JP2825883B2 - Polyamide resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a resin composition containing a polyamide resin and a cyclic olefin-based resin.

Technical Background of the Invention Many polyamide resins represented by 6,6-nylon, 6-nylon, 12-nylon, etc. are crystalline, have a relatively high melting point, and are widely used as engineering plastics. . Such a polyamide resin is often used by adding a filler and further improving heat resistance.

However, when the filler is blended in this way,
The moldability of the polyamide resin may be reduced, and the resulting molded article may have anisotropy depending on the orientation direction of the compounded filler.

In addition, a polyamide resin not containing a filler has a high molding shrinkage, so that the dimensional accuracy of the molded body is often not sufficiently high, and further, the heat resistance is lower than that of a polyamide resin containing a filler. In addition, when no filler is added, the water absorption of the polyamide resin increases, and the properties such as acid resistance and alkali resistance also decrease.

As described above, conventionally widely used polyamide resins are resins having excellent properties, and among these properties, further improvement is desired as described above.

By the way, a cyclic olefin having an ethylenic double bond in the ring has polymerizability, and for example, a cyclic olefin / α-olefin random copolymer can be obtained by reacting with an α-olefin such as ethylene. Are known. Furthermore, the above-mentioned cyclic olefins are used as copolymers with α-olefins, and are also used as optical materials excellent in transparency, water resistance and thermal properties by opening the ring of the cyclic olefin itself. It is already known that this is possible (see JP-A-60-26024).

Such a cyclic olefin resin has transparency, water resistance and thermal properties required as an optical material, but as a result of further studies by the present inventors, such a cyclic olefin resin was It has been found that a resin composition having more excellent properties that can be used for various applications can be obtained by blending it with a polyolefin resin.

An object of the present invention is to provide a resin composition having excellent heat resistance and chemical resistance, and having a low water absorption and a low molding shrinkage.

SUMMARY OF THE INVENTION The resin composition according to the present invention comprises: [A] a polyamide resin: 98 to 2 parts by weight, and [B] a ring-opening polymer obtained by ring-opening polymerization of a cyclic olefin represented by the following formula [I]. Or a cyclic olefin resin comprising a ring-opened copolymer or a hydrogenated product of these polymers or copolymers: 2 to 98 parts by weight. Here, the total amount of the polyolefin resin and the cyclic olefin resin is 100
Parts by weight.

However, in the above formula [1], n is 0 or 1, m is 0 or a positive integer, and R ^{1 to} R ¹⁸ are each independently a group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group forms a double bond. And R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group.

Furthermore, in the present invention, the cyclic olefin-based resin may be partially or entirely modified with a carboxylic acid or a derivative thereof.

Further, the present invention, the polyamide resin composition as described above, the polyamide resin composition 100 parts by weight of 1-1 to 1 part
Also provided is a composition comprising 00 parts by weight of a modified cyclic olefin random copolymer.

Here, the modified product of the cyclic olefin random copolymer (modified cycloolefin random copolymer) is obtained by converting a cyclic olefin random copolymer formed from ethylene and a cyclic olefin represented by the following formula [I] to an unsaturated olefin. Obtained by modification with an acid or a derivative thereof,
Intrinsic viscosity [η] measured in 135 ° C decalin is 0.05 to 10d
l / g, a resin having a content of a constituent unit derived from an unsaturated carboxylic acid or a derivative thereof of 0.05 to 10% by mole. The resin composition according to the present invention comprises a polyamide resin and a specific cyclic olefin ring-opened. Because it consists of a cyclic olefin-based resin obtained by polymerization or copolymerization,
The heat resistance and chemical resistance of the resin are excellent, and the resin has characteristics of low water absorption and molding shrinkage.

Moreover, by blending such a cyclic olefin resin, the excellent properties of the polyamide resin are not impaired.

Next, the polyamide resin composition according to the present invention will be specifically described.

The polyamide resin composition according to the present invention comprises a polyamide and a cyclic olefin-based resin formed by ring-opening polymerization of a specific cyclic olefin.

The polyamide used in the present invention has, for example, the following formula [A-
1] or a resin having a repeating unit represented by [A-2].

However, in the formulas [A-1] and [A-2], R ^{20 to} R ²² each independently represent a divalent hydrocarbon group. This hydrocarbon group may be an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. Further, R ²⁰ to R ²² may be different even in the same.

