JPH02232261A - Polyamide resin composition - Google Patents

Abstract

PURPOSE:To improve heat resistance, chem. resistance and mechanical strength and to reduce both water-absorbing ratio and shrinkage in molding by compounding a polyamide resin and a specified modified cyclic olefin addition polymer or a modified cyclic olefin ring-opening polymer. CONSTITUTION:A modified cyclic olefin addition polymer (a) is obtd. by graft- copolymerizing 0.001-5wt.% (in terms of COOH group) unsatd. carboxylic acid (or deriv. thereof) (i) onto an addition polymer consisting of 40-90mol% ethylene (ii) and 10-60mol% cyclic olefin component (iii) of formula I or II (wherein n and m are 0 or larger; l is 3 or larger; R<1-10> are each H, a halogen or a hydrocarbon group). Separately, a modified cyclic olefin ring-opening polymer (b) is obtd. by reacting a ring-opening polymer (or a hydrogenated product thereof) of the component (iii) with 0.001-5wt.% (in terms of COOH group) component (i). A polyamide resin (A) having a repeating unit of formula III or IV [p and q are each a positive integer; R<11-13> are each an aliph., alicyclic or arom. hydrocarbon group (or deriv. thereof)] and the component (a) or (b) (B) with a wt. ratio A/B of 98-2/2-98 and an intrinsic viscosity (measured in decalin at 135 deg.C) of 0.05-10dl/g are compounded.

Description

[Detailed description of the invention] [Industrial application field] This invention. This invention relates to a polyamide resin composition that has excellent heat resistance and chemical resistance, low water absorption and mold shrinkage, and high mechanical strength. [Prior art] Most polyamide resins are crystalline and have a relatively high melting point, so those containing fillers have a high heat distortion temperature.
Excellent heat resistance. However, when a filler is added, moldability deteriorates and anisotropy occurs in the physical properties of the molded product.

On the other hand, products without fillers have a high molding shrinkage rate, lack dimensional accuracy, and have poor heat resistance. Furthermore, polyamide resins have problems in that they have poor acid resistance and alkali resistance, and high water absorption.

[Problem to be solved by the invention]

The purpose of the present invention is to solve the above-mentioned problems by providing polyamide resin with excellent heat resistance and chemical resistance while maintaining its properties.
Another object of the present invention is to obtain a polyamide resin composition that has low water absorption and mold shrinkage, and high mechanical strength. [Means for Solving the Problems] The present invention provides the following polyamide resin composition. (1)
(A) Polyamide resin and (B) Intrinsic viscosity measured in decalin at 135°C [η
] is 0.05 to lodR/g (a) An addition polymer consisting of an ethylene component and a cyclic olefin component represented by the following general formula [1] and/or (II), an unsaturated carboxylic acid or its derivative component into a modified cyclic olefin addition polymer, or (b) a ring-opening polymer of a cyclic olefin component represented by the following general formula [I] and/or (II), or a hydrogenated product thereof, an unsaturated carboxylic acid or and a modified cyclic olefin ring-opening polymer into which the derivative component has been introduced, and the weight ratio of [A] component/[B] component is 987.
A polyamide resin composition characterized in that the ratio is 2 to 2/98. It is a general formula resin. [In the formula, n and m are both O or a positive integer, Q is an integer of 3 or more, and R1, NN, and H1a each represent a hydrogen atom, a halogen atom, or a hydrocarbon group. ] The polyamide resin (A) constituting the polyamide resin composition of the present invention has the following general formula (ml or general formula (IV)
A polyamide having a repeating unit represented by [Formula, p and q are positive integers, and RitHIZH11 each represents an aliphatic, alicyclic, or aromatic hydrocarbon or a derivative thereof. ] Specifically, such polyamide resins include ring-opened polymers of lactams, which are cyclic amides (for example, nylon 6 produced from E-cabralactam), and polycondensates of aminocarboxylic acids (for example, ω-aminoundecane). Nylon 11 produced from acid, nylon 12 produced from ω-aminododecanoic acid), polycondensates of dicarboxylic acids and diamines (e.g. nylon 6,6 produced from adivic acid and hexamethylene diamine, sebacin) Examples include nylon 6,10 manufactured from acid and hexamethylene diamine, and nylon 6.12) manufactured from dodecanedioic acid and hexamethylene diamine. These polyamide resins can be used alone or in combination of two or more.

