JPH03162448A - Polyamide resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition, composed of a polyamide resin and cyclic olefinic resin and excellent in heat and chemical resistance with low water absorptivity and molding shrinkage factor. CONSTITUTION:A polyamide resin composition obtained by blending (A) 98-2 pts.wt. polyamide resin with (B) 2-98 pts.wt. cyclic olefinic resin composed of a ring opening (co)polymer prepared by hydrogenating a cyclic olefin expressed by formula I (n is 0 or 1; m is 0 or a positive integer; R<1> to R<18> are H, halogen or hydrocarbon) or a hydrogenated substance thereof and, as necessary, further (C) a modified cyclic olefin random copolymer, obtained by modifying a cyclic olefin random copolymer composed of ethylene and the cyclic olefin expressed by formula I with an unsaturated carboxylic acid (derivative) and having 0.05-10dl/g intrinsic viscosity and 0.05-10mol% content of constituent units derived from the unsaturated carboxylic acid (derivative) in an amount of 1-100 pts.wt. based on 100 pts.wt. total amount of the components (A) and (B).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition containing a polyamide resin and a cyclic olefin resin.

Many of the polyamide resins represented by 6.6-nylon, 6-nylon, 12-nylon, etc. are crystalline and have relatively high melting points, and are used in a wide range of applications as engineering plastics. Such polyamide resins are often blended with fillers to further improve their heat resistance.

However, when the filler is blended in this way,
When the moldability of the polyamide resin decreases, anisotropy may occur in the resulting shaped body depending on the orientation direction of the filler added.

In addition, since polyamide resins containing no filler have a high shrinkage rate, the dimensional accuracy of certain shapes is often not sufficiently high, and furthermore, the heat resistance is lower than that of polyamide resins containing fillers. Furthermore, if a filler is not added, the water absorption rate of the polyamide resin will increase, and properties such as acid resistance and alkali resistance will also decrease accordingly.

Polyamide resins that have been widely used in the past are resins with excellent properties.Among these properties, there are some that require further improvement as mentioned above.

By the way, it is known that cyclic olefins having an ethylenic double bond in the ring have polymerizability, and for example, a cyclic olefin/a-olefin random copolymer can be obtained by reacting with an a-olefin such as ethylene. It is being

Furthermore, the above-mentioned cyclic olefin 14 can be used as an optical material with excellent transparency, water resistance, and thermal properties by ring-opening the cyclic olefin itself, which is used as a copolymer with a-olefin. is already known (see Japanese Unexamined Patent Publication No. 60-26024)
.

As a result of further research by the present inventors, it has been found that such cyclic olefin resins have the transparency, water resistance, and thermal properties necessary for optical materials. It was discovered that by blending it with resin, it was possible to obtain a resin composition with even better properties that can be used for various purposes. The object of the present invention is to provide a resin composition that has excellent properties and low water absorption and shrinkage.

Misato Tatsudan 1 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 formed by ring-opening polymerization of a cyclic olefin represented by the following formula [T]. A cyclic olefin resin comprising a polymer, a 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 cyclic olefin resin is 100
Parts by weight.

...[tl However, in the above formula [1], n is O or 1, m is O or a positive integer, and R1 to RI@ are each independently &; a hydrogen atom, a halogen atom, and a hydrocarbon Represents an atom or group selected from the group consisting of Rls to R I 8 19 may be combined with each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group is It may have a double bond, and RI
S and RI8 or RI7 and RII1 may form an alkylidene group.

Furthermore; in the present invention, the cyclic olefin resin +4 may be partially or entirely modified with a carboxylic acid or a derivative thereof.

Further, the present invention provides a polyamide resin composition as described above, and 1 to 10 parts by weight of the polyamide resin composition.
100 parts by weight of a modified cyclic olefin random copolymer.

Here, a modified product of a cyclic olefin random copolymer (modified cyclic olefin random copolymer) is a cyclic olefin random copolymer formed from ethylene and a cyclic olefin represented by the following formula [rl], and an unsaturated carboxylic acid. or a derivative thereof, which has an intrinsic viscosity [V] measured in decalin at 135°C of 0. 0 5 ~
10 di/i The resin composition according to the present invention, which is a resin containing 0.05 to 10 mol% of a structural unit derived from an unsaturated carboxylic acid or a derivative thereof, is a polyamide resin and a specific Since it is composed of a cyclic olefin resin obtained by ring-opening polymerization or copolymerization of a cyclic olefin, the resin has excellent heat resistance and chemical resistance.
It has the characteristics of low water absorption and certain shrinkage.

