temperature of this copolymer is wide. Below 0°C, preferably -20°C
below ℃. This copolymer is a non-quality or low-crystalline copolymer having a crystallinity of usually 10% or less, preferably 5% or less.

Such α-olefin copolymers (for example, (b-
There are 1) ethylene/σ-olefin copolymer and, for example, (b-2) propylene/a-olefin copolymer, and any of these copolymers can be used in the present invention. .

F”l of these copolymers, (b-1) ethylene.
As the a-olefin constituting the a-olefin copolymer, A usually has 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms.
of a-olefins are used. Specific examples of such a-olefins include propylene, 1-butene,
1-hexene, 4-methyl-1-pentene, 1-
Mention may be made of octene and 1-decene, which can be used alone or in combination. In such an ethylene/a-olefin copolymer, +
t Molar ratio method of ethylene and α-olefin Although it varies depending on the type of α-olefin, it is generally within the range of 30° to 95°5.

(b-2) As the α-olefin constituting the propylene/α-olefin copolymer, an α-olefin having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms is used. Specific examples of such α-olefins include 1-butene, 1-hexene, 4-methyl-
Mention may be made of 1-pentene, 1-octene and 1-decene, which can be used alone or in combination. In such a propylene/α-olefin copolymer, the molar ratio of propylene to α-olefin (J4) varies depending on the type of α-olefin, but is generally within the range of 30:70 to 95:5.

In the present invention, the α-olefin/diene copolymer (C) IL used as a soft polymer is formed from at least two types of α-olefins and at least one type of non-conjugated diene and has a glass transition temperature of usually 0. It is an α-olefin/diene copolymer with a temperature below ℃.

i! as the α-olefin/diene copolymer used in the present invention! , (c-1) Ethylene・α-olefin・
Diene copolymer rubber and (c-2) propylene/a-
There is olefin/diene copolymer rubber.

Here, the a-olefin constituting the (C() ethylene/a-olefin/diene copolymer rubber) is usually an a-olefin having 3 to 10 carbon atoms, preferably 3 to 10 carbon atoms. Specific examples of a-olefins include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene, which may be used alone or in combination. In such ethylene/a-olefin/diene copolymer rubber,
The molar ratio of ethylene to α-olefin varies depending on the type of α-olefin, but is generally 30 nia 0 to 9
5: Within the range of 5.

In addition, (c-2) propylene/α-olefin/diene copolymer rubber is used as the α-olefin (usually an a-olefin having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms). Specific examples of such a-olefins include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene, which may be used alone or in combination. In such a propylene/α-olefin/diene copolymer rubber, the molar ratio of propylene to α-olefin varies depending on the type of α-olefin, but is generally 30 to 0. ~95゛ 5
is within the range of

Specific examples of the diene component in the above copolymer rubber include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5- linear conjugated dienes such as hebutadiene and 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene- Cyclic nonconjugated dienes such as 2-norbornene and 5-impropylidene-2-norbornene; 2,3-diisopropylidene-5-norbornene and 2-propenyl-2,2
- Norbornagene, etc. can be mentioned. These diene components can be used alone or in combination.

The content of repeating units derived from the diene component in the above copolymer rubber is usually 1 to 20 mol%, preferably 2 to 15 mol%.

In the present invention, (d) an aromatic hydrocarbon/conjugated diene random or block copolymer or a hydride thereof (usually has a glass transition temperature of 0° C. or lower) used as the soft polymer.

Specifically, such aromatic hydrocarbon/conjugated diene random or block copolymers or hydrides thereof include (d-1) styrene/butadiene block copolymer rubber, (d-2) styrene/butadiene block copolymer rubber, and (d-2) styrene/butadiene block copolymer rubber. Butadiene-styrene block copolymer rubber, (d-3) Styrene-isoprene block copolymer rubber, ('d-4) Styrene-isoprene-styrene block copolymer rubber, (d-5) Hydrogenated styrene-butadiene - Styrene block copolymer rubber, (d-6) hydrogenated styrene/isoprene/styrene block copolymer rubber, and (d-7) styrene/butadiene random copolymer.

