JPH03210348A - Polyolefin resin composition - Google Patents

Abstract

PURPOSE:To improve the resistance to heat, mar, and chemicals and decrease the molding shrinkage by compounding a crystalline polyolefin resin with a specific cyclic olefin resin. CONSTITUTION:The title compsn. comprises 98-2wt.% crystalline polyolefin resin having a degree of crystallization of 5% or higher, an intrinsic viscosity (135 deg.C, in decalin) of 0.05-10dl/g, and a softening point of 70 deg.C or higher and 2-98wt.% cyclic olefin random copolymer which has an intrinsic viscosity of 0.05-10dl/g and a softening point of 70 deg.C or higher and which comprises 40-85mol% ethylene and 60-15mol% cyclic olefin selected from the group consisting of compds. of formula I, II, III (wherein l, m, and n are each 0 or a positive integer; R<1> to R<8> are each H, halogen, or a hydrocarbon group; R<15> to R<18> may combine with each other to form a mono- or polycyclic group optionally contg. a double bond; and R<15> and R<16>, R<17> and R<18>, and R<9> and R<10>, or R<11> and R<12> may combine to form an alkylidene group), and IV (wherein p is 0 or a positive integer; q and r are each 0-2; R<1> to R<15> are each H, halogen, an aliph. hydrocarbon group, an arom. hydrocarbon group, or alkoxy; and R<5> or R<6> may combine with R<9> or R<7> through a direct bond or a 1-3C alkylene group).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyolefin resin composition containing a polyolefin resin and a cyclic olefin resin, and more specifically, it has excellent heat resistance and scratch resistance.

The present invention also relates to a polyolefin resin composition having a small molding shrinkage rate.

Crystalline polyolefin resins represented by polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, etc. have sufficient strength at room temperature, as well as chemical resistance, electrical insulation, and weather resistance. It has excellent properties, has low water absorption, and is used for a wide range of purposes.

However, because it is crystalline, it has a large mold shrinkage rate, and even if its melting point is high, its glass transition temperature is relatively low, so it has the disadvantage of a low heat distortion temperature under high loads. Furthermore, depending on the application, the scratch resistance is not sufficient, and there is a demand for improvement.

Cyclic olefin has polymerizability, and for example, it can be copolymerized with ethylene to obtain a cyclic olefin/ethylene copolymer. It is known that
No. 305111 Komuki, JP 63-223013 Koho, JP 1-185307).

As a result of further research by the present inventors, the inventors have discovered that such cyclic olefin resins have the necessary transparency, water resistance, and thermal properties as optical materials. The present invention has discovered that by blending crystalline polyolefin resins with polyolefin resins, it is possible to obtain polyolefin resin compositions with even more excellent properties that can be used for various purposes. The purpose of the present invention is to provide a polyolefin resin composition that has excellent heat resistance, scratch resistance, and chemical resistance, and has low mold shrinkage while maintaining excellent properties.

and member I [A] a crystalline polyolefin resin, [B] ethylene, and at least the following formulas [I] to [rv
It is a copolymer with a cyclic olefin represented by one of the structural formulas selected from ℃ or higher, and the composition ratio of crystalline polyolefin resin [A] and cyclic olefin random copolymer CB] [A]/[B]
(weight ratio) is 9872 to 2798.

(Formula [ ] % Formula % [] 1 is O or a positive integer, Rl and R18 may be the same or different, and are from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group) are atoms or groups selected, and RIS to RI8 may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond, and , RIS and R”, or RIT and R111
may form an alkylidene group).

... [n] (In the formula [ml, m is O or a positive integer, and Rl
-, -Rl 1 are atoms or groups selected from the group consisting of a halogen atom and a hydrocarbon group, which may be the same or different, and R9 and Rts (may form an alkylidene group).

... [ml (in the formula [ml, n is 0 or a positive integer, and R1 to
RL2 may be the same or different, and are atoms or groups selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups, and even if R and RI2 form an alkylidene group. good).