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

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, the polyamide resin composition according to the present invention will be specifically explained.

The polyamide resin composition according to the present invention includes polyamide,
It consists of a cyclic olefin resin formed by ring-opening polymerization of a specific cyclic olefin.

For example, the following formula [A
-1] or [A-2].

[A-1] O 1122 -{C-R -NHTe11 [A-21 However, in the above formulas [A-1] and [A-2], R2@ to R22 each independently represent a divalent Represents a hydrocarbon group. This hydrocarbon group may be an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. Further, R2+1 to R2219 may be the same or different.

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

Specifically, as a ring-opening polymer of lactams, for example (
Examples of polycondensates of aminocarboxylic acids include nylon 6 produced from f, ε-cabrolactam, and nylon 1 produced from ω-aminoundecanoic acid.
Polycondensates of dicarboxylic acids and diamines include nylon 6,a produced from adipic acid and hexamethylene diamine; nylon 6,a produced from sebacic acid and hexamethylene diamine; 6
, 1α dodecanedioic acid and hexamethylene diamine.

Further, as the polyamide resin used in the present invention, in addition to the polyamides mentioned above, aromatic polyamides having repeating units as described below can also be preferably used.

However, in the above formula, ql41 or 2, p
represents an integer from 2 to 20. Such aromatic polyamides include, for example, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid and 4,4-diphenoxyethane dicarboxylic acid.

Moreover, an alicyclic polyamide can be obtained by using an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid instead of the above-mentioned aromatic dicarboxylic acid.

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

In the present invention, from among the above-mentioned polyamides, a polyamide having desired properties can be selected and used, taking into account the intended use of the resulting composition. is 1000-100
A polyamide within the range of 0,000 is used.

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

... [In the above formula [T], n is 0 or l, and m is O or a positive integer.

And R l and R I I 13 each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In addition, examples of hydrocarbon groups include alkyl groups usually having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 15 carbon atoms, and specific examples of alkyl groups include methyl groups, etc. Mention may be made of ethyl, propyl, isoprobil, amyl, hexyl, octyl, decyl, dodecyl and octadecyl groups. Moreover, a cyclohexyl group can be mentioned as a specific example of the cycloalkyl group.

Furthermore, in the above formula [I], even if RI5 and RI6 or RI7 and R1● and the force ζ are bonded (jointly with each other) to form a monocyclic or polycyclic group, Alternatively, the monocyclic or polycyclic group thus formed may have a double bond.

Furthermore, RIs and RI8 or Rl7 and Rl8 may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such alkylidene groups include ethylidene, propylidene, and isopropylidene groups.

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

Specifically, the cyclic olefin represented by the above formula [I] used in the present invention includes bicyclo[2, 2. 11 Hebuto-2-ene-derived tetracyclo[4, 4, 0. 12・S, 17.1@
Co-3-dodecene derivatives [6, 6, 1. 13.8.1l9-
13, Q27, Q9. +4]-4-heptadensene derivative octacyclo[8,8,0, 12. e, 14.7,
l++. +s, 113. +8Q3. s, Q+z. +
t]-5-docosene derivative book pentasic mouth [6, 6, 1
, 13.6, 02.7, 09. l']-4-hexadecene derivative, heptacyclo-5-icosene derivative, heptacyclo-5-heneicosene derivative, tricyclo[
4, 3, 0. 11']-3-f Se:/ 1st {
tc, trisic mouth [4, 3, 0. 12S]-3-undecene derivative pentacyclo[6, 5, 1. 13.
6,02・? , QII3] -4-pentadecene derivative, pentadecadiene derivative, pentadecadiene derivative [4, 7, 0, 12 . S,
O@・13.1112]-3-pentadecene induction book/< :/ 9 Shikuo [7,8,0,13. '+0
2. '+1''-'', O'''' 6112.1s Koh 4-eikosen induction imitation and nonasuku mouth [9, 10, 1, 1, 4.7, 03. @,0
2.1@,012.21113.211,Qth,l,l
ls. Mention may be made of I@co-5-pentacocene derivatives.

Specific examples of such compounds are shown below.

