JPH03203958A - Polyamide resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having excellent heat resistance, scratch resistance and chemical resistance and small water absorption and molding shrinkage and suitable for housings such as electrical tool or office automation equipment by compounding a polyamide resin with a modified cyclic olefin resin at a specific ratio. CONSTITUTION:The objective composition obtained by blending (A) a polyamide resin having 0.05-100g/10min melt flow rate (2.16kg load at 230 deg.C), 0.1-10dl/g intrinsic viscosity and 100-400 deg.C melting point with (B) an unsaturated carboxylic acid modified cyclic olefin based random copolymer obtained by modifying a copolymer of ethylene and cyclic olefin expressed by the structural formula selected from formula I to formula IV (I is 0 or integer; R<1> to R<18> are H, halogen or hydrocarbon; m is 0 or integer; n is 0 or integer; p is 0 or integer; q and r are 0, 1, 2) with an unsaturated carboxylic acid (derivative) and being 0.001-5wt.% in an unit derived from the unsaturated carboxylic acid (derivative) and having 0.05-10dl/g intrinsic viscosity at weight ratio of component A/ component B of 98/2-2/98.

Description

[Detailed description of the invention] i Mamedate Gogomon M Invention A A polyamide resin, an unsaturated carboxylic acid-modified cyclic olefin-based random copolymer resin (hereinafter sometimes abbreviated as modified cyclic olefin resin), More specifically, the present invention relates to a polyamide resin composition that has excellent heat resistance, scratch resistance, low water absorption and molding shrinkage, and high mechanical strength.

Many of today's popular polyamide resins are crystalline and have relatively high melting points, so by blending fillers with such polyamide resins, it is possible to create polyamide resin compositions with high heat distortion temperatures and excellent heat resistance. Obtainable. However, when a filler is added, the moldability of the resin deteriorates and anisotropy occurs in the physical properties of the molded product.

On the other hand, polyamide resins that do not contain fillers have a large mold shrinkage rate, lack dimensional accuracy, and are inferior in heat resistance. Furthermore, since polyamide resin has poor acid resistance and alkali resistance and high water absorption, there is a problem that if drying is insufficient, it will be hydrolyzed during molding and its physical properties will deteriorate.

By the way, it is known that cyclic olefins having an ethylenic double bond in the ring have polymerizability, and can react with α-olefins such as ethylene to yield cyclic olefin/a-olefin random copolymers. (JP 60-168708, JP 63-243
No. 111 revolution, JP-A-63-305111, JP-A-63-223,013, JP-A-1-185307).

Further research by the present inventors revealed that such cyclic olefin resins have the transparency, water resistance, and thermal properties necessary for optical materials. By introducing a structural unit derived from an acid or its derivative and blending the resulting unsaturated carboxylic acid-modified cyclic olefin resin (modified cyclic olefin resin) with a polyamide resin, even more excellent products that can be used for various purposes can be created. The present invention has the knowledge that it is possible to obtain a polyamide resin composition having the following characteristics.The present invention has been developed to improve heat resistance, scratch resistance, and water absorption while maintaining the excellent characteristics of polyamide resin. The purpose of this invention is to provide a polyamide resin composition with low molding shrinkage and high mechanical strength.

The polyamide resin composition according to the present invention is a copolymer of polyamide resin [A], ethylene, and a cyclic olefin represented by a structural formula selected from the following formulas [l] to [■]. An unsaturated carboxylic acid-modified cyclic olefin random copolymer modified with an unsaturated carboxylic acid or its carboxylic acid derivative Consisting of a polymer resin [B] (modified cyclic olefin resin [B]), the composition ratio of the polyamide resin [A] and the unsaturated carboxylic acid-modified cyclic olefin random copolymer resin [B] [A]/ [B] (weight ratio) 9872~2
/98.

RIS to R1e may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond, or RIS and R11+, or R1? and R11
1 may form an alkylidene group).

... [Eng.] (In the formula [Eng.], l is O or a positive integer, and R1
-R11l may be the same or different, and each is an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, (in formula [n], m is 0 or a positive An integer, R1~
RI a 11 Each may be the same or different, and is an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, even if R9 and R1@ form an alkylidene group. good).