... [■] (In the formula [rvl, p is an integer of 0 or 1 or more, and q
and r is 0. 1 or 2, and R+ to R+5 each independently represent an atom or group from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an alkoxy group, and R6 (or R6) and R
e (or RT) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group. ) The polyolefin resin composition according to the present invention has the characteristics of the crystalline polyolefin resin [A], such as a specific cyclic olefin having excellent heat resistance, scratch resistance, and chemical resistance, and a low molding shrinkage rate.

Next, the polyolefin resin composition according to the present invention will be specifically explained.

The polyolefin resin composition according to the present invention is a copolymer of a crystalline polyolefin resin rA], ethylene, and a specific cyclic olefin represented by one of the structural formulas selected from the above formulas CI] to [rvl. It is characterized by containing a certain cyclic olefin random copolymer [B].

The crystalline polyolefin resin [A] constituting the polyolefin resin composition of the present invention has at least the general formula
〇H2-CHR (In the formula, R is H or an alkyl group having 1 to 20 carbon atoms.) A polymer containing an a-olefin as one component and having crystallinity, Specifically, polyethylene, ethylene/1-butene combined, ethylene/3-methyl-1-butene combined, ethylene/4-methyl-
1-pentene copolymerization Ethylene/1-hexene copolymerization Ethylene/vinyl acetate copolymerization Ethylene/acrylic acid copolymer and its metal salts, polypropylene, propylene/ethylene copolymerization, propylene/1-butene copolymerization Poly 1-butene, 1-butene/ethylene copolymerization 1-butene/propylene copolymer, 1-butene/4-
Methyl-1-Pentene Kyoden Combined Poly4-Methyl-1-
Examples include pentene, poly-3-methyl-1-butene, etc. These can also be used alone or in combination.

The crystallinity of the crystalline polyolefin resin [A] measured by X-ray diffraction is 5% or more, preferably 10% or more.
It is desirable that it is 5 or more.

Further, the intrinsic viscosity [η] of the crystalline polyolefin resin [A] measured in decalin at 135°C is 0.05 to 10.
dim is preferably in the range of 0.1 to 5 dl/$i.

In addition, the softening temperature (TMA) of the crystalline polyolefin resin [A] measured with a thermomechanical analyzer
It is desirable that the temperature is 70°C or higher, preferably in the range of 90 to 2501″.

The cyclic olefin random copolymer [B] constituting the polyolefin resin composition of the present invention is a cyclic olefin composed of a structural unit (a) derived from ethylene and a structural unit Cb'' derived from a specific cyclic olefin. It is a random copolymer.

The cyclic olefin has at least the formula [11 to [r
It is a cyclic olefin represented by one of the structural formulas selected from vl.

In the above formula [11], 1 is 0 or a positive integer, preferably 0 to 3. In the above formula [nl, m is O or a positive integer, preferably 0 to 3. In the above formula [n+], n is O or a positive integer, preferably O-3. Further, in the above formula [eco], p is an integer of 0 or 1 or more, preferably 0 to 3.

And R1~R18 (formula [Eco), R1~R1-
(Formula [■]), R1-R12 (Formula [m]) or R
1, Re6 (formula [■]) are the same and 4
They are different from each other and are often an atom or group selected from the group consisting of a halogen group, a halogen group, and a hydrocarbon group. Here, as a halogen atom, even If,
Mention may be made of fluorine, chlorine, bromine and iodine atoms. In addition, as the hydrocarbon group, each independently usually includes an alkyl group having 1 to 10 carbon atoms.
Examples include cycloalkyl groups having 5 to 15 carbon atoms, and specific examples of alkyl groups include methyl group, ethyl isopropyl group, isobutyl & n-amyl group.
Neopentylmin n-hexyl f, n-octyl5n-decyl 2-ethylhexyl group, etc.
Specific examples of the cycloalkyl group include cyclopentyl group, cyclohexyl group, methylcyclohexyl group, and ethylcyclohexyl group.

Further, in the above formula [1], RIS and R16 or R'' and R18 may form an alkylidene group, and in the above formula [nl, R9 and Rlfl may form an alkylidene group. Alternatively, in the above formula [IIl], R11 and RI2 may form an alkylidene group. Such an alkylidene group usually includes an alkylidene group having 3 to 10 carbon atoms,
Specific examples include ethylidene, propylidene, isopropylidene, butylidene, and isobutylidene.