The component CB) used in the present invention may be either the modified cyclic olefin addition polymer (a) or the modified cyclic olefin ring-opening polymer (b).

Hereinafter, among components CB), the modified cyclic olefin addition polymer (a) will be explained first, and then the modified cyclic olefin ring-opening polymer (b) will be explained.

The cyclic olefin represented by the general formula CI] or [■] mainly forms repeating units having a structure represented by the following general formula (V) or (VI) in the modified cyclic olefin addition polymer (a). ing.

General formula [in the formula. n, m. Q and R1 to R1B are the same as above. ] The cyclic olefin constituting the modified cyclic olefin addition polymer (a) component in the present invention has the general formula (i) and CI! ) is at least one cyclic olefin selected from the group consisting of unsaturated monomers represented by The cyclic olefin represented by the general formula (1) can be easily produced by condensing cyclopentadiene and a corresponding olefin by Diels-Alder reaction. Similarly, the cyclic olefin represented by the general formula (II) can be easily produced by condensing cyclopentadiene and the corresponding cyclic olefin by the Diels-Alder reaction. Specifically, as the cyclic olefin represented by the general formula (1), the compounds listed in Table 1, or 1, 4, 5.8
-dimethano-1.2,3,4,4a,5,8,8a-octahydronaphtha L/n, as well as 2-methyl-1.4,
5.8-dimethano-1. ,2,3,4,4a,5,8,
8a-octahyde naphthalene, 2-ethyl-1,4,
5.8-dimethano-1,2,3,4,4a,5,8,8
a-octahyde naphthalene, 2-probyl-1.4,
5.8-dimethano-1,2,3,4,4a,5,8,8
a-octahyde naphthalene, 2-hexyl-1.4,
5.8-dimethano-1,2,3,4,4a, 5,
8, 8a-octahyde-naphthalene, 2,3-dimethyl-I,4,5,8-dimethano-1.2,3,4,
4a,5,8,8a-octahydride naphthalene, 2-methyl-3-ethyl-1.4,5.8-dimethano-1,2
,3,4,4a,5,8,8a-octahyde-naphthalene,2-chloro-1.4,5.8-dimethano-1.2,
3,4,4a,5,8.8a-octahyde naphthalene, 2-bromo 1,4,5,8-dimethano-1.2,3
,4.4a,5,8,8a-octahyde naphthalene,
2-fluoro1.4,5.8-dimethano-1,2,3
．． 4.4a,5,8,8a-octahyde naphthalene,
2,3-diqO O-1.4,5.8-dimethano-1,
2,3,4,4a,5,8.8a-octahyde naphthalene, 2-cyclohexyl-1.4,5.8-dimethano-1.2,3,4,4a,5,8,8a-octahyde Naphthalene, 2-n-butyl-1,4,5.8-dimethano-1.2,3,4,4a,5,8Ja-octahyde naphthalene, 2-inbutyl-1,4,5.8-dimethano-1. Examples include octahyde naphthalenes such as 2,3,4,4a,5,8,8a-octahydronaphthalene, and the compounds listed in Table 2. Furthermore, specific examples of the cyclic olefin represented by the general formula [■] include the compounds shown in Tables 3 and 4. Examples of the unsaturated carboxylic acid or its derivative component which is a component of the modified cyclic olefin addition polymer (a) constituting the resin composition of the present invention include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, itaconic acid, Citraconic acid, undecylenic acid, maleic anhydride, tetrahydrophthalic acid, isocrotonic acid, nadic acid (endocyto-(2,2,1)hept-5-ene-2,3-dicarboxylic acid), citraconic anhydride, nadic anhydride Examples include unsaturated carboxylic acids such as acids, and derivatives such as their acid anhydrides. Modified cyclic olefin addition polymer (a) constituting the resin composition of the present invention
has an ethylene component, the cyclic olefin component, and the unsaturated carboxylic acid or its derivative component as essential components, but in addition to these essential components, other substances may be added as necessary to the extent that the purpose of the present invention is not impaired. It may also contain other unsaturated monomer components. Specifically, examples of unsaturated monomers that may be optionally copolymerized include propylene, 1-butene, and 4-methyl-l-pentene in an amount less than equimolar to the ethylene component unit in the resulting copolymer. ,■
α- with 3 to 20 carbon atoms such as -hexene, l-octene, 1-decene, ■-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, l-eicosene, etc.
Olefins; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, styrene, α-methylstyrene, dicyclopentadiene, ethylidene norbornene, 2, 3,3
a,7a-tetrahydro-4,7-methanol-111-indene, 3a,5,6.7s-tetrahydro-4,7-
Examples include methanol, IH-indene, and the like.
Those with double bonds in the molecule can also be hydrogenated to improve weather resistance and heat aging resistance. In the modified cyclic olefin addition polymer (a) constituting the resin composition of the present invention, the ethylene component is 40 to 90 mol%, preferably 50 to 80 mol%, and the cyclic olefin component is 10 to 60 mol%, preferably 20 The unsaturated carboxylic acid or its derivative component is suitably in the range of 0.001 to 5% by weight, preferably 0.05 to 2% by weight as a carboxyl group or its derivative group. The intrinsic viscosity [η] of the modified cyclic olefin addition polymer (a) constituting the resin composition of the present invention measured in decalin at 135°C is 0.05 to lodl2/g, preferably 0.
It is in the range of 08 to 5 dl/g. The modified cyclic olefin addition polymer (a) constituting the resin composition of the present invention has a softening temperature (TMA) of 70°C or higher, preferably 90 to 250°C, more preferably 100°C or higher, as measured by a thermomechanical analyzer. ~20
0℃ range, glass transition temperature (Tg) is usually 50-23
0°C, preferably in the range of 70 to 210°C, crystallinity measured by X-ray diffraction method is 0 to 10%, preferably O to
7%, particularly preferably in the range of 0 to 5%. The modified cyclic olefin addition polymer (a) constituting the resin composition of the present invention is prepared by first preparing 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 is common to produce an ethylene/cyclic olefin addition polymer by polymerizing the above, and then graft copolymerizing an unsaturated carboxylic acid or its derivative. It can also be introduced by polymerization.

