JPH04353540A - Polyolefin resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition excellent in heat, scuff and chemical resistance and mechanical characteristics by blending a specific cyclic olefin resin with a crystalline polyolefin resin. CONSTITUTION:A composition is obtained by blending (A) a crystalline polyolefin with (B) a cyclic olefin resin, selected from copolymers of ethylene and cyclic olefins expressed by formula p and q are 0 or >=1; m and n are 0, 1 or 2; R<1> to R<19> are hydrogen, halogen, aliphatic hydrocarbon, etc.; R<9> and R<13> or R<10> and R<11> may directly be linked or bound through 1-3C alkylene; R<15> and R<12> or R<15> and R<11> may mutually be bound to form monocyclic or polycyclic aromatic ring when (n) and (m) are 0 and hydrogenated copolymers thereof and having 0.05-10dl/g intrinsic viscosity measured in decalin at 135 deg.C and >=0 deg.C softening temperature (TMA) at a weight ratio within the range of (98/2)-(2/98). The component (A) preferably has >=20% crystallinity measured by an X-ray diffractometory.

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD OF THE INVENTION The present invention relates to a polyolefin resin composition containing a polyolefin resin and a cyclic olefin resin. More specifically, the present invention provides heat resistance, scratch resistance,
This invention relates to a polyolefin resin composition that has excellent mechanical properties and low mold shrinkage.

0002

[Technical background of the invention] Polyethylene, polypropylene,
Crystalline polyolefin resins, such as poly-1-butene and poly-4-methyl-1-pentene, have sufficient strength at room temperature, as well as excellent chemical resistance, electrical insulation, and weather resistance. It has a low water absorption rate and is used for a wide range of purposes.

[0003] However, these polyolefin resins
Since it is crystalline, it has a large molding shrinkage rate, and even if its melting point is high, its glass transition temperature is relatively low, so there is a problem that its heat distortion temperature is low under high loads. In addition, the scratch resistance may not be sufficient depending on the application, and there is room for improvement in this respect.

By the way, cyclic olefins having an ethylenic double bond in the ring are polymerizable, and it is known that, for example, a cyclic olefin/ethylene copolymer can be obtained by copolymerizing with ethylene. (Example: JP-A-60-1
No. 68708, Japanese Patent Application Laid-open No. 63-243111,
JP-A-63-305111, JP-A-63-223
013 and JP-A-1-185307).

[0005] Such cyclic olefin resins have transparency, water resistance, and thermal properties necessary for optical materials, but as a result of further research by the present inventors, cyclic olefin resins Among them, by blending a cyclic olefin resin (aromatic group-containing cyclic olefin resin) with a repeating unit derived from a specific cyclic olefin having an aromatic group into a polyolefin resin, it can be used for various purposes. It has been found that a polyolefin resin composition having excellent properties can be obtained.

[0006]

[Object of the invention] The present invention provides a polyolefin resin composition that maintains the excellent properties of crystalline polyolefin resin, has excellent heat resistance, scratch resistance, chemical resistance, and mechanical properties, and has a low molding shrinkage rate. The purpose is to

[0007]

Summary of the Invention The polyolefin resin composition according to the present invention comprises [A] a crystalline polyolefin resin, [B] a copolymer of ethylene and a cyclic olefin represented by the following formula [I], or a cyclic olefin. The intrinsic viscosity [η] measured in decalin at 135°C selected from the group consisting of ring-opening polymers and hydrogenated products thereof is 0.05 to 10 dl/g, and the softening temperature (
Cyclic olefin resin whose TMA) is 0°C or higher,
Weight ratio within the range of 98/2 to 2/98 ([A]/[B]
).

[0008]

[Case 2]

... [I] However, in the above formula [I], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R1 to R19 are each independently represents an atom or 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 R9 and R13 or R10 and R11 are It may be bonded directly or through an alkylene group having 1 to 3 carbon atoms, and when n=m=0, R
15 and R12 or R15 and R19 may be bonded to each other to form a monocyclic or polycyclic aromatic ring.