Further, in the above formula [■], R6 (or R11) and R9 (or R〒) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded without any group. They may be directly combined.

Furthermore, in the above formula [y], R11 to R+o may be bonded to each other (together) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring has a double bond. You can.

The cyclic olefins represented by the formulas [r] to [rvl are:
It can be easily produced by condensing cyclopentadiene and the corresponding olefin or cyclic olefin by Diels-Alder reaction.

The cyclic olefins represented by the formulas [11 to [rvl] are as follows: If, (blank below) 12, s, 1v 11-3-dodecene 8-ethylidene-9-iso-dodecene, 12 S , 17 +@]-3-dodecene5.17・+1-3-dodecene8-impropylidene8-impropylidene-dodecene@]-3-dodeceneC11°[4,4,0,12 5,17 Tetracyclo[4,4,0,12s, 1t, te such as Co3-dodecene
l-3-dodecene derivatives; diene compounds such as; ,8,0,1'・8. Q2. ?
, 1111.17. Q-th, 111,112・+5 Cor 4
-Eicosene derivative; 21.11.2@, Q10.19
．． IS, l]-5-bentacocene 3.2@, Q14.119. lls, I@]-5-bentacocene and other nonacyclo[g, 10.1.1a, ? , □ff
,@,02. Ie, 0Iz21.113.21. Q14
．． 19,116.1@] -5-bentacocene derivatives and the like.

And furthermore, can be mentioned.

The cyclic olefin random copolymer [B] constituting the resin composition according to the present invention has a structure in which the constituent units (a) derived from ethylene and the constituent units (b) derived from the cyclic olefin are essential constituent units. ＼In addition to these two essential structural units, it may contain other copolymerizable structural units derived from unsaturated monomers as necessary, as long as the object of the present invention is not impaired. . Specific examples of unsaturated monomers that may be added as necessary include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, a having 3 to 20 carbon atoms such as 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene;
-Olefins can be exemplified. The structural units derived from these unsaturated monomers are the structural units derived from ethylene (a
The structural unit (a) derived from a cyclic olefin constituting the resin composition according to the present invention may be contained in an amount less than equimolar to 40 to 85 mol%, preferably 50 to 75 mol% It is desirable that the content be within the range of mol%. In addition, the structural unit (b) derived from a cyclic olefin is 1
It is desirable that the content is in the range of 5 to 60 mol%, preferably 25 to 50 mol%. In the present invention, the structural units (a) derived from ethylene and the structural units (b) derived from cyclic olefins are randomly arranged to form a substantially linear cyclic olefin random copolymer.

The intrinsic viscosity [W] of the cyclic olefin random copolymer [B] constituting the resin composition of the present invention measured in decalin at 135°C is 0.05 to 10 dl/g, preferably 0°08 to It is in the range of 5 dl/g.

Furthermore, the cyclic olefin random copolymer [B] constituting the resin composition according to the present invention has a softening temperature (TMA) of 70% as measured by a thermomechanical analyzer.
℃ or less preferably in the range of 90 to 250C, more preferably in the range of 100 to 200C.

Glass transition temperature of reflexine random copolymer [B] (
Tg) is usually 50 to 230°C, preferably 70 to 210
It is desirable to be in the range of ℃.

In addition, the crystallinity of the cyclic olefin random copolymer constituting the resin composition of the present invention [B) determined by X-ray diffraction analysis is 0 to 10%, preferably 0 to 7%, particularly preferably It is desirable that it be in the range of 0 to 5%.

As the cyclic olefin random copolymer [B] constituting the resin composition according to the present invention, only a copolymer having physical properties within the above range may be used, and some copolymers outside the above range may be used. In this case, it is sufficient that the physical property values of the cyclic olefin random copolymer [B] as a whole fall within the above range.

The cyclic olefin random copolymer [B] constituting the resin composition according to the present invention is disclosed in Japanese Patent Application Laid-Open No. 60-16870.
No.8 Public/Private JP-A-61-120816 Public-Private JP-A-6
1-115912 Public/Private JP 61-115916 Public/Private JP 61-271308 Public/Private JP 61-
No. 272216 public sail JP 62-252406 public beast
It can be manufactured by a method similar to the method proposed by the present applicant in JP-A-62-252407 and the like.