In these copolymer rubbers, the molar ratio of aromatic vinyl hydrocarbon to conjugated diene is generally 10:90 to 7.
It is set within the range of 0.030.

In addition, among the above copolymer rubbers, (d-5) hydrogenated styrene/butadiene/styrene block copolymer rubber remains in (d-2) styrene/butadiene/styrene block copolymer rubber. It is a copolymer rubber in which some or all of the ethylenic double bonds are hydrogenated,
(d-6) Hydrogenated styrene/isoprene/styrene block copolymer rubber tk (d-4) Styrene/
This is a copolymer rubber in which some or all of the ethylenic double bonds remaining in the isoprene/styrene block copolymer rubber are hydrogenated.

(e) Specific examples of the conjugated diene polymer or its hydride include polybutadiene, polyisoprene, and rubbers in which part or all of these double bonds are hydrogenated.

The soft polymers mentioned above can be used alone or in combination.

In the cyclic olefin resin composition of the present invention, the above-mentioned soft polymer is the cyclic olefin resin 1 described above.
It is used in an amount within the range of 5 to 150 parts by weight relative to 00 parts by weight. By using a soft polymer within the above range, the impact strength is high, and the decrease in rigidity, heat distortion temperature and hardness is also small. By adjusting the amount of the soft polymer to the cyclic olefin resin, preferably within a range of 5 to 1°O weight, and more preferably 10 to 80 parts by weight, impact strength, rigidity, heat distortion temperature, hardness, etc. A well-balanced resin composition with excellent properties can be obtained.

Organic peroxides used in the present invention include 11 ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; 1.1-bis(
1-butylperoxy)cyclohexane and 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.

Sheet-t-butyl peroxide, 2,5-dimethyl-2,
5-di(t-buty, ruberoxy)hexane and 2,
Dialkyl peroxides such as 5-dimethyl-2,5-di(t-butylperoxy)hexyne-3: Diacyl peroxides such as lauroyl peroxide and benzoyl peroxide.

Peroxy esters such as t-butylperoxyacetate, t-butylperoxybenzoate, and 2,5-dimethyl-2,5-di(benzoylperoxy)hexane can be mentioned. These organic peroxides can be used alone or in combination.

The above organic peroxide is used in an amount of 001 to 1 part by weight, especially 005 to 05 parts by weight, based on 100 parts by weight of the total weight of the cyclic olefin resin and soft polymer. is preferred.

By blending such an organic peroxide into a resin consisting of a cyclic olefin resin and a soft polymer and allowing them to react, a crosslinked structure is created in the cyclic olefin resin and the soft polymer that are mutually dispersed. is formed, and
It is believed that a crosslinked structure is also formed between the cyclic olefin resin and the soft polymer.The formation of such a crosslinked structure significantly improves properties such as mechanical properties.

Olefin-based resin composition cutting margin according to the present invention The above-mentioned cyclic olefin-based random co-electropolymer resin A car that is essential to be formed from a soft polymer and an organic peroxide In addition, a radically polymerizable functional group is incorporated in the molecule. It is preferable to mix a compound having two or more of these. By blending such a compound, a composition with excellent impact resistance can be obtained.

Examples of compounds having two or more radically polymerizable functional groups in the molecule that can be used in the present invention include: divinylbenzene, vinyl acrylate, vinyl methacrylate, ethylene dimethacrylate, triallyl cyanurate, and diallyl phthalate. can be mentioned.

The blending amount of the components of such a compound is based on 100 parts of the total amount of the cyclic olefin resin and the soft polymer,
It is usually 1 part by weight or less, preferably 0.1 to 0.5 parts by weight.