The polyolefin resin composition of the present invention comprises a polyolefin resin [A] and a specific cyclic olefin resin [B] having an aromatic group (that is, a cyclic olefin random copolymer, a cyclic olefin ring-opening polymer, or This hydrogenated product) provides excellent heat resistance, scratch resistance, chemical resistance, and mechanical properties, as well as low molding shrinkage.

[0011]

DETAILED DESCRIPTION OF THE INVENTION Next, the polyolefin resin composition of the present invention will be explained in detail. The polyolefin resin composition of the present invention is a composition comprising a crystalline polyolefin resin [A] and a specific cyclic olefin resin [B].

The crystalline polyolefin resin [A] constituting the polyolefin resin composition of the present invention is a polymer obtained by (co)polymerizing at least one component of an α-olefin represented by the following formula [i]. This polyolefin resin has crystallinity.

CH2=CHR
... [i] However, in the above formula [i], R is either a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

[0014] Such crystalline polyolefin resin [A
] Specific examples include polyethylene, ethylene・1
-Butene copolymer, ethylene/3-methyl-1-butene copolymer, ethylene/4-methyl-1-pentene copolymer, ethylene/1-hexene copolymer, ethylene/vinyl acetate copolymer, ethylene・Acrylic acid copolymer and its metal salt, polypropylene, propylene/ethylene copolymer, propylene/1-butene copolymer, poly-1-butene, 1-butene/ethylene copolymer, 1-butene/propylene copolymer Polymers, 1-butene/4-methyl-1-pentene copolymers, poly-4-methyl-1-pentene, poly-3-methyl-1-butene, and the like can be mentioned. In the present invention, these resins can be used alone or in combination.

The polyolefin resin [A] has crystallinity, and the crystallinity of the polyolefin resin [A] measured by X-ray diffraction is usually 5% or more, preferably 10% or more. , more preferably 20%
That's all.

[0016] Furthermore, the above-mentioned crystalline polyolefin resin [A
The intrinsic viscosity [η] measured in decalin at 135°C is usually 0.05 to 10 dl/g, preferably 0.1 to 10 dl/g.
It is in the range of 5 dl/g.

Furthermore, the above crystalline polyolefin resin [
A] The softening temperature (TMA) measured with a thermo-mechanical analyzer is usually 70°C or higher, preferably 90°C or higher.
It is in the range of 0 to 250°C.

Next, the cyclic olefin resin [B] constituting the polyolefin resin composition of the present invention will be explained. The cyclic olefin resin [B] constituting the polyolefin resin composition of the present invention includes a structural unit (a) derived from ethylene and a structural unit (b) derived from a cyclic olefin represented by formula [I]. There are cyclic olefin-based random copolymers that are randomly bonded, ring-opened polymers of cyclic olefins represented by formula [I], and hydrogenated products of these ring-opened polymers.

This cyclic olefin can be represented by the following formula [I].

[0020]

[Chemical formula 3]

[I] However, in the above formula [I], p is 0 or a positive integer, preferably 0 to 3. Further, in the above formula [I], m and n are 0, 1 or 2. moreover,
q is 0 or a positive integer, preferably 0 or 1.

[0022] R1 to R19 are each independently an atom or group selected from the group consisting of a hydrogen atom, 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 hydrocarbon groups include alkyl groups having 1 to 10 carbon atoms,
Examples include a cycloalkyl group having 5 to 15 carbon atoms and an aromatic group having 6 to 12 carbon atoms. Specific examples of alkyl groups include methyl group, ethyl group, isopropyl group, isobutyl group, n-amyl group, neopentyl group,
n-hexyl group, n-octyl group, n-decyl group, 2-
Specific examples of cycloalkyl groups include cyclohexyl, methylcyclohexyl, and ethylcyclohexyl groups. Specific examples of aromatic groups include: Examples include phenyl group, naphthyl group, and biphenyl group.