...[ml (in the formula [ml, n is 0 or a positive integer, and R1 to
RI 244 Each may be the same or different, and is an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and the R and RI2 may form an alkylidene group. ).

...[yvl (in formula [■], p is 0 or an integer of 1 or more, q and r13 are 0.1 or 2, R1-R11s
each independently represents an atom or group from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an alkoxy group, and represents R6 (or R11) and R・(or R?). Number of carbon atoms: 1 -3 may be bonded via an alkylene group, or may be bonded directly without any group. ) Polyamide resin composition storage according to the present invention Since it contains a polyamide resin [A] and a specific unsaturated carboxylic acid-modified cyclic olefin random copolymer resin [B] (modified cyclic olefin resin [B]), it has high heat resistance, It has excellent scratch resistance, low water absorption and molding shrinkage, and high mechanical strength.

Moreover, by blending such modified cyclic olefin resin [B], the excellent properties of 1 polyamide resin [A] are not impaired.

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

Polyamide resin composition 14 according to the present invention Polyamide resin [A] and cyclic olefin random which is a copolymer of ethylene and a cyclic olefin represented by a structural formula selected from the above formulas [■] to [■] Copolymer (unmodified cyclic olefin copolymer) Unsaturated carboxylic acid-modified cyclic olefin random copolymer resin partially or completely modified with an unsaturated carboxylic acid or its carboxylic acid derivative [B]
(Modified cyclic olefin resin [B]).

Polyamide resin [A] constituting the polyamide resin composition of the present invention i & the following general formula [il or general formula [i
It is a polyamide resin having a repeating unit represented by il.

... [il ... [iil [wherein S and t are positive integers, R1・, R2・
R21 each represents an aliphatic, alicyclic or aromatic hydrocarbon or a derivative thereof. ] Examples of such polyamide resins [A] include ring-opening polymers of lactams that are cyclic amides (for example, nylon 6 produced from C-cabralactam), polycondensates of aminocarboxylic acids (for example, ω- Nylon 1 made from aminoundecanoic acid
1. Nylon 12 manufactured from ω-aminododecanoic acid
), polycondensates of dicarboxylic acids and diamines (for example, nylon 6, produced from adipic acid and hexamethylene diamine, a, nylon 6.1, produced from sebacic acid and hexamethylene diamine, and dodecane doublet). Nylon 6, 12) manufactured from xamethylene diamine
etc. can be mentioned. These polyamide resins can be used alone or in combination of two or more.

The melt flow rate of the above polyamide resin [A] at 230°C and a load of 2.16 kg is 0.05 to 100 g/10
mm Preferably 0.1 to 50 g/10 m1n.

Further, the intrinsic viscosity [l] of the polyamide resin [A] measured in concentrated sulfuric acid at 30°C is in the range of 0.1 to 10 dl/&, preferably 0.5 to 5 dl/g.

Further, the melting point (Tm) of the polyamide resin [A] is 100
It is desirable that the temperature is in the range of ~400°C, preferably 150~350°C.

Next, the unsaturated carboxylic acid-modified cyclic olefin random copolymer resin [
B] (modified cyclic olefin resin [B]) will be explained.

Unsaturated carboxylic acid-modified cyclic olefin random copolymer resin [B] constituting the polyamide resin composition of the present invention
(Modified cyclic olefin resin [B]) A structural unit derived from an IL ethylene component (ω, a structural unit (b) derived from a specific cyclic olefin, and a structural unit derived from an unsaturated carboxylic acid or its carboxylic acid derivative (c) ) is a copolymer formed from

The above cyclic olefin has at least the above formulas [I] to [■]
It is a cyclic olefin represented by one of the structural formulas selected from.

In the above formula [I], l is 0 or a positive integer, preferably 0 to 3. In the above formula [nl, m is 0 or a positive integer, preferably 0 to 3. In the above formula [ml, n is 0 or a positive integer, preferably 0 to 3. Also, p of the above formula [■]
is an integer of 0 or 1 or more, preferably an integer of 0 to 3.