Bicyclo[2, 2. 11 Hepto 2-
Ene derivative; ene5.10-dimethyltetraCHsCHa2,7. 9- }Limethylte9-isobutyl-2.7-9,11.12-} Limethyl9-ethyl-11. 12-dime9-isobutyl 11.12 5, 8, 9. 10-Tetramethy (blank below) 8-methyltetrasic 8-ethyltetrasic 1@co3 Dodecene 8-hexyltetrasic C,. H,, +e]-3-dodecene・l @]-3-dodecene8-methyl-9-ethylte8-chlorotetrasic-13-dodecene8-promotetrasic-3-dodecene+eco-3-dodecene1@] -3-dodecene 5.17 IJ-3-dodecene + 11]-3-dodecene-3-dodecene 3-dodecene, 12 5.17 +11]-3-dodecene 8-ethylidene-9-yne-dodecene, 12 5 , 1 chop I] 13-dodecene s. 1 cho 1 8 ]-3-dodecene 8-n-propylidene-9 -dodecene 8-n-propylidene-9 [4, 4, 0. 12・5,17 +a. 1-3 Dodesenkuro [4, 4, 0. 12 17 +11]-3-dodecene 8-n-propylidene-9 [4, 4, 0. 12 5.17 111 Cor 3 1-dodecene-dodecene 8-impropylidene-dodecene 1 @ ]-3-dodecene CH. [4, 4, 0. 12 5.17・1@Co3-Tetrasic compounds such as dodecene [4, 4, 0. 12 5.17 +11]-3-dodecene derivative, (margin below)! 4-co-4-heptadecenedeceneheptadecene+3, Q2.7, Q11. I4]-4-heptadecene and other hexacyclo[6. 6, 1. 138.11
@・+ 3, Q2・7.09+4]-4-heptadecene derivative; docosene+1.1@, 113.1@. Q3 ●,01 1 unit] Octacyclo[8, 8, 0. 129.14 7.1 ■ Gate, 1 + 6, Q3 +1, Ql 2 +? ]-5-docosene derivative; pentacyclo[6. 6, 1. 13.6,
Q2. 7, Q914-4-hexadecene derivative; heptase [8, 7. 0 hebutacyclo-5-icosene derivatives such as cosene or hebutacyclo-5-eicosene derivatives; tricyclo[4, 3, 0. 125 ko 3-
Decene derivatives; tricyclo[4, 4, 0. 12 5] -3-undecene derivative; 1,3-dimethyl-benta 1,6-dimethylbenta 14. Pentacyclo[6. 5, 1. 1”8.
Q2. ? ．． (p.+3] = 4-pentadecene derivatives; diene compounds such as; pentacyclo[4, 7, 0.12 5.08 13.19 12] -3-pentadecene derivatives such as cosene 15-4-eicosene, etc. Heptacyclo[ 7, 8, 0. 1' 6.02 7.1111 17.0 1,112 15 Co-4-eicosene derivative: .21.113211,Ql4.+9.11518 Co-5-pentacocene 3.2@ , Q111, lIIi.IJ - Nonacyclo [9, 10, 1. 1'・T, such as 5-pentacocene
Q3. 8, Q2・l @, Ql 221,
113.2@, QIj. l*. llSl@] -5-
F: / 9:7 Sen derivative book (below, blank space) The cyclic olefin represented by the above formula [I] is subjected to ring-opening polymerization or The ring-opening polymer or ring-opening copolymer used in the present invention can be produced by ring-opening copolymerization.

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

The ring-opening polymerization catalyst used here includes ruthenium,
A catalyst consisting of a metal halide, nitrate or acetylacetone compound such as rhodium, palladium, osmium, indium or platinum, and a reducing agent such as an alcohol; , organoaluminium, and the like.

The ring-opening polymer or copolymer used in the present invention contains repeating units derived from the cyclic olefin represented by the above formula [I], usually in an amount of 50 mol% or more, preferably 8
The content is 0 mol% or more, particularly preferably 90 mol% or more. The molecular weight of such a ring-opened polymer or ring-opened copolymer is usually 1,000 to 500,000, preferably 1,000 to 500,000.
It is within the range of 10,000 to 100,000. This molecular weight can be controlled by adjusting the reaction conditions. For example, it can also be adjusted by blending a small amount of olefin or other cycloolefin.