The resin composition of the present invention further contains a heat stabilizer, a weathering stabilizer, an antistatic K, a slip agent, an anti-blocking agent, an anti-fog agent, a lubricant, a dye, a pigment, a natural liquid, and a synthetic method.
Wax, organic fillers, inorganic fillers, etc. can be blended.

Examples of the stabilizers used in the present invention include tetrakis[methylene-3(3,5-di-t-butyl-4hydroxyphenyl)propionate comethane, β-(3,
Phenolics such as 5-di-t-butyl-4-hydroxyphenyl)propionic acid alkyl esters and 2,2'-oxamidobis[ethyl-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate] Oxidation stabilizers zinc stearate, calcium stearate and 12
- Fatty acid metal salts such as calcium hydroxystearate: polyhydric alcohol fatty acid esters such as glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate and pentaerythritol tristearate, etc. can be mentioned.

These can be used alone or in combination. Examples of such combinations include tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate comethane, zinc stearate, and glycerol monostearate. be able to.

Further, examples of organic or inorganic fillers that can be used in the present invention include silica, diatomaceous earth, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate,
Dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber, Silicon carbide fiber, polyethylene fiber,
Mention may be made of polypropylene fibers and polyamide fibers.

For 100 parts by weight of such organic or inorganic filling life 1 + cyclic olefin resin and soft polymer,
It is usually used in an amount of 1 to 100 parts by weight, preferably 5 to 100 parts by weight, particularly preferably 5 to 50 parts by weight.

In addition, other resins can also be blended into the resin composition of the present invention within a range that does not impair its properties. Examples of resins that can be blended in this case include polyester, polyolefin, polyamide, polycarbonate, polyacetal, polyphenylene oxide, polyphenylene sulfide, polyimide, fluororesin, and epoxy resin.

For example, after mixing the above-mentioned cyclic olefin resin, soft polymer, and organic peroxide at the same time,
Or 14: After mixing the cyclic olefin resin and the soft polymer, an organic peroxide is mixed and reacted.

At this time, the cyclic olefin resin and the soft polymer can be mixed by blending the cyclic olefin resin and the soft polymer in a molten state using an extruder, or by using a method such as heptane, hexane, decane, or cyclohexane. Saturated hydrocarbon milk can be mixed by dissolving a cyclic olefin resin and a soft polymer in an aromatic hydrocarbon such as toluene, benzene, or xylene, and then removing the solvent. .

After the components are mixed in this manner, the reaction is usually carried out by heating to a temperature equal to or higher than the one-minute half-life of the organic peroxide used. Further, even when a compound having two or more radically polymerizable functional groups in the molecule is used as an optional component, it is preferable to heat the resin to a temperature equal to or higher than the 1 minute half-life of the organic peroxide. By doing so, a crosslinked structure is effectively formed.

The cyclic olefin resin composition thus obtained has the excellent properties that cyclic olefin resins inherently have, and is particularly excellent in properties such as impact resistance and rigidity.

The cyclic olefin resin composition obtained in this manner can be used in the same manner as a cyclic olefin resin.

For example, compositions from low molecular weight resins can be used as synthetic waxes, pine wood impregnated, paper processed and sized.
Rubber anti-aging valve L Corrugated cardboard waterproof vein Chemical fertilizer slowing agent, heat storage agent, ceramic binder e.g. paper capacitor
Electrical insulation for TA or cables, neutron moderation, textile processing, support building materials, water replenishment, paint protection materials, polishing, thixotropic additives, pencil/crayon core hardness imparting, pure carbon ink base, electrostatic copying Toner binder Synthetic resin molding lubricant K Mold release port Resin coloring Qi L It can be used as a hot melt adhesive, lubricating grease, etc. In addition, compositions made of high molecular weight resins are used in water tanks for electric irons, microwave ovens, printed circuit boards, high frequency circuit boards, conductive sheet materials, camera bodies, housings for various instruments and equipment, films, seat covers, helmets, etc. It can be used as

The cyclic olefin resin composition obtained by the method of the present invention can be molded using known methods.