And R1 to R18 (formula [■]), R1 to R1・
(formula [■]), R1=RI2 (formula [ml)] or R14
R16 (Formula [■l)ldai] They may be the same or different, and are atoms or groups selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups. Here, we also compare 6 as a halogen atom: a fluorine atom,
Mention may be made of chlorine, bromine and iodine atoms. In addition, as a hydrocarbon group, L each independently &-
Usually an alkyl group having 1 to 10 carbon atoms 5 carbon atoms
~15 cycloalkyl groups can be mentioned, and specific examples of alkyl groups include 11 methyl group ethyl group
Isopropyl group, isobutyl An-amyl group, neopentyl & n-hexyl 1IiP, n-octyl in-decyl & 2-ethylhexyl group, etc. Specific examples of cycloalkyl group include melon cyclohexyl group, methylcyclohexyl group, ethylcyclohexyl group, etc. can be mentioned.

In addition, in the above formula [tl, R11a and R16,
Alternatively, RIT and R11B may form an alkylidene group, and in the above formula [■], R9 and R11 may form an alkylidene group; in the above formula [ml, R11 and RI 2 may form an alkylidene group; It may form a group. Such alkylidene groups usually include alkylidene groups having 3 to 10 carbon atoms, and specific examples thereof include ethylidene groups, propylidene groups, isopropylidene groups, butylidene groups, isobutylidene groups, etc. . The above formula [■]
In the above, R6 (or R6) and R. (or R7) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group.

Furthermore, in the above formula [1], RI@ to R1@ may be bonded to each other (jointly) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring has a double bond. may have.

Cyclic olefin +L represented by the above formulas [r] to [rvl
It can be easily produced by condensing cyclopentadiene and the corresponding olefin or cyclic olefin by Diels-Alder reaction.

, 12 S, ill@]-3 Dodese The cyclic olefins represented by the above formulas [I] to [■] are as follows: , (Left below) n-Propylidene-9 8-isopropylidene [4,4,0,12・S, 17-1]-3-dodecene-dodecene 1.]-]3-dodecene 1.]-]3-dodecene-n-propylidene -9 [4,4,0,12・S, 17 111]-3 - Tetracyclo [4,4,0,12・s, 1)・l such as 1-dodecene-dodecene
]-3-dodecene derivatives; diene compounds such as 116 ]-4-eicosene, hebutacyclo[7,3,Q, 13.6. Q2. ? , 11@, +7. Q
+6,112 15] -4-eicosene derivatives; 21.113.2@, Ql4 I*lI+ 11·] -5-bentacyclo[4,7,0,12·S, Ql·+a, 1 *12] -3-pentadecene derivative.

21, Ql4 +I, IIs +1] -5-bentacocene and other nonacyclo[9,10,1,l', ? , α11. Q2. II, QI
2.21,113 2s, 0+4 1.111116] -5-bentacocene-derived cocene derivatives, and the like.

Furthermore, gamma to 5-phenyl-bicyclo[2,2,1] can be mentioned.

The weight ratio of the structural units derived from unsaturated carboxylic acids or their carboxylic acid derivatives in the unsaturated carboxylic acid-modified cyclic olefin random copolymer resin [B] forming the resin composition of the present invention is usually 69. It ranges from 0.001 to 5% by weight, preferably from 0.01 to 3% by weight.

The modified cyclic olefin resin used in the present invention [the entire 81st group may be graft-modified with an unsaturated carboxylic acid or the like, or it may be a modified cyclic olefin resin in which only a portion is modified.

Note that the resin that is only partially modified includes a resin prepared by mixing a modified resin and an unmodified resin.

The structural unit (C
) such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, undecylenic acid, maleic anhydride, tetrahydrophthalic acid, isocrotonic acid, nadic acid (endocys-bicyclo[2,2, 1] hepto-5-ene-2,3-dicarboxylic acid), citraconic anhydride, nadic anhydride, and other unsaturated carboxylic acids, or derivatives of these acid anhydrides. The structural units (C) derived from these unsaturated carboxylic acids or derivatives thereof can be used alone or in combination.

In the unsaturated carboxylic acid-modified cyclic olefin random copolymer resin [B] constituting the resin composition according to the present invention, the composition of the structural units excluding the unsaturated carboxylic acid +L
Structural unit derived from ethylene (a) Ka\ 40-8
It is desirable that the content is 5 mol%, preferably in the range of 50 to 75 mol%. The structural unit (b) derived from a cyclic olefin is 15 to 60 mol%, preferably 25 to 60 mol%.
It is desirable that the content is in the range of 50 mol%.