In the present invention, a part of the cyclic olefin random copolymer as described above may be modified with an unsaturated carboxylic acid such as maleic anhydride. Such a modified product can be produced by reacting a cyclic olefin resin as described above with an unsaturated carboxylic acid, an anhydride thereof, and a derivative such as an alkyl ester of an unsaturated carboxylic acid. In this case, the content of structural units derived from the modifier in the modified cyclic olefin resin is usually 0.001 to 5% by weight.

Such a modified cyclic olefin resin can be produced by blending a modifier with a cyclic olefin resin and graft polymerizing it to a desired modification rate, or by preparing a modified product with a high modification rate in advance. However, it can also be produced by subsequently mixing this modified product with an unmodified cyclic olefin resin.

In the polyolefin resin composition of the present invention, the composition ratio of the crystalline polyolefin resin component mA] and the cyclic olefin random copolymer component [B] is [Aj component/[B]
] acid component weight ratio) is 9872 to 2/98, preferably,
9515-5/95.

Furthermore, in the present invention, when producing the above-mentioned cyclic olefin-based random copolymer, the above-mentioned formulas [I] to [■
] It is also possible to polymerize cyclic olefins other than the cyclic olefins represented by. Examples of such cyclic olefins include cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclohexene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, 2,
3.3a, 'IB-tetrahydro4.7-methano-
In addition to IH-indene, 3a, 5.6.7a-tetrahydro-4.7-methano-IH-indene; bicyclo[2,2,11 hept-2-ene derivatives such as .10-dimethyltetraCH.

CH.

2,7.9-) Remethylte 9-Inbutyl-2,7- 9,11,12-)limethyl 9-isobutyl-11,12 −Dodecene 5,8.9.10-tetramethy 8-methyltetrashif 8-ethyltetrashif ”]-]3-dodese N,,H,.

・II]-3-dodecene ・]-]3-dodecene-methyl-9-ethyl 3-dodecene-3-dodecene 1@]-3-dodecene+ @]-3-dodecene@, 1+11]-3 -dodecene+11]-3-dodecene-3-dodecene and other tetracyclo[4,4,0,12・5.17・I
@Coco-dodecene derivatives (blank below) ・14] -4-hebutadecenedecenedecenehebutadecene 13, Qa・7.09 14] Hexacyclo[6,6,1,13e, such as -4-heptadecene, 1+・13, Qa, 7, (p・+a]-4-hebutadecene derivative; 3, +11.(p@, Q12 + 7]-5- tococene 1@, I+8 16, Q3 meeting, 01 1ma]- 5-tococene 17 code Octacyclo [8,8,0,1214 〒11 111 118, Q3.ll, Q12.+?]-5-)' Near Sen9 conductor; Pentacyclo [6 such as decene ,6,1,11@ ,Qa
, Te, 09. ■]-4-hexadecene derivatives: Hebutacyclo-5-icosene derivatives such as cosene or hebutacyclo-5-heneicosene i conductors: Tricyclo[4,3,0,12 5]-3-decene derivatives such as 10-methyl- tricyclo[4,4,0,12S]-3-undecene derivatives such as trisif; pentacyclo[6,5,1,118, Ql? such as 1,6-dimethylbenta14,15-dimethylben; ,Q
9+3]-,4-pentadecene derivatives and the like.

(Left below) Such other cyclic olefins can be used alone or in combination, and are usually 0 to 20 mol%.
used in amounts of

Furthermore, the resin composition of the present invention includes the above [A] and [B].
] In addition to acid components, rubber components are added to improve impact strength, heat-resistant stabilizers II, weather-resistant stabilizers, antistatic II, slip agents, anti-blocking anti-fog agents, lubricants, dyes, pigments, natural ingredients. Oil, synthetic oil, wax, etc. can be blended, and the blending ratio is appropriate. Specifically, as a stabilizer that may be added as an optional component, tetrakis[methylene-3 (3°5-di-t
-butyl-4-hydroxyphenyl)propionate comethane, β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate alkyl ester, 2,2
Phenolic antioxidants such as oxamidobis[ethyl-3(3,5-di-t-butyl-4-hydroxyphenyl) coprobionate, fatty acid metals such as zinc stearate, calcium stearate, and calcium 12-hydroxystearate Examples include salts, fatty acid esters of polyhydric alcohols such as glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. These may be blended alone or in combination, even if 1f
Examples include a combination of 1 tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate comethane, zinc stearate, and glycerin monostearate.