By carrying out ring-opening polymerization or ring-opening copolymerization as described above, it is assumed that at least a part of the polymer 19 obtained has a repeating unit represented by the following formula [[+] It will be done.

... [■] However, in the above formula [nl, n and m and R
1 to R1814 Same meaning as above.

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

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

Examples of such heterogeneous catalysts include catalysts in which nickel, palladium, platinum, or these metals are supported on a carrier such as carbon, silica diatomaceous earth, alumina, or titanium oxide. ,nickel/
Mention may be made of silica, nickel/diatomaceous earth, palladium/carbon, palladium/silica, palladium/diatomaceous earth and palladium/alumina.

In addition, examples of homogeneous catalysts include catalysts based on metals in group Ⅰ of the periodic table; a specific example is C
Oxide containing N1 or CO compounds such as nickel naphthenate/triethylamine, n-butyllithium naphthenate, nickel acetylacetonate/triethylaluminum, and organometallic compounds of metals from Groups Ⅰ to M of the Periodic Table.Additionally, Rh compounds are listed. be able to.

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

The pressure of hydrogen gas during hydrogen addition is usually 1 turn.
~150 atm, reaction temperature C9 usually 0~100℃,
Preferably, it is set within a pure range of 20 to 100°C.

The hydrogenation rate can be adjusted arbitrarily by changing the hydrogen pressure, reaction temperature, reaction time, catalyst concentration, etc. It is preferable that 50% or more of the double bonds present are hydrogenated, particularly 80% or more, and more preferably 90% or more.

For example, the following formula [
It is thought that it has a repeating unit as shown in [lI1].

... [ml However, in the above formula [ml, n and m and R
I-'fl l●13 Same meaning as above.

In addition, in the present invention, [9] Ring-opened polymer and... The ring-opened copolymer, the hydrogenated product, and If can be used individually or in combination.

Furthermore, in the present invention, when producing a ring-opening copolymer or a hydrogenated product as described above, the IL expressed by the above formula [1] may be used within a range that does not impair the properties of the obtained polymer, etc. It is also possible to polymerize cyclic olefins other than the cyclic olefins used. Examples of such cyclic olefins include cyclobutene, cyclobentene, cyclohexene, 3,4-dimethylcyclohexene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, 2,
3, 3a, 7a-tetrahydro 4.7-methanol DI-inde 3a, 5, 6, 7a-tetrahydro tff -4. Examples include 7-methanol IH-indene. Such other cyclic olefins are
They can be used alone or in combination, and are usually used in an amount of 0 to 20 mol%.

Such a cyclic olefin resin, that is, a ring-opening copolymer imitating these ring-opening polymers, a hydrogenated compound 1, and an unsaturated carboxylic acid such as maleic anhydride may be partially or completely modified. It may also be a degenerated product.

Such a modified product IL can be produced by reacting a cyclic olefin resin as described above with an unsaturated carboxylic acid, an anhydride thereof, and a derivative such as an alkyl ester of an unsaturated carboxylic acid. The method for producing a modified cyclic olefin copolymer disclosed in JP-A-62-27412 can be used as a guideline for the reaction. The content of power units derived from the modifier in the modified cyclic olefin resin is usually 0.
．． 01 to 10i amount%.

Such a modified cyclic olefin resin can be manufactured by blending a modifier with the cyclic olefin resin and graft polymerization to obtain a desired modification ratio, or by preparing a modified product with a high modification ratio in advance. It can also be produced by subsequently mixing this modified product with an unmodified cyclic olefin resin.

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

In the cyclic olefin random copolymer used to prepare the modified cyclic olefin random copolymer, the amount of repeating units derived from ethylene is usually 40 to 85 mol%, preferably 50 to 70 mol%. A copolymer containing repeating units derived from a cyclic olefin is usually used in a range of 15 to 60 mol%, preferably 25 to 50 mol%. And in this cyclic olefin random copolymer,
The repeating units derived from ethylene and the repeating units derived from cyclic olefins are arranged in a substantially linear manner. That is, this filthy olefin random copolymer has substantially no gel-like crosslinked structure.

In such a cyclic olefin random copolymer, at least a portion of the cyclic olefin represented by the above formula [I] is randomly copolymerized with ethylene in the form represented by the formula [■] shown below. It is thought that the

...[■] However, in the above formula [■], R1 to R1@ and n
and m have the same meanings as in the above formula [+].