The intrinsic viscosity [wa] of the modified cyclic olefin resin [B] constituting the resin composition according to the present invention measured in decalin at 135°C is usually 0.05 to 10 (il/g, preferably O,OS to 5 It is in the range of dl/g.

Furthermore, the modified cyclic olefin resin [B] constituting the resin composition according to the present invention has a softening temperature (TMA) of usually 70°C as measured with a thermomechanical analyzer.
Preferably 90 to 250°C, more preferably 1
It is desirable that the temperature is in the range of 00 to 200°C.

Furthermore, the glass transition temperature (Tg) of the modified cyclic olefin resin CB constituting the resin composition according to the present invention is usually 50 to
It is desirable that the temperature is 230°C, preferably in the range of 70 to 210°C.

Further, the degree of crystallinity determined by X-ray diffraction analysis of the modified cyclic olefin resin [B] constituting the resin composition according to the present invention is usually 0 to 10%, preferably 0 to 7%, particularly preferably 0 to 7%. It is desirable that it be at 5%.

Modified cyclic olefin resin [B] 1L A structural unit derived from ethylene (ω, the structural unit (b) derived from the cyclic olefin and the structural unit (c) derived from an unsaturated carboxylic acid or its derivative are essential structural units. In addition to these essential structural units, the resin may contain other copolymerizable structural units derived from unsaturated monomers, as necessary, as long as the object of the present invention is not impaired.

If necessary, it may be added as an optionally copolymerized unsaturated monomer. Specifically, propylene, 1-butene,
a- with 3 to 20 carbon atoms such as 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. Examples include olefins.

The constituent unit 11 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, in the present invention, the above unsaturated carboxylic acid-modified cyclic olefin random copolymer CB] may be used within the range of not impairing the physical properties of the obtained polymer, etc.
] to [■] It is also possible to contain cyclic olefin units other than the cyclic olefins represented by [■]. 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-I
In addition to H-indene, 3a, 5.6.7a-tetrahydro-4,7-methano-IH-indene, etc.; ] Conductor; hept-2-ene derivative 5.10-dimethyltetraCH.

CHs 2.1 dimethyltetra2,7.9-trimethylte5,8.9.1tetramethy8-methyltetrasif8-ethyltetrasif1.]-]3-dodecene-hexyltetracy9-isobutyl-2 ,7-9,11,12-trimethyl9-ethyl-11,12-dime9-isobutyl-11,12-dodecene,111-3-dodecene8-methyl-9-ethylte8-chlorotetracyph-3-dodecene 8-promotitrasif 8-fluorotetracy 1·]-3-dodecene, 1@]-3-dodecene, +4]-4-heptadecene S,p,l@]-3-dodecenedecene7,1·]-]3- Tetracyclo [4,4,0,1"5.17・l] such as dodecene-3-dodecene
-3-dodecene derivative; heptadecene (the following margin) 15-ethyl octashif+S, Q2. ? , Q11.14]-4-hep2·I? ]
Octacyclo[8,8,0,12...,14...] such as -5-tococentadecene
Hexacyclo[6,6,
1,1”・e, l+s, +3.Q2・7.Is, Is,
03. s, 012. I? 1-5-tococene derivative; ・I
4]-4-hebutadecene derivative; 1, l @
. ,6,1,1”@ , 02.
-4-hexadecene derivatives; tricyclo[4,3,0,12.6]-3-decene derivatives such as 5-methyl-tricyclo; hebutacyclo-5-icosene derivatives such as cosene or he1
．． Pentacyclo[6,5,1,IS, I
, 02.7ge,! *]-4-form; Examples include pentadecene derivatives.

(Left below) 1.3-dimethyl-benta Other cyclic olefins such as these can be used alone or in combination, and are usually 0 to 20 mol%
used in amounts of

The modified cyclic olefin resin [B] constituting the polyamide resin composition according to the present invention is obtained by graft polymerizing the above-mentioned unsaturated carboxylic acid or its carboxylic acid derivative onto a hexa-unmodified cyclic olefin copolymer by a known method. In addition to graft copolymers, random copolymers of ethylene, a cyclic olefin represented by one of the structural formulas selected from formulas [11 to [■]], and unsaturated carboxylic acids or their carboxylic acid derivatives are also available. Polymers and the like can also be used.