Examples of such polyamide resins include ring-opened polymers of lactams, which are cyclic amides, polycondensates of aminocarboxylic acids, and polycondensates of dicarboxylic acids and diamines.

Specifically, as the ring-opening polymer of lactams, for example, nylon 6 produced from ε-caprolactam can be mentioned, and as the polycondensate of aminocarboxylic acid, produced from ω-aminoundecanoic acid Nylon 12
Examples of polycondensates of dicarboxylic acids and diamines include nylon 6,6 produced from adipic acid and hexamethylene diamine, and nylon 6, produced from sebacic acid and hexamethylene diamine. 10. Nylon 6,12 produced from dodecanedioic acid and hexamethylenediamine.

Further, as the polyamide resin used in the present invention, in addition to the above polyamide, for example, an aromatic polyamide having a repeating unit as described below can also be preferably used.

However, in the above formula, q is 1 or 2,
p represents an integer of 2 to 20. Examples of such aromatic polyamides include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and 4,4-diphenoxyethanedicarboxylic acid.

Also, an alicyclic polyamide can be obtained by using an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid instead of the aromatic dicarboxylic acid.

Such polyamides can be used alone or in combination of two or more.

In the present invention, from the above polyamides, pyramide having desired properties can be selected and used in consideration of the use of the obtained composition and the like, but usually, a number average molecular weight is used. Is used in the range of 1,000 to 100,000.

The cyclic olefin-based resin used in the present invention is a resin formed by ring-opening a specific cyclic olefin represented by the following formula [I].

However, in the above formula [I], n is 0 or 1, and m is 0 or a positive integer.

R ^{1 to} R ¹⁸ each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. Here, as the halogen atom,
For example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be mentioned. Examples of the hydrocarbon group include, independently of each other, usually an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms. Specific examples of the alkyl group include: Methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl and octadecyl groups can be mentioned. A specific example of the cycloalkyl group includes a cyclohexyl group.

Further, in the above formula [I], R ¹⁵ and R ¹⁶ are
R ¹⁷ and R ¹⁸ are each bonded (in cooperation with each other),
A monocyclic or polycyclic group may be formed, and the monocyclic or polycyclic group thus formed may have a double bond.

Further, R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms,
Specific examples of such an alkylidene group include an ethylidene group, a propylidene group and an isopropylidene group.

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

That is, specific examples of the cyclic olefin represented by the above formula [I] used in the present invention include bicyclo [2,2,1] hept-2-ene derivative and tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -3-dodecene derivatives, hexacyclo [6,6,1,1 ^3.6, 1 ^10.13, 0 ^2.7, 0 ^9.14]
4 Heputadensen derivatives, octacyclo [8,8,0,1 ^2.9, 1 ^4.7, 1 ^11.18, 1 ^13.16,
0 ^3.8, 0 ^12.17] -5-docosene derivatives, pentacyclo [6,6,1,1 ^3.6, 0 ^2.7, 0 ^9.14] -4-hexadecene derivative, heptacyclo-5-icosene derivatives, heptacyclo-5-heneicosene derivatives, tricyclo [4,3,0,1 ^2.5] -3-decene derivatives, tricyclo [4,3,0,1 ^2.5] -3-undecene derivatives, pentacyclo [6,5,1,1 ^3.6, 0 ^2.7, 0 ^9.13] 4-pentadecene derivatives, penta cyclopentadiene decadiene derivative, pentacyclo [4,7,0,1 ^2.5, 0 ^8.13, 1 ^9.12] -3-pentadecene derivatives, pentacyclo [7,8,0,1 ^3.6, 0 ^2.7, 1 ^10.17 , 0 ^11.16 ,
1 ^12.15] -4-eicosene derivatives, and Nonashikuro [9,10,1,1,4.7,0 ^3.8, 0 ^2.10, 0 ^12.21, 1
^13.20 , 0 ^14.19 , 1 ^15.18 ] -5-pentacocene derivative.

 Specific examples of such compounds are shown below.