The method for producing the above-mentioned ethylene/cyclic olefin addition polymer is already known, and is disclosed in JP-A-60-1.68708,
JP-A-61-120816, JP-A-61-115
912, JP 61-1159, JP 61-271308, JP 61-272216
Publication cap, JP-A-62-252406, JP-A-62
It can be manufactured by appropriately selecting conditions according to a method such as that disclosed in Japanese Patent No. 252407.

In order to graft-copolymerize the unsaturated carboxylic acid or its derivative component to the ethylene/cyclic olefin addition polymer, for example, the ethylene/cyclic olefin addition polymer is melted using the unsaturated carboxylic acid or its derivative component as a graft monomer, A method of graft copolymerization by adding a graft monomer, or a method of dissolving an ethylene/cyclic olefin addition polymer in a solvent, and adding a graft monomer to perform graft copolymerization. It can be produced by adding dissolved graft monomers, mixing thoroughly, and graft copolymerizing. When such graft copolymerization is carried out, the reaction is usually carried out at a temperature of 60 to 350°C, and is preferably carried out in the presence of a radical initiator in order to efficiently graft copolymerize the graft monomer. Examples of radical initiators include organic peroxides, organic bersesters, and other azo compounds. As the component (B) of the present invention, instead of the modified cyclic olefin addition polymer (a), the general formula [I] and/or
Alternatively, a modified cyclic olefin ring-opening polymer (b) in which an unsaturated carboxylic acid or a derivative component thereof is introduced into the ring-opening polymer of the cyclic olefin component represented by (II) or its hydrogenated product may be used. Ring-opened polymers of cyclic olefin components are disclosed in, for example, JP-A-60
-26024, and hydrogenated products of ring-opened polymers can be easily prepared by applying known hydrogenation methods. As the unsaturated carboxylic acid or its derivative component which is a component of the modified cyclic olefin ring-opening polymer (b), the same ones as in the case of the modified cyclic olefin addition polymer (a) can be used. In the modified cyclic olefin ring-opening polymer (b) constituting the resin composition of the present invention, the unsaturated carboxylic acid or its derivative component contains 0.0% as a carboxyl group or its derivative group.
A range of 0.001 to 5% by weight, preferably 0.05 to 2% by weight is suitable.