For example, a single screw extruder, a vented extruder, a two-screw extruder, a conical two-screw extruder, a co-kneader, a plateificator, a mixtruder, a gear-type extruder,
Extruded adult pigs, injection adult pigs, blow adult pigs, rotary molding, foam molding, etc. can be performed using screwless extruders, planetary screw extruders, etc.

Injection molding plate manufactured using resin manufactured by the method of the present invention The various copolymers described above can be molded by injection molding methods known per se, and the following molded products can be manufactured.

■Automotive parts Instrument panels, console boxes, meter clusters, column covers, grill door mirrors, fender bonnets, radiator grills.

■Machine housing tools (1! Power tools), office equipment (word processors, personal computers, copiers, printers, FDD, CRT), precision equipment (cameras), home appliances (microwave ovens, electric cookers, refrigerators, pots, cleaning 8) the law of nature.

■Machine parts Sirocco fan for air conditioner.

In addition, the above-mentioned forming methods (vacuum grown pigs using L sheets, heat forming such as air pressure forming, fusion, adhesion, etc.)
Secondary processing can also be performed using methods such as hot stamping, painting, and flocking.

i and Ω momme] According to the present invention, 1f1 Since a resin composition is formed by the reaction of a cyclic olefin resin formed from a specific cyclic olefin, a soft polymer, and an organic peroxide, the resin composition is formed in a mutually mixed state. A cross-linked structure is formed between a certain cyclic olefin resin and a soft polymer.Although the rigidity of the cyclic olefin resin decreases slightly, its impact resistance is significantly improved, resulting in an overall composition with an excellent balance between rigidity and impact resistance. can manufacture things.

(The following is a blank space.) Next, the present invention will be explained in more detail by showing examples of the present invention.The present invention should not be construed as being limited by these examples.

In addition, the measuring method and evaluation method of various physical property values in this invention are shown below.

(1) Melt flow index (MFR, OC) Temperature T℃, load 216k according to ASTM D1238
(2) Preparation of test piece Molded under the following molding conditions using an injection molding machine IS-35 manufactured by Toshiba Machine ■ and a specified mold for making a test piece.
Test piece was left at room temperature for 48 hours after molding. Molding conditions: Cylinder temperature: 270°C Mold temperature: 60°C Injection pressure: 1000/800 kg/c
m2 injection speed (-next) 30% Screw rotation speed: 150 rpm (3) Bending test A S T M D 790 k: Semi-shite row Test piece shape: 5 x 1/2 x 1/84 inch Distance between spans: 51 mm Test speed: 20 mm/min Test temperature: 23°C (4) Izot impact test conducted in accordance with ASTM D256 Test piece shape: 5/2 x 1/8 x 1/2' inch (with notch) Test temperature: 23°C (5) Heat Deformation temperature (HDT) Test specimen shape: 5 x 1/4 x 1/2 + inch Load: 264 psi (6) Softening temperature (TMA) DuPont, Thermo Mechanical
The thermal deformation strength of a 1 mm thick sheet was measured using an 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 until the needle penetrated 0.635 mm. The temperature was defined as TMA (
7) Glass transition temperature (Tg) Measured using DSC-20 manufactured by SEIKON, Kogyo ■ at a heating rate of 10°C/min. (Synthesis of ring-opening polymer) 700 ml of toluene was added to one flask ．． 1, 4, 5.
8-dimethanol, 1.2.3.4.4a, 5.8.
93 ml of 8a-octahydronaphthalene (DMON),
2-norbornene (NB) 7ml, 1-hexene 0.5
mL and millimoles of wcQe and tetraphenyltin were added and polymerization was carried out at HSO℃ for 2 hours.The polymerization solution was poured into a large amount of methanol to precipitate the polymer, and after washing three times each with methanol and acetone, 8
It was dried under reduced pressure at 0°C overnight to obtain 98 g of a polymer, and the intrinsic viscosity [V] of the obtained polymer measured in toluene at 30°C was 0. The NB content measured by 78 dl/c 13C-NMR was 10 mol%. t4 (Hydrogenation reaction of ring-opening polymer) 20 g of the ring-opening polymer was dissolved in 250 ml of tetrahydrofuran, and 1 g of Pd was supported on 50 g of silica! Medium 1.5g
After charging the autoclave with H2 and pressurizing it to 50 kg/cm2 G, the temperature was raised to 50°C and stirring was continued for 15 hours. The combined product was filtered off, dissolved in cyclohexane, and the catalyst was filtered off. After drying at 100°C under reduced pressure day and night, the hydrogenation rate was 97%. The glass transition temperature (Tg) measured at a heating rate of min was 155 °C. Ethylene-propylene random copolymer (ethylene content 80mol%, Tg knee 54℃, MFR230-C: 07g/10m
1n, [v]: 2. After thoroughly mixing 0.5 kg of 2d, ffi/g), the cylinder temperature was increased to 220°C using a twin-screw extruder (PCM45 manufactured by Ikegai Iron Works Co., Ltd.).
The mixture was melt-blended and pelletized using a pelletizer.For 1 kg of the obtained pellets consisting of the [A] acid component and [B] the acid component, Perhexine 25B (trademark) manufactured by NOF ■ was added as the [C] acid component. Divinylbenzene was added at a ratio of 3 g as the Ig and [D] acid components and thoroughly mixed.
The pellets were pelletized using a pelletizer, and the resulting pellets were used to prepare test pieces according to the method described above, and their physical properties were measured. The results are shown in Table 1.