In the present invention, it is particularly preferable to use a phenolic antioxidant and a fatty acid ester of a polyhydric alcohol in combination. Polyhydric alcohol fatty acid esters are preferred.

As fatty acid esters of such polyhydric alcohols,
Specifically, +L glycerin fatty acid esters such as glycerin monostearate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate, glycerin dilaurate, pentaerythritol monostearate, pentaerythritol monolaurate, pentaerythritol monolaurate, etc. Fatty acid esters of pentaerythritol such as erythritol dilaurate, pentaerythritol distearate, and pentaerythritol tristearate are used.

Such a phenolic antioxidant is used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 3 parts by weight, and more preferably 0.1 parts by weight per 100 parts by weight of the polyolefin resin composition.
The fatty acid ester of polyhydric alcohol is used in an amount of 0.01 to 1 part by weight per 100 parts by weight of the composition.
It is used in an amount of 10 parts by weight, preferably 0.05 to 3 parts by weight.

The polyolefin resin composition of the present invention includes silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, as long as the object of the present invention is not impaired.
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 peas, calcium silicate, montmorillonite, bentonite , graphite, aluminum powder,
Fillers such as molybdenum sulfide, boron fibers, silicon carbide fibers, polyethylene fibers, polypropylene fibers, polyester fibers, and polyamide fibers may be blended.

As a method for producing the polyolefin resin composition according to the present invention, L
A known method can be applied, and the crystalline polyolefin resin component [A] and the cyclic olefin random copolymer [
extruder, as well as other ingredients added as desired
A method of mechanically blending using a kneader etc., or a method of dissolving each component simultaneously or separately in a suitable good solvent such as a hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene, xylene, etc. Examples include a method of post-mixing and removing the solvent, and a method of combining these two methods.

The polyolefin resin composition obtained by the above manufacturing method is
The crystalline polyolefin resin component [A] has a heat distortion temperature,
By blending the cyclic olefin random copolymer [B] with high pencil hardness and low molding shrinkage, it maintains the properties of crystalline polyolefin resin while improving heat resistance, scratch resistance, and molding shrinkage. A small polyolefin resin composition is obtained.

Since the crystalline polyolefin resin composition according to the present invention has the above-mentioned properties, it can be widely used in fields where heat resistance, scratch resistance, dimensional stability, etc. are required, in addition to the conventional uses of crystalline polyolefins. be able to.

Examples of applications include housings for electricians, OA machinery cameras, pumps, etc., chassis parts, precision equipment parts, instrument panels, radiator grills, cluster grills, console pockets, garnishes, foil covers, column covers, fenders, and bonnets. , Automotive interior and exterior materials such as trunks, seats, cases for connectors, coil bobbins, switches, etc., cover skins Bottle gourd Film gourds such as cast films, biaxially stretched films, and multilayer films Extrusion foaming Foams such as injection foams It will be done.

As mentioned above, according to the present invention, the cyclic olefin random copolymer component [B] is blended with the crystalline polyolefin resin component [A], which improves heat resistance, scratch resistance, and moldability. Moreover, a polyolefin resin composition having a small molding shrinkage rate can be obtained.

[Examples] Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited to these Examples.