Furthermore, in the above formula [I], R9 and R1
3 or R10 and R11 may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group.

Furthermore, when n=m=0, R15 and R1
2 or R15 and R19 may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Preferred examples in this case include the groups described below in which R15 and R12 further form an aromatic ring when n=m=0.

[0025]

[C4]

In the above formula, q has the same meaning as in formula [I]. Specifically, the cyclic olefin represented by the formula [I] is, for example,

[0027]

[C5]

[0028]

[C6]

[0029]

[C7]

[0030]

[Chemical formula 8]

[0031]

[Chemical formula 9]

[0032]

[Chemical formula 10]

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

The cyclic olefin random copolymer used as the cyclic olefin resin [B] constituting the resin composition of the present invention contains a structural unit derived from ethylene (
a) is usually 40 to 97 mol%, preferably 50 to 95 mol%
The structural unit (b) derived from the cyclic olefin is usually contained in an amount of 3 to 60 mol%, preferably 5 to 50 mol%.

In the cyclic olefin random copolymer, repeating units derived from ethylene and repeating units derived from cyclic olefin are arranged randomly and substantially linearly. The fact that this cyclic olefin random copolymer is substantially linear and has no gel-like crosslinks can be confirmed by completely dissolving this random copolymer in decalin at 135°C. can.

The cyclic olefin-based random copolymer can be produced, for example, by polymerizing ethylene and a cyclic olefin in a hydrocarbon medium in the presence of a catalyst formed from a hydrocarbon-soluble vanadium compound and a halogen-containing organoaluminum compound. It can be manufactured by

[0037] In such polymerization, for example, JP-A-60-168708, JP-A-61-120816,
No. 61-115912, Japanese Patent Application Laid-Open No. 1983-115912
-115916, JP 61-271308, JP 61-272216, JP 62-2
Methods disclosed in Japanese Patent Application Laid-open No. 52406, Japanese Patent Application Laid-Open No. 62-252407, etc. can be used.

In such a cyclic olefin random copolymer, for example, at least a part of the cyclic olefin represented by the above formula [I] has a structure represented by the following formula [I-A] and is composed of ethylene. It is thought that it is randomly bonded to the derived repeating unit.

[0039]

[Chemical formula 11]

[IA] However, in the above formula [IA], R1 to R19, p, q, m and n have the same meanings as in formula [I].

The cyclic olefin random copolymer has the constituent unit (a) derived from ethylene and the constituent unit (b) derived from the cyclic olefin as essential constituent units. may contain structural units derived from other copolymerizable unsaturated monomers, if necessary, within a range that does not impair its properties. Examples of unsaturated monomers that may be added and copolymerized as necessary include propylene, 1
-butene, 4-methyl-1-pentene, 1-hexene,
1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1
- C3-C20 α-olefins such as eicosene can be exemplified. The constituent units derived from these unsaturated monomers may be contained in an amount less than equimolar to the constituent unit (a) derived from ethylene in the generated random copolymer.

Furthermore, the above-mentioned cyclic olefin-based random copolymer may contain cyclic olefins (other cyclic olefins) other than the cyclic olefin represented by the above formula [I] within a range that does not impair the physical properties of the copolymer. ) can also have a constituent unit derived from Examples of such cyclic olefins include cyclobutene, cyclopentene,
Cyclohexene, 3,4-dimethylcyclohexene, 3
-Methylcyclohexene, 2-(2-methylbutyl)-
1-cyclohexene, 2,3,3a,7a-tetrahydro-4,7-methano-1H-indene, 3a,5,6,
In addition to 7a-tetrahydro-4,7-methano-1H-indene;

[0043]

[Chemical formula 12]

[0044]

[Chemical formula 13]

[0045]

[Chemical formula 14]

[0046]

[Chemical formula 15]

[0047]

[Chemical formula 16]