Modified cyclic olefin resin [B] Force ζ In case it is a graft copolymer obtained by graft polymerizing the above unsaturated carboxylic acid or its derivative to an unmodified cyclic olefin copolymer JP-A-62-2/412 It can be manufactured according to the method disclosed in the publication. Specifically, if you want to talk about it.

A method of dissolving an unmodified cyclic olefin copolymer using an unsaturated carboxylic acid or a derivative thereof as a graft monomer, and graft copolymerizing with the graft monomer.A method of dissolving an unmodified cyclic olefin copolymer in a solvent and adding a graft monomer. A method of graft copolymerization of the unmodified cyclic olefin copolymer, a method of adding a graft monomer dissolved in a solvent to the unmodified cyclic olefin copolymer, mixing thoroughly, and graft copolymerization of the unmodified cyclic olefin copolymer and the graft monomer, etc. can be manufactured.

Such a graft copolymerization method is usually carried out at a temperature of 60 to 350°C, preferably 80 to 300°C. In order to efficiently graft copolymerize the graft monomer, it is preferable to carry out the reaction in the presence of a radical initiator. .

Examples of radical initiators include organic peroxides, organic bersesters, and other azo compounds, particularly dicumyl peroxide, di-tert-butyl peroxide, and 2.
5-dimethyl-2,5-di(tert-butylperoxy)hexyne-a2.5-dimethyl-2,5-di(te
rt-butylperoxy)hexas 1,4-bis(t
Dialkyl oxides such as ert-butylperoxyisopropylbenzene are preferred.

In the polyamide resin composition of the present invention, the composition ratio IL of the polyamide resin component [A] and the unsaturated carboxylic acid-modified cyclic olefin random copolymer resin [B] (modified cyclic olefin resin [B]) [A] component / [B] acid component weight ratio) 9872 to 2/98, preferably 9515
~5/95.

Let the polyamide resin composition of the present invention, the above [A
] and [B] In addition to acid components, compounded with rubber components to improve impact strength, heat-resistant, stable, weather-resistant, anti-static, slip, anti-blocking, anti-fog, dyes, pigments, natural sources, synthetic liquids. Wax etc. can be blended, and the blending ratio is appropriate. Parable I
f. Specific examples of stabilizers that may be added as optional ingredients include tetrakis[methylene-3(3,5-di-7-butyl-4-hydroxyphenyl)propionate comethane, β-(3,5-di-t- Butyl-4-hydroxyphenyl)propionic acid alkyl ester, 2.2°-
Phenolic antioxidants such as oxamide bis[ethyl-3(3,5-di-7-butyl-4-hydroxyphenyl) copropionate; fatty acid metal salts such as zinc stearate, calcium stearate, and calcium 12-hydroxystearate; glycerin monostearate;
Examples include fatty acid esters of polyhydric alcohols such as glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. These may be blended alone or in combination, such as tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate comethane and zinc stearate and Examples include combinations with glycerin monostearate.

In the present invention, it is preferable to use a combination of a phenolic antioxidant and a fatty acid ester of a polyhydric alcohol.
It is preferable to use a polyhydric alcohol fatty acid ester in which a part of the alcoholic hydroxyl groups of a polyhydric alcohol having a higher valence or higher are esterified.

Such fatty acid esters of polyhydric alcohols include:
Specifically, glycerin fatty acid esters such as glycerin monostearate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate, and glycerin dilaurate;
Fatty acid esters of pentaerythritol such as pentaerythritol monostearate, pentaerythritol monolaurate, pentaerythritol dilaurate, pentaerythritol distearate, and pentaerythritol tristearate are used.

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

The polyamide resin composition of the present invention may also include 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 woven edge glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder,
Molybdes sulfide Boron fiber paper Silicon carbide wire edged polyethylene fiber paper Polypropylene fiber paper Polyester woven edge Filler such as polyamide fiber may be blended.