Such a cyclic olefin random copolymer {L135
The ultimate temperature measured in decalin at °C is usually 0.01~
10 dl, preferably O. OS~7dl/g,
It is a cyclic olefin random copolymer whose glass transition temperature is usually 70°C or higher.

Such a modified cyclic olefin random copolymer is produced using a modifying agent such as maleic anhydride, and is disclosed in Japanese Patent Application Laid-open No. 62-27.
It can be produced by modifying the method disclosed in Japanese Patent No. 412 as a guideline.

Modified product IL of addition polymer of cyclic olefin and ethylene
It can be produced by reacting the polymer with unsaturated carboxylic acids, their anhydrides, and derivatives such as alkyl esters of unsaturated carboxylic acids. In addition,
In this case, the content of component units derived from the modifier in the modified cyclic olefin resin is usually 0.0.
1-10% by weight.

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

The resin composition of the present invention contains a cyclic olefin resin and a polyester resin as described above in a 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. Note that here, the total content of the cyclic olefin resin and the polyamide resin is 100 parts by weight.

And more preferably, cyclic olefin resin 30~
70 parts by weight, and 70 to 30 parts by weight of polyamide resin.

As mentioned above, the cyclic olefin resin may be partially or completely modified.

In addition, resin composition 1 of the present invention; when a modified product of an addition polymer of a cyclic olefin and ethylene (i.e., a modified cyclic olefin random copolymer) is included, this modified product is a polyamide resin and an unmodified cyclic copolymer. Per 100 ffiffi parts of total weight of olefin resin, i゛ is
1-100ffi amount per prefecture, preferably 2-20ffl
It is recommended to mix in the amount of rt part.

The resin composition of the present invention further contains heat stabilizers, weather-resistant 7'Fl, antistatic agents, slip agents, anti-blocking agents, antifogging agents, lubricants, dyes, pigments, natural nL, synthetic waxes, organic fillers. Also, inorganic fillers and the like may be added.

For example, stabilizers used in the present invention include tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)probionate comethane, β-(3.
Phenolic oxidative stabilizers such as 5-di-t-butyl-4-hydroxyphenyl)probionic acid alkyl ester and 2,2'-oxamidobis[ethyl-3(3,5-di-t-butyl-4-hydroxyphenyl)brobionate; stearin acid zinc, 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 etc. can be mentioned.

These can be used alone or in combination. Examples of such combinations include tetrakis[methylene-3(3.5-di-t-butyl-4-hydroxyphenyl)probione7to]methane, zinc stearate, and glycerol monothureate. can.

Further, examples of organic or inorganic fillers 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 flakes, glass beads, calcium silicate, montmorillonite, pentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber , silicon carbide fibers, polyethylene fibers, polypropylene fibers and polyamide fibers.

Such an organic or inorganic filler is usually used in an amount of 1 to 100 FFI, preferably 5 to 100 FFI, per 100 FFI in total of the cyclic olefin resin and polyamide resin.
The amount of ffi is particularly preferably 5 to 50 parts.

Note that other resins may be blended into the resin composite of the present invention within a range that does not impair its properties. Examples of resins that can be blended in this case include polyester, polyolefin, polyamide, polycarbonate,
Synthesis of halogen-containing vinyl polymerization Simulation of polymers or copolymers from σ,β monounsaturated carboxylic acids or their derivatives Polymerization of epoxides Polyacetal, polyphenylene oxide, polysulfone, polyurethane resin, urea resin,
Mention may be made of alkyd resins, phenolic resins, olefin rubbers and diene rubbers.

The resin composition of the present invention can be manufactured by, for example, a method of mixing each component simultaneously, a method of mixing polyamide and a cyclic olefin resin, and then mixing other components as desired. Can be done.

The cyclic olefin resin and the polyamide resin can be mixed by blending the cyclic olefin resin and the polyamide in a molten state using an extruder or the like. Hydrocarbonized water milk The cyclic olefin resin and the polyamide resin may be dissolved and mixed in an aromatic hydrocarbon such as toluene, benzene, or xylene, and then the solvent may be removed.

The thus obtained resin composition of the present invention has excellent properties essentially possessed by polyamide, and is particularly excellent in heat resistance and chemical resistance.

Furthermore, by blending cyclic olefin resin,
As the water absorption rate decreases, the progress of the hydrolysis reaction is suppressed during oxidation. Furthermore, the shrinkage rate of the molded product is reduced.