Bicyclo [2,2,1] hept-2-ene derivatives such as; Tetracyclo such [4,4,0,1 ^2.5, 1 ^7.10] -3-dodecene derivatives; Hexacyclo such as [6,6,1,1 ^3.6, 1 ^10.13, 0 ^2.7, 0
^9.14 ] -4-Heptadecene derivatives; Octacyclo such as [8,8,0,1 ^2.9, 1 ^4.7, 1 ^11.18, 1
^13.16, 0 ^3.8, 0 ^12.17] -5-docosene derivatives; Pentacyclo such as [6,6,1,1 ^3.6, 0 ^2.7 0 ^9.14] -4
-Hexadecene derivatives; A heptacyclo-5-icosene derivative or a heptacyclo-5-heneicosene derivative; Tricyclo [4,3,0,1 ^2.5] -3-decene derivatives such as; Tricyclo [4,4,0,1 ^2.5] -3-undecene derivatives such as; Pentacyclo such as [6,5,1,1 ^3.6, 0 ^2.7 0 ^9.13] -4
-Pentadecene derivatives; Diene compounds such as; Heptacyclo such [4,7,0,1 ^2.5, 0 ^8.13, 1 ^9.12] -3
-Pentadecene derivatives; Pentacyclo such as [7,8,0,1 ^3.6, 0 ^2.7, 1 ^10.17, 0
^11.16 , 1 ^12.15 ] -4-Eicosene derivatives; Nonacyclo [9,10,1,1 ^4.7 , 0 ^3.8 , 0 ^2.18 ,
0 ^12.21 , 1 ^13.28 , 0 ^14.19 , 1 ^15.18 ] -5-Pentacose derivatives.

The cyclic olefin represented by the formula [I] is converted to the cyclic olefin by a method known per se (see JP-A-60-26024).
The ring-opening polymer or ring-opening copolymer used in the present invention can be produced by ring-opening polymerization or ring-opening copolymerization.

That is, such a ring-opening polymer or ring-opening copolymer can be produced by polymerizing or copolymerizing the cyclic olefin represented by the above formula [1] in the presence of a ring-opening polymerization catalyst.

Examples of the ring-opening polymerization catalyst used here include a catalyst comprising a metal halide such as ruthenium, rhodium, palladium, osmium, indium or platinum, a nitrate or an acetylacetone compound, and a reducing agent such as an alcohol; titanium, palladium, The catalyst includes a metal halide such as zirconium or molybdenum or an acetylacetone compound, and an organic aluminum.

Ring-opening polymer or copolymer used in the present invention,
The repeating unit derived from the cyclic olefin represented by the above formula [I] is used in an amount of usually at least 50 mol%, preferably at least 80 mol%.
Mol% or more, particularly preferably 90 mol% or more. The molecular weight of such a ring-opening polymer or ring-opening copolymer is usually in the range of 1,000 to 500,000, preferably 10,000 to 100,000. The molecular weight can be controlled by adjusting the reaction conditions, and can also be adjusted by, for example, blending a small amount of olefin or other cycloolefin.

By performing ring-opening polymerization or ring-opening copolymerization as described above, the obtained polymer is considered to have at least a part thereof having a repeating unit represented by the following formula [II]. Can be

However, in the above formula [II], n and m and
R ^{1 to} R ¹⁸ have the same meaning as described above.

In the present invention, as the cyclic olefin-based resin, a hydrogenated product of the above-mentioned ring-opening polymer or copolymer can be used together with or separately from the above-mentioned ring-opening polymer or ring-opening copolymer. This hydrogenated product
The compound can be produced by hydrogenating a double bond remaining in the ring-opened polymer or ring-opened copolymer produced as described above by a method known per se.

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

Examples of such a heterogeneous catalyst include nickel, palladium, platinum or a catalyst in which these metals are supported on a carrier such as carbon, silica diatomaceous earth, alumina, and titanium oxide. Specific examples include , Nickel / silica, nickel / diatomaceous earth, palladium / carbon, palladium / silica, palladium / diatomaceous earth and palladium / alumina.

Examples of the homogeneous catalyst include a catalyst based on a metal belonging to Group VIII of the periodic system. Specific examples include nickel / triethylamine naphthenate, n-butyllithium naphthenate, and nickel acetylacetonate. / A catalyst comprising a Ni or Co compound such as triethylaluminum and an organometallic compound of a Group I-III metal, and a Rh compound.

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

The pressure of the hydrogen gas at the time of such hydrogenation is usually set at 1 to 150 atm, and the reaction temperature is usually set at 0 to 100 ° C, preferably at 20 to 100 ° C.

The hydrogenation rate can be arbitrarily adjusted by changing the hydrogen pressure, the reaction temperature, the reaction time, the catalyst concentration, etc., and the hydrogenated product used in the present invention may be a polymer or a copolymer. Preferably, at least 50% of the existing double bonds are hydrogenated, particularly preferably at least 80%, more preferably at least 90%.