[0048]

[Chemical formula 17]

[0049]

[Chemical formula 18]

[0050]

[Chemical formula 19]

[0051]

[C20]

[0052]

[C21]

[0053]

[C22]

[0054]

[C23]

[0055]

[C24]

[0056]

[C25]

[0057]

[C26]

[0058] Such other cyclic olefins can be used alone or in combination, and usually 0
It is used in an amount of ~20 mol%. Among the cyclic olefin resins used in the present invention, the cyclic olefin ring-opening polymer includes a single ring-opening polymer of a cyclic olefin represented by the above formula [I], and a copolymer of a plurality of cyclic olefins. There are ring copolymers.

The ring-opening polymer used as the cyclic olefin resin [B] in the present invention can be prepared by ring-opening polymerization of the above-mentioned cyclic olefins alone or in combination.

That is, a ring-opening polymer is prepared by subjecting the cyclic olefin represented by the above formula [I] to ring-opening polymerization in the presence of a ring-opening polymerization catalyst. Examples of the ring-opening polymerization catalyst used here include halides of metals such as ruthenium, rhodium, osmium, indium, platinum, molybdenum, and tungsten, nitrates of these metals, and acetylacetone compounds of these metals,
Catalysts consisting of reducing agents such as alcohols or tin compounds, as well as titanium, vanadium, zirconium,
Examples include catalysts consisting of halogen compounds of metals such as tungsten and molybdenum, acetylacetone of these metals, and metal aluminum compounds.

In addition, in preparing the above ring-opening polymer, in addition to the cyclic olefin represented by the above formula [I], within a range that does not impair the properties of the cyclic olefin resin,
Still other cyclic olefins can be used.

Examples of other cyclic olefins that can be used here include cyclobutene, cyclopentene,
Cyclooctene, cyclononene, methylcyclopentene, methylcycloheptene, methylcyclooctene, methylcyclononene, methylcyclodecene, ethylcyclopentene, ethylcycloheptene, ethylcyclooctene, ethylcyclononene, dimethylcycloheptene, dimethylcyclooctene, Mononuclear olefins having 4 or more carbon atoms such as dimethylcyclononene, dimethylcyclodecene, cyclooctadiene and cyclodecadiene, and other cyclic olefins exemplified in the explanation of the cyclic olefin random copolymer can be mentioned. Moreover, as a molecular weight regulator, alkenes such as propylene, 1-butene, 1-pentene, and 1-hexene can be used as a copolymerization component.

In such a ring-opened polymer, at least a portion of the cyclic olefin represented by the above formula [I] is considered to have a structure represented by the following formula [I-B].

[0064]

[C27]

[I-B] However, in the above formula [I-B], R1 to R19 and p, q, m and n have the same meanings as in formula [I].

In the present invention, the cyclic olefin resin [B
] The hydrogenated product of the ring-opened polymer used as the above-mentioned ring-opened polymer can be obtained by hydrogenating the cyclic olefin ring-opened polymer prepared as described above. For hydrogenation of ring-opening polymers,
A conventional hydrogenation method carried out in the presence of a hydrogenation catalyst can be employed.

[0067] The hydrogenation catalyst used here is:
Hydrogenation catalysts such as heterogeneous catalysts or homogeneous catalysts that are commonly used in the hydrogenation of olefin compounds can be used. Specific examples of heterogeneous catalysts include metals such as nickel, palladium and platinum, and solid catalysts (e.g. , nickel/silica, nickel/diatomaceous earth, palladium/carbon, palladium/silica,
palladium/diatomaceous earth, palladium/alumina, etc.). Further, examples of homogeneous catalysts include catalysts based on metals of group VIII of the periodic table; examples of such catalysts include cobalt naphthenate/triethylaluminum, cobalt octenoate/n-butyllithium, Examples include organometallic compounds formed from nickel compounds such as nickel acetylacetonate/triethylaluminum or cobalt compounds and metals from groups I to III of the periodic table, and Rh compounds can also be used.