The intrinsic viscosity [η] of the modified cyclic olefin ring-opening polymer (b) constituting the resin composition of the present invention measured in decalin at 135°C is 0.05 to 10 S/g, preferably 0.08
It is in the range of ~5 dl/g. The modified cyclic olefin ring-opening polymer (b) constituting the resin composition of the present invention has a softening temperature (TMA) of 70°C or higher, preferably 90 to 250°C, more preferably 90 to 250°C, as measured by a thermomechanical analyzer. 100-20
0℃ range, glass transition temperature (Tg) is usually 50-23
0°C, preferably in the range of 70 to 210°C, crystallinity measured by X-ray diffraction method is 0 to 10%, preferably 0 to 210°C.
7%, particularly preferably in the range of 0 to 5%.

In the ring-opening polymer before hydrogenation of the hydrogenated product of the ring-opening polymer of the cyclic olefin component, the general formula (1
) or (Il) mainly forms repeating units of the structure represented by the following general formula [■] or [■].General formula [wherein nm.Q and R1 to Hie is the same as above.] The method for producing the modified cyclic olefin ring-opening polymer (b) is to carry out ring-opening polymerization of the heptanomer selected from the general formulas [I] and (II) in advance, and to A common method is to graft-copolymerize a ring polymer as it is or after hydrogenation with an unsaturated carboxylic acid or a derivative component thereof.

The ring-opening polymer before hydrogenation is prepared by a conventional ring-opening polymerization method for cyclic olefins, using monomer components selected from the above general formulas [I] and [II) and other heptamer components to be polymerized as necessary. It can be manufactured by

Examples of other heptamer components include cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, dicyclopentadiene, ethylidene norbornene, 2,3, 3a, 7a
-Tetrahydride-4.7-methanol IH-indene.
Examples include cyclic olefins such as 3a,5,6,7a-tetrahydride-4,7-methanol-IH-indene. Examples of polymerization catalysts include systems consisting of halides such as ruthenium, rhodium, palladium, osmium, iridium, platinum, molybdenum, and tungsten, nitrates or acetylacetone compounds, and reducing agents such as alcohols and tin compounds, or titanium, vanadium, zirconium, A system consisting of a halogen compound such as tungsten or molybdenum, an acetylacetone compound, etc., and an organic aluminum compound, etc. can be used.

The hydrogenated ring-opened polymer of the cyclic olefin component can be obtained by hydrogenating the ring-opened polymer obtained above. Hydrogenation of ring-opened polymers is carried out using conventional hydrogenation methods. As the hydrogenation catalyst, those used in the hydrogenation of olefin compounds can generally be used. Specifically, heterogeneous catalysts include nickel, palladium, platinum, etc., or solid catalysts in which these metals are supported on supports such as carbon, silica, diatomaceous earth, alumina, titanium oxide, etc., such as nickel/silica, nickel, etc. /diatomaceous earth, palladium/carbon, palladium/silica, palladium/diatomaceous earth, palladium/alumina, etc. Homogeneous catalysts include those based on metals from group Ⅰ of the periodic table, such as nickel naphthenate/triethylaluminum, cobalt octenoate/n
- Ni such as butyllithium, nickel acetylacetonate/triethylaluminum, etc. Examples include compounds consisting of Go compounds and organometallic compounds of metals from Groups I to II of the periodic table, or Rh compounds. The hydrogenation reaction of the ring-opening polymer of the cyclic olefin component is 1
It is carried out under a hydrogen pressure of ~150 atm at a temperature range of 0~180°C, preferably 20~100°C. The hydrogenation rate can be adjusted by hydrogen pressure, reaction temperature, reaction time, catalyst concentration, etc., but the weather resistance of the resin composition of the present invention,
In order to improve heat aging resistance, it is preferable that 50% or more, preferably 80% or more, and more preferably 90% or more of the main chain double bonds in the polymer be hydrogenated. In the case of the modified cyclic olefin addition polymer (a), in order to graft copolymerize the unsaturated carboxylic acid or its derivative component to the ring-opened polymer of the cyclic olefin component obtained as described above or its hydrogenated product, It can be done in the same way.