The hydrogenated product thus produced is considered to have, for example, a repeating unit represented by the following formula [III].

However, in the above formula [III], n and m and R ^{1 to} R ¹⁸ have the same meaning as described above.

In the present invention, the ring-opening polymer and the ring-opening copolymer and the hydrogenated product can be used individually or in combination.

Further, in the present invention, when producing the above-described ring-opened polymer, ring-opened copolymer or hydrogenated product, the above-mentioned formula [I] may be used as long as the properties of the obtained polymer and the like are not impaired. And a cyclic olefin other than the cyclic olefin represented by Examples of such a cyclic olefin 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, 5,6,7a-tetrahydro-4,7-methano-1H-indene and the like can be mentioned. Such other cyclic olefins can be used alone or in combination, and are usually used in an amount of 0 to 20 mol%.

Such a cyclic olefin-based resin, that is, a ring-opened polymer, a ring-opened copolymer and a hydrogenated product thereof may be partially or entirely modified with an unsaturated carboxylic acid such as maleic anhydride. . May be further modified.

Such a modified product can be produced by reacting the cyclic olefin resin as described above with an unsaturated carboxylic acid, an anhydride thereof, or a derivative such as an alkyl ester of an unsaturated carboxylic acid. In the reaction, the method for producing a modified cyclic olefin copolymer disclosed in JP-A-62-27412 can be used as a guide. The content of the component unit derived from the modifier in the modified product of the cyclic olefin resin is usually 0.01 to 10% by weight.

Such a modified cyclic olefin-based resin can be produced by blending a modifier with a cyclic olefin-based resin and graft-polymerizing the modified olefin-based resin so as to have a desired modification rate, or preparing a modified product having a high modification rate in advance. Then, it can also be produced by mixing this modified product with an unmodified cyclic olefin resin.

In the resin composition of the present invention, in addition to the above-mentioned cyclic olefin-based resin, ethylene and a repeating unit derived from ethylene and a repeating unit derived from the formula [I] are randomly arranged. A modified product of an addition polymer with a cyclic olefin random (modified cyclic olefin random copolymer) may be blended.

Here, as the cyclic olefin random copolymer used for preparing the modified cyclic olefin random copolymer, the amount of the repeating unit derived from ethylene is
Usually 40-85 mol%, preferably 50-70 mol%,
A copolymer having a repeating unit derived from a cyclic olefin in an amount of usually 15 to 60 mol%, preferably 25 to 50 mol% is preferably used. In the cyclic olefin random copolymer, the repeating units derived from ethylene and the repeating units derived from the cyclic olefin are arranged substantially linearly. That is, the cyclic olefin random copolymer has substantially no gel-like crosslinked structure.

In such a cyclic olefin random copolymer, at least a part of the cyclic olefin represented by the above formula [I] is randomly copolymerized with ethylene in a form represented by the following formula [IV]. It is thought that it is.

However, in the above formula [IV], R ^{1 to} R ¹⁸ and n and m have the same meanings as those in the above formula [I].

Such cyclic olefin random copolymer, 135
The ultimate temperature measured in decalin at ℃ is usually 0.01-10dl
/ g, preferably 0.08 to 7 dl / g, and is a cyclic olefin random copolymer having a glass transition temperature of usually 70 ° C or higher.

A modified product of such a cyclic olefin random copolymer is prepared by using a modifying agent such as maleic anhydride as disclosed in JP-A-62-27471.
It can be produced by modification using the technique disclosed in Japanese Patent Publication No. 2 as a guideline.

A modified product of an addition polymer of a cyclic olefin and ethylene can be produced by reacting the polymer with a derivative such as an unsaturated carboxylic acid, an anhydride thereof, or an alkyl ester of an unsaturated carboxylic acid. . In addition,
In this case, the content of the component unit derived from the modifier in the modified product of the cyclic olefin resin is usually 0.01 to
10% by weight.

Such a modified cyclic olefin-based resin can be produced by blending a modifier with a cyclic olefin-based resin and graft-polymerizing the modified olefin-based resin so as to have a desired modification rate, or preparing a modified product having a high modification rate in advance. Then, it can also be produced by mixing the modified product with an unmodified cyclic olefin-based resin.

In the resin composition of the present invention, the above-mentioned cyclic olefin-based resin and the polyester resin are blended in the polyester resin.