A known method can be applied as a method for producing the polyamide resin composition according to the present invention, and the polyamide resin component [A] and the unsaturated carboxylic acid-modified cyclic olefin random copolymer resin [B] (modified cyclic olefin resin), A method of mechanically blending other components added as desired using an extruder, kneader, etc., or a method of blending each component with a suitable melting arc, for example, a hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene, xylene, etc. Examples include a method in which the components are dissolved simultaneously or separately and then mixed and the solvent is removed, and a method in which these two methods are combined.

The polyamide resin composition obtained by the above manufacturing method includes polyamide resin component [A] polyamide resin component [A]
By blending modified cyclic olefin resin [B] with higher heat distortion temperature, higher pencil hardness, and lower molding shrinkage, it maintains the properties of polyamide resin while maintaining excellent heat resistance, scratch resistance, and molding shrinkage. Even when a small polyamide resin composition is obtained, anisotropy does not occur in the molded article even when a filler or the like is mixed therein.

6. Polyamide Resin Composition According to the Invention Since it has the above-mentioned characteristics, it can be widely used in fields where heat resistance, scratch resistance, dimensional stability, etc. are required, in addition to the conventional uses of polyamide.

Examples of applications include electrician J%, OA machine, camera,
Housing skin for pumps, etc. Chassis body Precision equipment department &
Instrument panels, radiator grills, cluster grills, console boxes, garnishes, foil covers, column covers, fender bonnets, automobile interior and exterior materials such as trunks, seats, cases for connectors, coil bobbins, switches, etc. Foams include films such as films, biaxially stretched films, and multilayer films; extruded foams; and injection foams.

As described above, according to the present invention, since the modified cyclic olefin resin [B] is blended into the polyamide resin component [A], the compatibility between the acid component [A] and the acid component [B] is good. Moreover, it is possible to obtain a polyamide resin composition that has excellent heat resistance, scratch resistance, and chemical resistance, and has low water absorption and mold shrinkage.

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

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

(1) Melt flow index (MFRa) According to ASTM D1238, specified temperature T°C, load 2.
9 (2) Preparation of test piece The test piece was molded under the following molding conditions using an injection molding machine Il5-50EP manufactured by Toshiba Machine ■ and the specified test piece mold. After molding, the test piece was molded at room temperature for 48 hours. Molding conditions measured after being left standing: Cylinder temperature 220t, mold temperature 60℃,
Injection pressure car secondary/secondary = 1000/800kg/cm2
Injection speed (-next) 30mm/see, screw rotation speed 150r (3) Bending test Test conducted according to ASTM D790 Test piece shape: 5x 1/2x 1/8t inch, distance between spans 1mm Test speed: 20mm/min Test temperature: 23°C (4) Tensile test Test piece shape conducted according to ASTM D638: ASTM-TYPE! V thickness 2m
m Test speed: 50mm/min Test temperature: 23°C (5) Heat distortion temperature (HDT) Test piece shape conducted according to ASTM D628: 5X 1/4X 1/2t inch load
Weight: 264psi (6) Softening temperature (TMA) 'l'hermo Mechanical manufactured by DuPont
The thermal deformation behavior of a 1 mm thick sheet was measured using an analyzer. That is, a quartz needle was placed on the sheet, a load of 49 g was applied, and the temperature was increased at a rate of 5°C/min, until the needle became 0.635 mm. (7) Glass transition temperature (Tg), melting point (Tm) SEI with the temperature at which it entered as TMA
(8) Rockwell hardness Measured at 23°C in accordance with ASTM D785 (9) Pencil hardness 23 in accordance with JIS K 5400 Measured at °C (10
) Izot impact test was conducted according to ASTM D256.