The same procedure as in Example 1 was performed except that the type or amount of the [C] acid component used in Example 1 was changed.The results are shown in Table 1.

Table 2 shows the results of the same procedure as in Example 1 except that another polymer was used instead of the ethylene propylene lantum copolymer used as the [B] acid component in Example 1. show.

Onion j The same procedure as in Example 1 was carried out except that [C] acid component and [D] acid component were not used.

Claims (3)

[Claims] (1) A cyclic olefin resin consisting of a ring-opening polymer or copolymer obtained by ring-opening polymerization of a cyclic olefin represented by the following formula [I], or a hydrogenated product of these polymers or copolymers. A method for producing an impact-resistant cyclic olefin resin composition characterized by reacting a soft polymer with an organic peroxide; ▲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 selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. R^1^5-R^1^8 may be bonded to each other to form a single or polycyclic group, and the single or polycyclic group represents a double bond or Also, R^1^5 and R^1^6, or R^1^7
and R^1^8 may form an alkylidene group). (2) The soft copolymer is derived from (a) a repeating unit derived from ethylene, a repeating unit derived from an α-olefin other than ethylene, and a cyclic olefin represented by the above formula [I]. a cyclic olefin random copolymer consisting of repeating units, and having an intrinsic viscosity of 0.01 to 10 dl/g measured in decalin at 130°C and a glass transition temperature of 0°C or lower; (b) at least two types of α - An amorphous to low crystalline α-olefin copolymer with a glass transition temperature of 0°C or less formed from an olefin; (c) made from at least two types of α-olefins and at least one type of non-conjugated diene; An α-olefin/diene copolymer with a glass transition temperature of 0°C or less; and (d) an aromatic hydrocarbon/conjugated diene random or block copolymer or its hydrogen with a glass transition temperature of 0°C or less. 2. The method according to claim 1, wherein (e) at least one copolymer selected from the group consisting of heavy conjugated dienes or hydrides thereof. (3) The impact-resistant cyclic olefin resin composition further includes a total weight of 10% of the cyclic olefin resin and the soft copolymer.
Claim No. 1, characterized in that it is formed by blending and reacting a compound having two or more radically polymerizable functional groups in the molecule in an amount of 1 part by weight or less per 0 part by weight. The manufacturing method according to item 1.