The resin composition of the present invention contains 98 to 2 parts by weight of the above-mentioned cyclic olefin resin and 2 to 98 parts by weight of the polyamide resin. Here, the total content of the cyclic olefin resin and the polyamide resin is 100 parts by weight.

And, more preferably, the cyclic olefin resin 30 to
It consists of 70 parts by weight and 70 to 30 parts by weight of a polyamide resin.

Of course, as described above, the cyclic olefin-based resin may be partially or entirely modified.

When the resin composition of the present invention contains a modified product of an addition polymer of cyclic olefin and ethylene (that is, a modified cyclic olefin random copolymer), the modified product is a polyamide resin and an unmodified cyclic olefin. Usually, 1 to 100 parts by weight, based on 100 parts by weight of the total weight of the system resin,
Preferably, it is recommended to mix in an amount of 2 to 20 parts by weight.

The resin composition of the present invention further contains a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent, an anti-blocking agent, an anti-fogging agent, a lubricant, a dye, a pigment, a natural oil, a synthetic oil, a wax, and an organic filler. Agents and inorganic fillers can also be blended.

For example, the stabilizer used in the present invention includes tetrakis [methylene-3 (3,5-di-t-butyl-
4-hydroxyphenyl) propionate] methane, β
-(3,5-di-t-butyl-4-hydroxyphenyl)
Phenolic oxidation stabilizers such as alkyl propionate and 2,2'-oxamide bis [ethyl-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]; 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; Can be mentioned.

These can be used alone or in combination. As an example of such a combination, mention may be made of a combination of tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, zinc stearate and glycerin monostearate. it can.

Examples of the organic or inorganic filler 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 flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene Fibers and polyamide fibers can be mentioned.

Such an organic or inorganic filler is usually 1 to 100 parts by weight, preferably 5 to 100 parts by weight, based on a total of 100 parts by weight of the cyclic olefin resin and the polyamide resin.
Particularly preferably, it is used in an amount of 5 to 50 parts by weight.

The resin composition of the present invention may contain other resins as long as the properties are not impaired. Examples of resins that can be blended in this case include polyester, polyolefin, polyamide, polycarbonate,
Halogen-containing vinyl polymers, polymers or copolymers from α, β-unsaturated carboxylic acids or derivatives thereof, epoxide polymers, polyacetals, polyphenylene oxides, polysulfones, polyurethane resins, urea resins,
Examples include alkyd resins, phenolic resins, olefin-based rubbers, and diene-based rubbers.

The resin composition of the present invention can be produced by, for example, a method of simultaneously mixing the respective components, a method of mixing the polyamide and the cyclic olefin-based resin, and then mixing other components as desired.

Further, the mixing of the cyclic olefin resin and the polyamide resin is performed by blending the cyclic olefin resin and the polyamide in a molten state using an extruder or the like, or a saturated hydrocarbon such as heptane, hexane, decane or cyclohexane. The cyclic olefin resin and the polyamide resin can be dissolved and mixed in an aromatic hydrocarbon such as toluene, benzene or xylene, and then mixed, and then mixed using a method of removing the solvent.

The resin composition of the present invention thus obtained has not only the excellent properties inherent to polyamide but also particularly excellent heat resistance and chemical resistance. Furthermore, by incorporating a cyclic olefin-based resin, the water absorption is reduced, and the progress of the hydrolysis reaction during molding is suppressed.
Further, the molding shrinkage of the molded body is reduced.

Since the resin composition of the present invention has the above-mentioned properties, in addition to applications where a polyamide resin is conventionally used, heat resistance, chemical resistance, low water absorption or low molding shrinkage are required. Can be widely used in the field.

Effects of the Invention Since the resin composition of the present invention is composed of a polyamide resin and a cyclic olefin-based resin, it is particularly excellent in heat resistance and chemical resistance. Furthermore, by incorporating a cyclic olefin-based resin, the water absorption is reduced, and the progress of the hydrolysis reaction during molding is suppressed. Further, the molding shrinkage of the molded body is reduced.

Next, the present invention will be described in more detail with reference to Examples of the present invention. However, the present invention should not be construed as being limited by these Examples.

The methods for measuring and evaluating various physical properties in the present invention are described below.

(1) Melt flow index (MRF T ° C) Measured at a temperature T ° C and a load of 2.16 kg according to ASTM D1238.