Test piece shape: 5/2x 1/8x 1/2t inch (
(with notch) Test temperature = 23°C (11) Compatibility Judgment was made based on the appearance and condition of the fractured surface of the injection-molded bending test piece ○: Both the appearance and fractured surface were uniform Δ: There was some fluidity unevenness in the appearance, The fracture surface was slightly uneven ×: There was a skin layer, and the fracture surface was peeled off in layers, resulting in islands.
The maleic anhydride-modified resin, which is the unsaturated carboxylic acid-modified cyclic olefin resin [B], was prepared by the following method and had an ethylene content of 63 mo as measured by 13 cm NMR.
L% MFR2g m'c is 32g/10m1r1
The intrinsic viscosity [V] measured in decalin at 135°C is 0.
48dl TMA is 150℃, Tg is 140℃ (Tm
(not observed) and 1,4,5,8-dimethano-1,2,3,4,4a, 4b, 5.8.8a,
9a-octahydrofluorene (hereinafter abbreviated as DMDF)
Maleic anhydride organic peroxide (manufactured by NOF Corporation) dissolved in 25 g of acetone was added to 5 kg of pellets of random copolymer (ethylene/DMDF random copolymer) with
After adding 0.3 g of Verhexin 2 Nagi (Trademark) and thoroughly mixing, a twin-screw extruder (manufactured by Ikegai Iron Works, PCM 45) was used to carry out a melting reaction at a cylinder temperature of 250°C, and the resulting anhydrous product was pelletized using a pelletizer. The maleic anhydride content of the maleic acid-modified resin was 0.07% by weight (0.05% by weight as acid anhydride group content). Next, [A] acid component was added to polyamide resin (manufactured by Toshi ■, 6).
f iD :/ CM101'IS Trademark) (F
) / (1/7) 2. After thoroughly mixing 2.0 kg of pellets of the above maleic anhydride-modified resin as the OIH [B] acid component, a twin-screw extruder (manufactured by Ikegai Iron Works ■, PCM 4
5) by melt blending at a cylinder temperature of 250°C,
Test pieces were prepared by the method described above using the pellets obtained by pelletizing with a pelletizer, and the physical properties were evaluated. The results are shown in Table 1.

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

Back layer 11: Instead of the polyamide resin used as the [A] acid component in Example 1, 6.6-nylon 3001N (manufactured by Toshi ■, trademark) was used to form cylinders of extruder and injection molding machines. Table 1 shows the results of the same operations as in Examples 1 to 3 except that the temperature was 290°C.

6 Nylon CM used as the [A] acid component in Examples 1 to 6
1017 (Comparative Example 1), 6.6-nylon 3001N
(Comparative Example 2) was molded in the same manner as in Example 1,
Table 1 shows the results of evaluating the physical properties.

In Example 1, the same operation as in Example 1 was performed except that [B] an ethylene/DMDF random copolymer before modification with maleic anhydride was used as the acid component. The results are shown in Table 1. show.

Kanshobi 1 Instead of the maleic anhydride modified resin used in Example 1, ethylene/DMDF random copolymer (ethylene content:
63molX MFRtes”c: 32g/10m
Intrinsic viscosity [η] measured in decalin at 1rx135°C:
0.48dl/i TMA is 150℃, Tg is 140
°C (Tm not observed)) 80 parts by weight of ethylene/propylene random copolymer (ethylene content: 80 mo
1%, MFR2m s・c: 0.7g/10mm
Intrinsic viscosity [η] measured in decalin at 135°C: 2
．． A resin obtained by melt-blending 20 parts by weight of 2dl% (-54°C) using a twin-screw extruder (manufactured by Ikegai Iron Works, PCM 45) was modified with maleic anhydride in the same manner as in Example 1 (containing maleic anhydride). The results of the same operation as in Example 1 are shown, except that O, OS weight% (0.06 weight% as acid anhydride group content) was used instead of the [B] acid component in Example 1. Shown in 1.

Here, an example will be shown in which a mixture of a modified cyclic olefin copolymer and an unmodified cyclic olefin copolymer is used, and the three components are simultaneously melt-blended in the presence of a polyamide resin.