Since the resin composition of the present invention has the above-mentioned properties, it is suitable for applications where polyamide resins have traditionally been used, such as heat resistance, chemical resistance, low water absorption, or low shrinkage. It can be widely used in various fields.

Since the resin composition of the present invention is composed of a polyamide resin and a cyclic olefin resin, it has particularly excellent heat resistance and chemical properties.Furthermore, by blending the cyclic olefin resin, In addition, the water absorption rate is reduced, and the progress of hydrolysis reaction during molding is suppressed.Furthermore, the shrinkage rate of certain shapes is reduced.

Next, the present invention will be explained in more detail by showing Examples.8 The present invention should not be construed as being limited by these Examples.

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

(1) Melt flow index (MRFTOC) Temperature T'C, weight 2.16 according to ASTM D1238
(2) Preparation of test piece: Using an injection molding machine manufactured by Toshiba Machine IS-55EPN and a specified mold for making a test piece, the test piece was molded under the following conditions.
After molding, the test piece was left at room temperature for 48 hours before use.Cylinder temperature: 280℃ Mold temperature: 60℃ Injection pressure: 1000/800Kg/c
m2 injection speed (primary): 50% Screw rotation speed: 150 rpm (3) Bending test Conducted according to ASTM D790 T4 test piece shape:
5X 1/2X 1/81 inch, distance between spans: 50
mm Test speed: 20 mm/min Test temperature: 23°C (4) Izod impact test conducted according to ASTM D256 9 Test piece shape: 5 x 1/2 x 1/8' inch, Test temperature: 23°C (5) Thermal deformation Temperature (HDT) Conducted according to ASTM D648 T4 test piece shape 5
X 1/4X 1/21 inch Load: 264psi (6) Softening temperature (TMA) Manufactured by DuPont, Thermo Mechanical
The heat deformation strength of a sheet with a thickness of 1 mm was measured using an analyzer. A quartz needle was placed on the sheet, a load of 49 g was applied, and the humidity was raised at a rate of 5°C/min. TM is the temperature that penetrates 0.635mm.
I gave it an A.

(7) Glass transition temperature (Tg) S E I K O? It child engineer! Measurement was performed using a special DSC-zO at a heating rate of 10° C./min, and the value after 24 hours was measured according to the circle (8) water absorption rate JIS K 7209A method.

(9) Pencil hardness Measured at 23℃ according to JIS K 5400 and supervised 1
(Combination of ring-opening polymer) 700ml of toluene in 1 additional flask, 1, 4, 5
．． 8-dimethano-1. 2, 3, 4. 4a,
5, 8. 8a-octahydronaphthalene (DMON
)9 3ml, 2-norbornene (NB) 7ml, l-
Hexane 0. 5ml and 0. Add 1 mmol of W C Q a and tetraphenyltin at 50°C.
Polymerization was carried out for 2 hours, and the whole polymerization solution was poured into a large amount of methanol, and the resulting polymer was precipitated and collected by filtration. After washing this polymer three times each with methanol and acetone, it was incubated at 80°C overnight. 98 g of polymer was obtained by drying under reduced pressure. The intrinsic viscosity of the obtained polymer was measured in toluene at 30° C. [η] 14 0. 78 dl/g, and the NB content measured by 13c-NMR is 10
(Hydrogenation reaction of ring-opening polymer) Dissolve 20g of ring-opening polymer in 250ml of tetrahydrofuran.Catalyst 1 in which L, Pdlg and 50g of silica are supported on 50g of silica.
Next, this autoclave was filled with H2 and pressurized to 50 kg/cm2 G, then the temperature was raised to 50°C and stirring was continued for 15 hours.The resulting slurry solution Next, this polymer (containing the catalyst) was dissolved in cyclohexane, and the catalyst and polymer were separated by filtration, and then dried at 100°C under reduced pressure for one day and night.9 The hydrogenation rate was 97%. For the obtained polymer, DSC manufactured by HarkinElmer Co.
The glass transition temperature (Tg) measured at a heating rate of 10°C/min using
5 g of maleic anhydride, chopped into 5 g and dissolved in 25 g of acetone.
0g, organic peroxide (manufactured by Nippon Oil & Fats ■, Verhexin T”
25B) After adding 3 g and mixing thoroughly, twin screw extrusion 8! (manufactured by Ikegai Tekko tIl, PCM 45), the reaction was carried out under melting at a cylinder temperature of 250°C, and the maleic anhydride content of the resulting resin was 0.8% by weight.
1 unit [A] Made by Toray ■, nylon 6 nameplate (CM1
017) Nobe Left 2. 0 is the [B] component of the hydrogenated polymer obtained as described above}2k
After thoroughly mixing g,
M45) was melt-blended at a cylinder temperature of 280° C. and made into pellets using a pelletizer. Using the obtained pellets, test specimens were prepared by the method described above and the physical properties were evaluated. The results are shown in Table 1.