(2) Preparation of test piece The test piece was molded under the following molding conditions using an injection molding machine IS-55EPN manufactured by Toshiba Machine Co., Ltd. and a predetermined test piece preparation mold.
The test pieces were left at room temperature for 48 hours after molding before use.

Molding condition Cylinder temperature: 280 ° C Mold temperature: 60 ° C Injection pressure primary / secondary: 1000 / 800Kg / cm ² Injection speed (primary): 50% Screw rotation speed: 150rpm (3) Bending test Performed according to ASTM D790 Was.

Test specimen shape: 5 x 1/2 x 1/8 ^t inch, distance between spans: 50 mm Test speed: 20 mm / min Test temperature 23 ° C (4) Izod impact test The test was performed according to ASTM D256.

Test specimen shape: 5 × 1/2 × 1/8 ^t inch, test temperature 23 ° C. (5) Heat distortion temperature (HDT) This was performed according to ASTM D648.

Specimen shape: 5 × 1/4 × 1/2 ^t inch, Weight: 264 psi (6) Softening temperature (TMA) Measured by thermal deformation strength of a 1 mm thick sheet using a Thermo Mechanical Analyzer manufactured by DuPont. That is, place a quartz needle on the sheet, apply a weight of 49 g, and apply 5 ° C /
The temperature was raised at a speed of one minute, and the temperature at which the needle penetrated 0.635 mm into the sheet was defined as TMA.

(7) Glass transition temperature (Tg) Using SEIKO Electronics Co., Ltd.
Measured in ° C / min.

(8) Water absorption The value after 24 hours was measured according to the JIS K 7209A method.

(9) Pencil hardness Measured at 23 ° C. according to JIS K 5400.

Reference Example 1 (Synthesis of ring-opening polymer) 700 ml of toluene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene (DMO
N) 93 ml, 2-norbornene (NB) 7 ml, 1-hexane 0.
5 ml and 0.1 mmol of WCl ₆ and tetraphenyltin were added and polymerization was carried out at 50 ° C. for 2 hours.

The polymerization solution was poured into a large amount of methanol, and the formed polymer was precipitated and collected by filtration. The polymer was washed with methanol and acetone three times each, and dried at 80 ° C. overnight under reduced pressure to obtain a 98 g weight. A coalescence was obtained.

The intrinsic viscosity [η] of the obtained polymer measured in toluene at 30 ° C. was 0.78 dl / g, and the NB content measured by ¹³ C-NMR was 10 mol%.

(Hydrogenation reaction of ring-opening polymer) Dissolve 20 g of ring-opening polymer in 250 ml of tetrahydrofuran,
1.5 g of a catalyst having 1 g of Pd supported on 50 g of silica was placed in 1 autoclave, and then the autoclave was charged with H ₂ and pressurized to 50 kg / cm ² G, and then heated to 50 ° C. for 15 hours. Stirring was continued.

The polymer was filtered from the obtained chiller solution, and then the polymer (containing the catalyst) was dissolved in cyclohexane to separate the catalyst from the polymer, followed by drying at 100 ° C. under reduced pressure for 24 hours. . The hydrogenation rate was 97%.

About the obtained polymer, DSC manufactured by Harkin Elmer Co.
The glass transition temperature (Tg), which was measured at a heating rate of 10 ° C./min using, was 155 ° C.

Reference Example 2 Pellets of the hydrogenated ring-opened polymer obtained in Reference Example 1 5k
g, maleic anhydride 50 g dissolved in acetone 25 g,
An organic peroxide (manufactured by NOF Corp., Pahekishin ^TM 25
B) After adding 3 g and mixing well, the mixture was melted at a cylinder temperature of 250 ° C. by a twin-screw extruder (PCM 45, manufactured by Ikegai Iron Works Co., Ltd.) and pelletized by a pelletizer.

The maleic anhydride content of the obtained resin was 0.8% by weight.
Met.

Example 1 Nylon 6 nameplate (CM) manufactured by Toray Industries, Inc. as the component (A)
After sufficiently mixing 2.0 kg of the pellet of 1017) and 2 kg of the hydrogenated polymer pellet obtained as described above as the component [B], a twin-screw extruder (PCM 45, manufactured by Ikegai Iron Works Co., Ltd.) The mixture was melt-blended at a cylinder temperature of 280 ° C. and pelletized with a pelletizer.

Test pieces were prepared from the obtained pellets by the method described above, and the physical properties were evaluated.