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

(1) Melt flow index (MFRy) According to ASTM D1238, at a predetermined temperature T°C and a load of 2.
8 (2) Preparation of test piece The test piece was molded under the following molding conditions using an injection molding machine manufactured by Toshiba Machine ■ 15-55EPN and the specified test piece mold. After molding, the test piece was molded at room temperature for 48 hours. Molding conditions measured after standing: Cylinder temperature: 220't::, Mold temperature: 6
0℃, injection pressure car secondary/secondary = 1000/800kg/
cm2 Injection speed (-) 30mm/s Screw rotation speed 150rpm (3) Bending test Test conducted according to ASTM D790 Test piece shape: 5X 1/2X 1/8t inch, distance between spans 1mm Test speed: 20mm/min Test temperature: 23℃ (4) Heat distortion temperature (HDT) Test piece shape: 5 x 1/4 x 1/21 inch load
Weight: 264psi (5) Softening temperature (TMA) Thermo Mechanical A manufactured by DuPont
The thermal deformation behavior of a 1 mm thick sheet was measured using a nalyzer. 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 became 0.635 mm. The temperature at which it entered was defined as TMA.

(6) Glass transition temperature (Tg) and melting point (Tm) SE
Temperature increase rate 10 using DSC-20 manufactured by IKO Electronics Industry ■
Rockwell hardness measured at 23°C according to ASTM D785 (8) Pencil hardness measured at 23°C according to JIS K 5400 A pellet of crystalline polypropylene resin (crystallinity 6 (XMFR2s*・c Log/10m1n) of 3.5 is [B] acid component and the ethylene content measured by 13C-NMR is 63 molX, MFR,
,,-, is 32g/10mja, and the intrinsic viscosity [7] measured in decalin at 135°C is 0.48dl/liL TM
Ethylene and 1.4.5.8-dimethano-1,2,3,4 with A at 150°C and Tg at 140°C (Tm not observed).
, 4a.

4b, 5.8.8a, 9a-decahite o 7 rut
After thoroughly mixing 1.5 kg of pellets of random copolymer (ethylene/DMDF random copolymer) with L/"y (abbreviated as DMDF under fi), cylinder temperature 220℃
Using the pellets obtained by melt-blending using a pelletizer, test pieces were prepared by the method described above, and the physical properties of the test pieces were evaluated. Table 1 shows the results.

Table 1 shows the results of carrying out the same operation as in Example 1 except that the ratio of [A] acid component and [B] acid component was changed.

The results are shown in Table 2. The same operation was carried out except that another polyolefin resin was used in place of the polypropylene used in Example 3. The results are shown in Table 2.

In Example 1, [B] In place of the ethylene/DMDF copolymer used as the acid component, ethylene and other cyclic olefins were used as BI51. A similar operation was performed. Table 3 shows the physical property values of the [B] acid component used.

The results are shown in Table 4.

"Foot last 1" The polypropylene used as the acid component [A] in Example 1 was individually molded, and its physical properties were evaluated.The bending strength, bending elasticity If, HE Rockwell hardness (R scale), and pencil hardness were 430 kg each. /cm2.1
4000kg/cm2.60℃, 106.3B4

Claims (1)

[Claims] (1) A copolymer of [A] a crystalline polyolefin resin, [B] ethylene, and a cyclic olefin represented by at least one of the structural formulas selected from the following formulas [I] to [IV], Intrinsic viscosity [η] measured in decalin at 135°C is 0.05 to 10 dl/g, softening temperature (TMA)
a cyclic olefin random copolymer having a temperature of 70°C or higher, and the composition ratio of the crystalline polyolefin resin [A] and the cyclic olefin random copolymer [B] is [A]/[B](
A polyolefin resin composition having a weight ratio of 98/2 to 2/98. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ... [I] (In the formula [I], l is 0 or a positive integer, and R^
1 to R^1^8 may be the same or different, and each is an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R^1^5 to R^ 1^8 may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and R^1^5 and R With ^1^6 or R^1^7
and R^1^8 may form an alkylidene group). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ... [II] (In formula [II], m is 0 or a positive integer, and R^1
~R^1^0 may be the same or different, and are atoms or groups selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups, and R^9 and R^1^0 may form an alkylidene group). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ... [III] (In formula [III], n is 0 or a positive integer, and R^
1 to R^1^2 may be the same or different, and are atoms or groups selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups, and R^1^1 and R^ 1^2 may form an alkylidene group). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ... [IV] (In formula [IV], p is 0 or an integer of 1 or more, q and r are 0, 1 or 2, and R^1 ~R^1^5
each independently represents an atom or group from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an alkoxy group, and R^5 (or R^6
) and R^6 (or R^7) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group. )