The hydrogenation reaction using the hydrogenation catalyst as described above can be carried out in either a heterogeneous system or a homogeneous system depending on the type of catalyst. The reaction conditions in such a system are usually set at a temperature of 0 to 180°C, preferably 20 to 100°C, under hydrogen pressure of 1 to 150 atmospheres. The hydrogenation rate under these conditions can be adjusted by appropriately setting conditions such as hydrogen pressure, reaction temperature, reaction time, and catalyst concentration. Usually, 50% or more, preferably 80% or more, and more preferably 90% or more is hydrogenated.

In such a hydrogenated ring-opening polymer,
For example, at least a portion of the cyclic olefin represented by the above formula [I] is considered to have a structure represented by the following formula [I-C].

[0070]

[C28]

...[I-C] However, in the above formula [I-C], R1 to R19, and p, q, m and n have the same meanings as in formula [I].

[0072] In the cyclic olefin resin,
The fact that the cyclic olefin used as a raw material has a structure represented by the above formulas [IA], [IB], and [IC] means that the 13C of the cyclic olefin resin
- It can be confirmed from the NMR measurement results.

The intrinsic viscosity [η] of the cyclic olefin resin [B] constituting the resin composition of the present invention, measured in decalin at 135° C., is in the range of 0.05 to 10 dl/g, and Preferably, the cyclic olefin resin is within the range of .08 to 5 dl/g.

[0074] Furthermore, the softening temperature (TMA) of the cyclic olefin resin [B] constituting the resin composition of the present invention measured with a thermomechanical analyzer is 0°C or higher; Cyclic olefin resin [
B] is preferably used.

Further, the glass transition temperature (Tg) of the cyclic olefin resin [B] constituting the resin composition of the present invention by DSC is usually -20 to 230°C, preferably -10°C.
~210°C. Furthermore, the degree of crystallinity of this cyclic olefin resin [B] measured by X-ray diffraction is usually 0 to 40%, preferably 0 to 7%, particularly preferably 0 to 5%.

In the present invention, a part of the above-mentioned cyclic olefin resin, especially the cyclic olefin random copolymer, may be modified with an unsaturated carboxylic acid such as maleic anhydride or glycidyl acrylate. . Such modified products are produced by reacting the above-mentioned cyclic olefin resin with unsaturated carboxylic acids, their anhydrides, and derivatives such as alkyl esters of unsaturated carboxylic acids or glycidyl esters of unsaturated carboxylic acids. It can be manufactured by 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.
It is as follows. Such a modified product of cyclic olefin resin can be produced by blending a modifier with a cyclic olefin resin and graft polymerizing it to a desired modification rate, or by preparing a modified product with a high modification rate in advance. It can also be produced by preparing the modified product and then mixing this modified product with an unmodified cyclic olefin resin. Moreover, a polysensitive monomer such as divinylbenzene can be reacted with this cyclic olefin resin in the presence of a radical reaction initiator.

In the polyolefin resin composition of the present invention, the polyolefin resin component [A] and the cyclic olefin resin [B] have a weight ratio of 98/2 to 2/98 ([
A] component/[B] component). In the present invention, the weight ratio of component [A]/component [B] is
It is preferably within the range of 95/5 to 5/95.

The polyolefin resin composition of the present invention includes:
In addition to the above [A] and [B] components, rubber components for improving impact strength may be blended, heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, slip agents, anti-blocking agents,
Antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, etc. can be blended, and the blending ratios are appropriate. For example, as a stabilizer that may be added as an optional component, tetrakis[methylene-3 (3,5-di-
t-Butyl-4-hydroxyphenyl)propionate] methane, 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)]propionate, fatty acid metal salts such as zinc stearate, calcium stearate, and calcium 12-hydroxystearate. , 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; for example, tetrakis[methylene-3(3,5-di-t-butyl-4-
Examples include combinations of hydroxyphenyl)propionate]methane, 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. It is preferable that the polyhydric alcohol fatty acid ester is partially esterified.