The maleic anhydride-modified resin, which is an unsaturated carboxylic acid-modified cyclic olefin random copolymer, has an ethylene content of 63 moK as measured by 13C-NMR prepared by the following method.
MFR2s s'c is 32g/10mln, intrinsic viscosity [v] measured in decalin at 135°C is 0.48dl/g
, 7MA25f 150t:', Tg is 140℃ (
5 kg of random copolymer pellets of ethylene and DMDF (Tm not observed)! After adding 3 g of maleic anhydride organic peroxide (manufactured by Nippon Oil & Fats Corporation, Perhexin 2 Nagi trademark) dissolved in 25 g of acetone and thoroughly mixing, a twin screw extruder (manufactured by Ikegai Iron Works, PCM 45) was added. The reaction was carried out under melting at a cylinder temperature of 250°C, and the resulting maleic anhydride-modified resin was made into pellets using a pelletizer.The maleic anhydride content of the resulting maleic anhydride-modified resin was 0.8% by weight. (Toshi III 6 Nylon CM1017. Trademark) Beret 2.0 Seed [
B] Acid component +s Ethylene content measured by C-NMR is 63 molX, MFRtss"c is 32 g/
10mln, 135°C Intrinsic viscosity [1] measured in decalin is 0.48dl/11TMA at 150°C, Tg
unmodified ethylene and DMON (1,4,
5,8-dimethano-1,2,3,4,4a, 5.8.
After thoroughly mixing 1.6 kg of random copolymer with 8a-octahydronaphthalene) and 0.4 kg of the above random copolymer of maleic anhydride-modified ethylene with DMDF, The cylinder temperature was 280℃ using an extruder (Ikegai Tekko PCM 45).
The mixture was melted at ℃ and pelletized using a pelletizer.

A test piece was prepared using the obtained pellet by the method described above, and the physical properties were evaluated. Table 1 shows the results.

Sm Kameji”.

Instead of the ethylene/DMDF copolymer used in Example 1,
A maleic anhydride-modified cyclic olefin copolymer was prepared in the same manner as in Example 1 using a copolymer of ethylene and another cyclic olefin, and this was used as the [B] acid component.
Table 2 shows the physical property values of the [B] acid component obtained. [B] Table 1 shows the results of the same operation as in Example 1 except for using the acid component.

It can be seen that the impact strength has increased.

From the above results, the polyamide resin composition of the present invention containing [A] acid component [B] acid component has a higher heat distortion temperature and a lower water absorption rate than the conventional polyamide resin containing [A] acid component. You can see that it's small.

In addition, compared to a polyamide resin composition using a cyclic olefin copolymer that does not contain an unsaturated carboxylic acid as the acid component [B], it has better compatibility, Display of the case 1999 Patent Application No. 340,902 Patent application filed on December 29, 1999 (2) 2, Name of the invention Polyamide resin composition 3, Name of the person making the amendment Related to the case

Claims (3)

[Claims] (1) A polyamide resin [A] and a cyclic olefin-based random copolymer, which is a copolymer of ethylene and a cyclic olefin represented by a structural formula selected from the following formulas [I] to [IV], are Unsaturated carboxylic acid-modified cyclic olefin random copolymer resin modified with saturated carboxylic acid or its carboxylic acid derivative [B
], the polyamide resin [A] and the unsaturated carboxylic acid-modified cyclic olefin random copolymer resin [
The composition ratio with [A]/[B] (weight ratio) is 98/
A polyamide resin composition characterized in that it has a polyamide resin composition of 2 to 2/98. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ... [I] (In the formula [I], 1 is 0 or a positive integer, and R^
1 to R^1^8 may be the same or different, and each is an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R^1^5 to R^ 1^8 may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and R^1^5 and R With ^1^6 or R^1^7
and R^1^8 may form an alkylidene group). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ... [II] (In formula [II], m is 0 or a positive integer, and R^1
~R^1^8 may be the same or different, and are atoms or groups selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups, and R^9 and R^1^8 may form an alkylidene group). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ... [III] (In formula [III], n is 0 or a positive integer, and R^
1 to R^1^2 may be the same or different, and are atoms or groups selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups, and R^1^1^ and R may form an alkylidene group with ^1^2). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ... [IV] (In formula [IV], p is 0 or an integer of 1 or more, q and r are 0, 1 or 2, and R^1 ~R^1^5
each independently represents an atom or group from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an alkoxy group, and R^5 (or R^6
) and R^9 (or R^7) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group. ) (2) The weight ratio of the structural units derived from the unsaturated carboxylic acid or its derivative in the unsaturated carboxylic acid-modified cyclic olefin random copolymer resin [B] is 0.
2. The polyamide resin composition according to claim 1, wherein the polyamide resin composition has a content of 0.001 to 5% by weight. (3) The unsaturated carboxylic acid-modified cyclic olefin random copolymer resin [B] is characterized in that the intrinsic viscosity [η] measured in decalin at 135°C is 0.05 to 10 dl/g. The polyamide resin composition according to claim 1.