Same as Example 1 except that the amount of [A] component and [B] a certain amount ([A] a certain amount/[B] a certain amount) was changed as described below. A test piece was prepared in the same manner except that pellets were produced using the pellets, and the physical properties of the test pieces were evaluated. O
/3. 0 (Example 2) [A] Precept/[B] component = 3. 0/1. 0 (Example 3) The results are shown in Table 1.

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 added as [C] in the proportions shown below. A pellet was manufactured in the same manner except that it was used in
Its physical properties were evaluated.

Polyamide resin/hydrogenated ring-opening polymer/maleated hydrogenated ring-opening polymer=2/1. 670. 4 results are shown in Table 1.

2 kg of the hydrogenated ring polymer obtained in Reference Example 1 was added with an ethylene/propylene random copolymer (ethylene content =
80 mol%, Tg: 54°C, MFR23sQCo0.
7g/10min, [η: 2.2dl/g)
After thoroughly mixing 0.5 kg of Belen, the mixture was melt-blended using a twin-screw extruder (manufactured by Ikegai Iron Works, PCM 45) at a cylinder temperature of 220°C, and made into pellets using a pelletizer. 1g of Verhexin T” 25B manufactured by Nippon Juzai 1g of vinylbenzene 3
The mixture was added to the twin screw extruder (cylinder temperature: 230 g) and thoroughly mixed.
°C), and then pelletized using a pelletizer to form a pellet using a pelletizer. A test piece was prepared in the same manner except that the beret produced in the above manner was used. Table 1 shows the results of evaluating the physical properties of the test piece.

In Example 1 of Shinai Ayu, without using [B] precepts, [A]
A test piece was prepared in the same manner as in Example 1, except that only the polyamide was used.The physical properties of the test piece were evaluated, and the results are shown in Table 1.

Claims (3)

[Claims] (1) Polyamide resin: 98 to 2 parts by weight, and the following formula [ I
] Cyclic olefin resin consisting of a ring-opening polymer or copolymer formed by ring-opening polymerization of a cyclic olefin represented by However, the total amount of the polyolefin resin and cyclic olefin resin is 100 parts by weight)
A polyamide resin composition characterized by consisting of; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ... [I] (In the formula, n is 0 or 1, m is 0 or a positive integer, , R^1 to R^1^8 each independently represent 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 are They may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group 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). (2) The polyamide resin composition according to claim 1, wherein a part or all of the cyclic olefin resin is modified with a carboxylic acid or a derivative thereof. (3) Polyamide resin: 98 to 2 parts by weight, and the following formula [ I
] Cyclic olefin resin consisting of a ring-opening polymer or copolymer formed by ring-opening polymerization of a cyclic olefin represented by However, the total amount of the polyolefin resin and cyclic olefin resin is 100 parts by weight)
and, obtained by modifying a cyclic olefin random copolymer formed from ethylene and a cyclic olefin represented by the following formula [I] with an unsaturated carboxylic acid or a derivative thereof,
Intrinsic viscosity [η] measured in decalin at 135°C is 0.0
5 to 10 d1/g, and a modified cyclic olefin random copolymer having a content of 0.05 to 10 mol% of structural units derived from unsaturated carboxylic acids or derivatives thereof, the modified cyclic olefin random copolymer A polyamide resin composition characterized in that the content of the combined substance is 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 cyclic olefin resin; ▲ Numerical formula, chemical formula, There are tables, etc. ▼ (In the formula, n is 0 or 1, m is 0 or a positive integer, and R^1 to R^1^0 each independently represent a hydrogen atom, a halogen atom, and a hydrocarbon atom. R^1^5 to R^1^8 may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic Or the polycyclic group may have a double bond, and R^1^5 and R^1^6, or R^1^7
and R^1^8 may form an alkylidene group).