Examples of such fatty acid esters of polyhydric alcohols include glycerin monostearate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate, glycerin dilaurate, etc. fatty acid ester, pentaerythritol monostearate,
Fatty acid esters of pentaerythritol such as pentaerythritol monolaurate, pentaerythritol dilaurate, pentaerythritol distearate, and pentaerythritol tristearate are used.

[0081] Such a phenolic antioxidant is usually used in an amount of 0 per 100 parts by weight of the polyolefin resin composition.
．． 01 to 10 parts by weight, preferably 0.05 to 3 parts by weight,
More preferably, it is used in an amount of 0.1 to 1 part by weight, and the fatty acid ester of polyhydric alcohol is usually 0.01 to 10 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the composition. Used in parts by weight.

The polyolefin resin composition of the present invention includes:
Silica, diatomaceous earth,
Alumina, 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,
Fillers such as montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fibers, silicon carbide fibers, polyethylene fibers, polypropylene fibers, polyester fibers, and polyamide fibers may be blended.

The polyolefin resin composition of the present invention can be produced using known methods. For example, polyolefin resin component [A] and cyclic olefin resin [B], and other components added as desired,
A method of mechanically blending using an extruder, a kneader, etc., or a method of simultaneously dissolving each component in a suitable good solvent (e.g., a hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene, and xylene), Alternatively, a method may be used in which separate solutions are prepared and then mixed, and then the solvent is removed, or a method in which these two methods are combined.

The polyolefin resin composition of the present invention as described above has the following characteristics. In the composition of the present invention, when a cyclic olefin resin [B] having a TMA softening temperature of 100°C or higher, preferably 130°C or higher is used as the cyclic olefin resin, the crystalline polyolefin resin component [A] is heated. Since the cyclic olefin resin [B] is blended with a high deformation temperature, high pencil hardness, and low molding shrinkage, various properties of crystalline polyolefin resin are maintained, and it also has excellent heat resistance, scratch resistance, and molding shrinkage. becomes smaller.

[0085] Also, as a cyclic olefin resin, TM
A Cyclic olefin resin with a softening temperature of 70°C or less [B]
In the composition of the present invention when using the crystalline polyolefin resin component [A], the cyclic olefin resin [B] which has excellent toughness and has a small mold shrinkage rate is blended with the crystalline polyolefin resin component [A]. In addition to maintaining various properties, it has excellent mechanical properties such as tensile elongation and impact strength, and has a low molding shrinkage rate.

Since the crystalline polyolefin resin composition of 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. can be used.

The resin composition of the present invention having such characteristics can be used for various purposes. Examples of this application include housings for power tools, OA equipment, cameras, pumps, etc.; chassis; precision equipment parts; instrument panels, radiator grills, cluster grills, console boxes, garnishes, foil covers, column covers. , automotive interior and exterior materials such as fenders, bonnets, and trunks; sheets; cases or covers for connectors, coil bobbins, switches, etc.; bottles; films such as cast films, biaxially stretched films, and multilayer films; extruded foam; injection Examples include foams such as foam.

[0088]

[Effect of the invention] The polyolefin resin composition of the present invention has
By blending [B] a cyclic olefin resin containing an aromatic group into the [A] polyolefin resin component, a polyolefin resin composition with excellent heat resistance, scratch resistance, moldability, and mechanical properties and a low molding shrinkage rate can be obtained. can get.

[0089]

EXAMPLES The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to these Examples.