In the polyamide resin composition of the present invention, the blending ratio of component (A) and component CB) is [A] component/[B] component by weight.
] Ingredients are 9872-2798, preferably 95/5-5
/95.

In addition to the components (A) and CB), the resin composition of the present invention may also contain unsaturated materials such as an ethylene-propylene random copolymer graft-copolymerized with maleic anhydride to the extent that the object of the present invention is not impaired. Resins containing carboxylic acids or derivatives thereof, heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, slip agents, anti-blocking agents, antifogging agents, lubricants,
Nucleating agents, dyes, pigments, natural oils, synthetic oils, waxes, rubber components for improving impact strength, and the like can be blended in appropriate amounts. For example, as a stabilizer that may be added as an optional component, specifically, tetrakis[methylene-3 (3.5-di-t-butyl-4-
hydroxyphenyl)brobionate] methane, β-(3,5-di-t-butyl-4-hydroxyphenyl)
Propionic acid alkyl esters, phenolic antioxidants such as 2,2'-oxamidobis[ethyl-3(3,5-di-t-butyl-4-hydroxyphenyl]probionate), zinc stearate, calcium stearate, 12-hydroxystearate Fatty acid metal salts such as calcium phosphate, polyhydric alcohol fatty acid esters such as glycerin monostearate 2 glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, etc. These may be blended alone or in combination, for example, tetrakis[methylene-3(3
, 5-di-t-butyl-4-hydroxyphenyl)propionate] A combination of methane, zinc stearate, and glycerin monostearate. Furthermore, the 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, Tanorek, clay, Myriki, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, Montmoly stomatite, bentonite, graphite, aluminum powder , molybdenum sulfide, boron fiber, silicon carbide fiber, polyethylene M!
Fillers and reinforcing materials such as fibers, polypropylene fibers, polyester fibers, and polyamide fibers may also be blended.

As a method for producing the polyamide resin composition according to the present invention, a known method can be applied, and components (A) and (B) and other components added as necessary are mechanically mixed using an extruder, seconder, etc. Examples include a method of blending, a method of dissolving each component in a suitable good solvent, a method of dissolving each component separately and then mixing and removing the solvent, and a method of combining these two methods. can.

The polyamide resin composition obtained as described above has a polyamide resin (A) and a component (B) which has better chemical resistance than polyamide resins, has a lower water absorption rate, is substantially ungradeable, and has a lower molding shrinkage rate. Because of the blending process, a polyamide resin composition can be obtained that maintains the various properties of polyamide resin, has excellent heat resistance and chemical resistance, and has low water absorption and molding shrinkage. Here, when polyamide resin (A) and a cyclic olefin polymer are blended, mechanical strength such as impact strength is low due to poor compatibility between the two, but modified cyclic olefin polymer is used instead of the cyclic olefin polymer. By blending the addition polymer or modified cyclic olefin ring-opening polymer [B), compatibility with the polyamide resin (A) can be improved, thereby increasing mechanical strength.

Due to the above characteristics, the polyamide resin composition of the present invention can be used not only for the purposes in which polyamide resins are used, but also for heat resistance,
It can be widely used in fields that require chemical resistance, low water absorption, and low mold shrinkage.