 Table 1 shows the results.

Examples 2 and 3 Pellets were produced in the same manner as in Example 1 except that the blending amounts of the [A] component and the [B] component ([A] component / [B] component) were changed as described below. A test piece was prepared in the same manner except that this pellet was used, and its physical properties were evaluated.

[A] component / [B] component = 1.0 / 3.0 (Example 2) [A] component / [B] component = 3.0 / 1.0 (Example 3) The results are shown in Table 1.

Example 4 In Example 1, in addition to the polyamide resin and the hydrogenated ring-opening polymer, the maleic anhydride-modified hydrogenated ring-opening polymer produced in Reference Example 2 was further used as a component [C] in the ratio shown below. A pellet was produced in the same manner except that the pellet was used, and a test piece was prepared in the same manner except that this pellet was used, and its physical properties were evaluated.

Pyrimamide resin / hydrogenated ring-opened polymer / maleated hydrogenated ring-opened polymer = 2 / 1.6 / 0.4 The results are shown in Table 1.

Example 5 An ethylene / propylene random copolymer (ethylene content: 80) was added to 2 kg of the hydrogenated ring-opened polymer obtained in Reference Example 1.
Mol%, Tg: 54 ° C, MFR ₂₃₀ ° C: 0.7 g / 10 min, [η]: 2.2 dl /
g) After sufficiently mixing 0.5 kg of the pellet, the cylinder temperature is set to 220 with a twin-screw extruder (PCM 45, manufactured by Ikegai Iron Works Co., Ltd.).
The resulting mixture was melt-blended at ℃ and pelletized with a pelletizer.

For 1 kg of the obtained pellets, manufactured by NOF Corporation,
1 g of Perhexin ^™ 25B and 3 g of vinylbenzene were added and mixed well.

This mixture was mixed with the twin-screw extruder (cylinder temperature: 230
C.) and then pelletized with a pelletizer.

Pellets were produced in the same manner as in Example 1 except that the pellets produced as described above were used instead of the hydrogenated ring-opened polymer prepared in Reference Example 1 used as the component [B]. Specimens were prepared in the same manner except that pellets were used, and their physical properties were evaluated.

 Table 1 shows the results.

Comparative Example 1 In Example 1, [A] was used without using the component [B].
Components [Test pieces were prepared in the same manner except that only the polyamide used in Example 1 was used, and the physical properties thereof were evaluated.

 Table 1 shows the results.

Claims (3)

(57) [Claims] 1. A ring-opening polymer or a ring-opening copolymer obtained by ring-opening polymerization of a polyamide resin: 98 to 2 parts by weight and a cyclic olefin represented by the following formula [I], or a polymer or copolymer thereof. Cyclic olefin resin comprising a hydrogenated polymer: 2 to 98 parts by weight (provided that the total amount of the polyolefin resin and the cyclic olefin resin is 100 parts by weight) Composition; (In the formula, n is 0 or 1, m is 0 or a positive integer, and R ^{1 to} R ¹⁸ are each independently an atom or a atom selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond. R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group). 2. The polyamide resin composition according to claim 1, wherein part or all of the cyclic olefin resin is modified with a carboxylic acid or a derivative thereof. 3. A ring-opened polymer or ring-opened copolymer obtained by ring-opening polymerization of a polyamide resin: 98 to 2 parts by weight and a cyclic olefin represented by the following formula [I], or a polymer or copolymer thereof. Cyclic olefin resin composed of hydrogenated polymer: 2 to 98 parts by weight (however, the total amount of the polyolefin resin and the cyclic olefin resin is 100 parts by weight)
And a cyclic olefin random copolymer formed from ethylene and a cyclic olefin represented by the following formula [I], modified with an unsaturated carboxylic acid or a derivative thereof.
Intrinsic viscosity [η] measured in 5 ° C decalin is 0.05 to 10 dl /
g, a modified cyclic olefin random copolymer having a content of structural units derived from an unsaturated carboxylic acid or a derivative thereof of 0.05 to 10 mol%, wherein the content of the modified cyclic olefin random copolymer is: A polyamide resin composition characterized by being in the range of 1 to 100 parts by weight based on 100 parts by weight of the total weight of the polyamide resin and the cyclic olefin resin; (Wherein, n is 0 or 1, m is 0 or a positive integer, and R ^{1 to} R ¹⁸ are each independently an atom or a atom selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond. R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group).