[0090]Methods for measuring and evaluating various physical property values in the present invention are shown below. (1) Melt flow index (MFRT) According to ASTM D1238, specified temperature T°C, load 2
．． Measured at 16Kg. (2) Preparation of test piece A test piece was molded under the following molding conditions using an injection molding machine IS-50EPN manufactured by Toshiba Machinery Co., Ltd. and a predetermined test piece mold. After molding, the test piece was left at room temperature for 48 hours and then measured. Molding conditions: Cylinder temperature 220℃, mold temperature 60℃, injection pressure primary/secondary = 1000/800Kg/cm2 injection speed (primary) 30mm/sec, screw rotation speed 1
50 rpm (3) Bending test Measured according to ASTM D790. Test piece shape: 5 x 1/2 x 1/8 t inch, distance between spans 51 mm Test speed: 20 mm/min Test temperature: 23°C (4) Heat distortion temperature (HDT) Measured according to ASTM D648. Test piece shape: 5 x 1/4 x 1/2t 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, the temperature was raised at a rate of 5° C./min, and the temperature when the needle penetrated 0.635 mm into the sheet was defined as TMA. (6) Glass transition temperature (Tg) and melting point (Tm) SE
Measurement was performed using DSC-20 manufactured by IKO Electronics Co., Ltd. at a temperature increase rate of 10° C./min. (7) Rockwell hardness Measured at 23°C according to ASTM D785. (8) Pencil hardness Measured at 23°C according to JIS K 5400.

[0091]

[Example 1] As component [A], crystalline polypropylene resin (crystallinity: 60%, MFR230oC: 10g/
3.5 kg of pellets (10 min), ethylene content measured by 1H-NMR as component [B] is 61.7 mol%, MFR260oC is 15 g/10 min, 135
The intrinsic viscosity [η] measured in decalin at °C is 0.61 dl
/g, TMA is 169°C, Tg is 152°C (Tm not observed) and 1,4-methano-1,4,4
After thoroughly mixing 1.5 kg of pellets of a random copolymer (ethylene/MTHF random copolymer) with a,9a-tetrahydrofluorene (hereinafter abbreviated as MTHF),
The mixture was melt-blended using a twin-screw extruder (manufactured by Ikegai Tekko Co., Ltd., PCM 45) at a cylinder temperature of 220°C, and pelletized using a pelletizer.

[0092] Using the obtained pellets, test pieces were prepared by the method described above, and their physical properties were evaluated. The results are shown in Table 1.

[0093]

[Examples 2 and 3] In Example 1, [A] component and [B
] A composition (pellet) was prepared in the same manner except that the ratio of the components was changed as shown in Table 1, and a test piece was prepared using this composition according to the method described above, and its physical properties were evaluated. .

The results are shown in Table 1.

[0095]

[Examples 4 to 6] Compositions (pellets) were prepared in the same manner as in Example 3, except that other polyolefin resins listed in Table 2 were used in place of polypropylene. A test piece was prepared using the method and its physical properties were evaluated.

The results are shown in Table 2.

[0097]

Comparative Example 1 A molded article was prepared using only the polypropylene used as component [A] in Example 1, and its physical properties were evaluated.

As a result, bending strength, bending modulus, HDT
, Rockwell hardness (R scale), and pencil hardness are 430Kg/cm2, 14000Kg/cm2, and 6, respectively.
It was 0°C, 106, 3B. These values are shown in Table 1.

0099

[Table 1]

[0100]

[Table 2]

Claims (1)

[Claims] Claim 1: [A] Crystalline polyolefin resin; [B]
] Intrinsic viscosity measured in decalin at 135°C selected from the group consisting of copolymers of ethylene and cyclic olefins represented by the following formula [I], ring-opening polymers of cyclic olefins, and hydrogenated products thereof [ η] is 0.05 to 10 dl/g and a cyclic olefin resin having a softening temperature (TMA) of 0° C. or higher, in a weight ratio within the range of 98/2 to 2/98. Resin composition; [I] [Formula [I], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2,
R1 to R19 each independently represent an atom or 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 R9 and R13 or R10 and R11 may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when n=m=0, R15 and R
12 or R15 and R19 may be bonded to each other to form a monocyclic or polycyclic aromatic ring].