Examples of applications include injection molded products such as automobile interior parts (e.g. instrument panels, console boxes, column covers, etc.), automobile exterior parts (e.g. fenders, bonnets, trunks, etc.), office equipment, tools,
Examples include home appliance housings, etc., and as blow molded products.
Examples include bottles, sheets and films include cast films, biaxially stretched films, multilayer films, etc., and foams include extruded foams, injection foams, etc.

〔Effect of the invention〕

As described above, according to the present invention, component (A) and CB)
Because the ingredients are blended, it has excellent heat resistance and chemical resistance, and has low water absorption and molding shrinkage.
B) A polyamide resin composition with good compatibility of components and high mechanical strength such as impact strength can be obtained. [Examples] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples. In addition,
The methods for measuring and evaluating various physical property values in the present invention are shown below. (1) Melt flow index (MFRzsa< ) ASTM 0
123g, temperature 260℃, load 2. (2) Preparation of test piece Using an injection molding machine IS-35 manufactured by Toshiba Machine Corporation and a specified mold for test pieces, molding was performed under the following molding conditions.

After molding, the test piece was left at room temperature for 48 hours and then subjected to measurement.

Molding conditions: Cylinder temperature 250℃, mold temperature 60℃, injection pressure primary/secondary = 1000/800kg/aJ, injection speed (primary) 30m+a/see, screw rotation speed 15Orpm, cycle {(injection + holding pressure)/ cooling}=7
/15sec. (3) Bending test Conducted according to ASTM 0790.

Test piece shape: 5xl/2x1/8 inch, span distance 1
i51+am Test speed: 20 mm/win Test temperature = 23°C (4) Tensile test Conducted according to ASTN 063g.

Test piece shape: Type■ Test speed: 50+*m/win Test temperature: 23°C (5) Heat distortion temperature (HOT) Conducted according to ASTM 0648. Test piece shape: 5 x 1/4 x 1/2t inch Load: 264 psi (6) Softening temperature (TM^) DuPont WJ. Thermo Mechanical
The thermal deformation behavior of a 1+am thick sheet was measured using an analyzer. That is, a quartz needle was placed on a sheet, a load of 49 g was applied, and the temperature was raised at a rate of 5°C/win until the needle reached 0, . TM is the temperature that penetrates 635mm.
I gave it an A.

(7) Glass transition temperature (Tg) (D S c method) SE
A temperature increase rate of 10° C./IIin″c8l!l was determined using DSC-20 manufactured by IκO Electronics Co., Ltd. (8) Rockwell hardness Measured at 23° C. according to ASTM 0785.

(9) Pencil hardness Measured at 23°C according to JIS κ5400. (10)
Izod FLR bombardment test was conducted according to ASTM 0256.

Test piece shape: 5/2 x 1/8 x 1/2 inch (notched) Test temperature: 23°C (11) Compatibility Judgment was made based on the appearance of the injection molded bending test piece and the state of the fractured surface.

0: Both appearance and fracture surface were uniform.

Δ: The appearance was slightly uneven in flow, and the fracture surface was slightly non-uniform.

X: There was a skin layer, and the fractured surface was peeled off in layers Example 1 A maleic anhydride-modified resin, which is a modified cyclic olefin addition polymer (a), was prepared by the following method.

"Ethylene content measured by C-NMR is 62 mol%,
MFRzaoc is 35g/10min, intrinsic viscosity [η] measured in decalin at 135°C is 0.41dl/g
．． Ethylene with TMA of 148°C and Tg of 137°C, and 1
,4,5.8-dimethano-1.2,3,4,4a,
5 kg of pellets of random copolymer (ethylene/DMON random copolymer) with 5, 8, 8a-octahyde-natalene (abbreviated as DMON below the structural formula ω),
5 g of maleic anhydride dissolved in 25 g of acetone, organic peroxide (manufactured by NOF Corporation, Perhexine 25B,
After adding 0.3 g of the mixture (Trademark) and mixing thoroughly, a reaction was carried out under melting using a twin-screw extruder (manufactured by Ikegai Tekko Co., Ltd., PCM 45) at a cylinder temperature of 250°C, and the mixture was pelletized using a pelletizer. The maleic anhydride content of the resulting maleic anhydride-modified resin was 0.07% by weight (0.05% as acid anhydride group content). Next, as component (A), polyamide resin (6 nylon CM1017 manufactured by Toray Industries, Inc.) was used.
．． After thoroughly mixing 2.0 kg of pellets of CB) and 2.0 kg of maleic anhydride-modified resin Veresoto prepared by the above method as the CB component, they were mixed using a twin-screw extruder (same as above) at a cylinder temperature of 250°C. The mixture was melt-blended and pelletized using a pelletizer. Using the obtained pellets, test pieces were prepared using the method described above, and their physical properties were evaluated. The results are shown in Table 5. Examples 2 and 3 The same operations as in Example 1 were performed except that the amounts of component (A) and component CB) were changed. The results are shown in Table 5. Examples 4 to 6 In place of the polyamide resin used as component (A) in Examples 1 to 3, 6,6-nylon 3001N (manufactured by Toray Industries, Inc., trademark) was used to control the extruder and injection molding machine. Example 1 except that the cylinder temperature was 290°C.
The same operations as in steps 3 to 3 were performed. The results are shown in Table 5.

Comparative Examples 1 and 2 6 Nylon CM used as component (A) in Examples 1 to 6
1017 (Comparative Example 1), or 6,6 nines 300
Molding was performed in the same manner as in Example 1 using only 1N (Comparative Example 2), and the physical properties were evaluated. The results are shown in Table 5. Comparative Example 3 The same operation as in Example 1 was carried out except that an ethylene/DMON random copolymer before modification with maleic anhydride was used as the U component. The results are shown in Table 5. Example 7 Instead of the maleic anhydride modified resin used in Example 1, ethylene/DMON random copolymer (ethylene content =
62 mol%. MFRzsa<: 35g/Lol
llin. Intrinsic viscosity measured in decalin at 135°C [η
): 0.47dJl/g. TMA: 148℃
, Tg: 137°C) and 80 parts by weight of ethylene/brobylene random copolymer (ethylene content = 80 mol%,
Tg: -54℃, MFR2sl1: 0.7g/1
Intrinsic viscosity measured in decalin at 0+min, 135°C [
η]: 2.2 dl/g) was melt-blended using a twin-screw extruder (manufactured by Ikegai Tekko Co., Ltd., PCM 45), and the resin was modified with maleic anhydride (maleic anhydride) in the same manner as in Example]. The same operation as in Example 1 was performed except that the acid content of 0.08% by weight (acid anhydride group content: Q. (16% by weight)) was used in place of component (81) in Example 1. The results are shown in Table 5. From the above results, the polyamide resin composition of the present invention containing the components (A) and (B) has a lower heat distortion temperature than the conventional polyamide resin which is the component (A). It can be seen that the water absorption rate is high and the water absorption rate is low.Compared to polyamide resin compositions using cyclic olefin copolymers that do not contain unsaturated carboxylic acids as component CB), they have better compatibility and higher Izod impact strength. You can see that it is.

Claims (1)

[Claims] (1) [A] Polyamide resin and [B] Intrinsic viscosity [η] measured in decalin at 135°C
is 0.05 to 10 dl/g (a) An addition polymer consisting of an ethylene component and a cyclic olefin component represented by the following general formula [I] and/or [II] is added with an unsaturated carboxylic acid or its derivative component. An unsaturated carboxylic acid or its and a modified cyclic olefin ring-opening polymer into which a derivative component has been introduced, and the weight ratio of [A] component/[B] component is 98/
A polyamide resin composition characterized in that it has a polyamide resin composition of 2 to 2/98. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... [II] [In the formula, n and m are both 0 or positive integers. Yes, l is an integer greater than or equal to 3, and R^1 to R^1^0
each represents a hydrogen atom, a halogen atom, or a hydrocarbon group. ]