JPH05112656A - Blow-molded article - Google Patents

Abstract

PURPOSE:To obtain a blow-molded article having excellent high-temperature rigidity, surface gloss and surface smoothness by molding a resin composition containing a polyamide resin and a specific modified cyclic olefinic resin. CONSTITUTION:The objective blow-molded article is produced by molding a resin composition containing (A) a polyamide resin and (B) a modified cyclic olefinic resin having an intrinsic viscosity [eta] of 0.05-10dL/g measured in decalin at 135 deg.C and obtained from (i) a cyclic olefinic random copolymer produced by the addition polymerization of ethylene and a cycloolefin of formula, (ii) a ring-opened polymer of a cycloolefin produced by the ring-opening polymerization of the cycloolefin of formula or (iii) a cycloolefin resin obtained by the hydrogenation of the above ring-opened polymer by modifying the above polymer or resin with an unsaturated carboxylic acid (derivative) at a weight ratio (A/B) of 2/98 to 98/2.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a blow-molded article, and more particularly, the present invention relates to a blow-molded article formed from a polyamide resin and a cyclic olefin resin and having excellent high-temperature rigidity, surface gloss and surface smoothness.

[0002]

BACKGROUND OF THE INVENTION Molded articles made of polyamide resin are used in many products because they have high temperature rigidity, practical impact strength, and good paintability. However, molded products formed from polyamide resin are often manufactured by injection molding, and few molded products are manufactured by blow molding. This is because blow molding using a polyamide resin is difficult because the melt tension of the polyamide resin itself is not high enough for blow molding.

Therefore, when a blow molded article is manufactured from polyamide, a resin composition in which modified polyethylene, modified polypropylene rubber or the like is blended with a polyamide resin to improve melt tension is used. By blending with, the high temperature rigidity of the polyamide resin decreases. Attempts have been made to add an inorganic filler to compensate for this decrease in high-temperature rigidity, but the addition of an inorganic filler reduces the surface smoothness and surface gloss of the blow-molded product obtained. The blow-molded article having such surface properties has a poor appearance in the unpainted state, and it is difficult to obtain a blow-molded article having a good appearance even if the surface of the blow-molded article is coated.

[0004]

OBJECT OF THE INVENTION It is an object of the present invention to provide a blow molded product having high temperature rigidity and surface gloss using a polyamide resin.

[0005]

SUMMARY OF THE INVENTION The blow-molded article of the present invention is obtained by addition-polymerizing (A) a polyamide resin, (B) (Bi) ethylene and at least one cyclic olefin represented by the following formula [I]. Prepared cyclic olefin random copolymer,
(B-ii) a cyclic olefin ring-opening polymer prepared by ring-opening polymerization of at least one cyclic olefin represented by the following formula [I], and (B-iii) water of the ring-opening polymer The intrinsic viscosity [η] measured in decalin at 135 ° C. obtained by modifying a cyclic olefin resin selected from the group consisting of an additive and an unsaturated carboxylic acid or a derivative thereof is 0.05 to 10 dl /
2/9 with a modified cycloolefin resin within the range of g
The resin composition is contained in a weight ratio of 8 to 98/2.

[0006]

[Chemical 2]

[I] In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a And R ^b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are
R ¹⁵ and R ¹⁶ may be combined with each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond. Alternatively, R ¹⁷ and R ¹⁸ may form an alkylidene group.

[0008]

DETAILED DESCRIPTION OF THE INVENTION Next, the blow-molded article of the present invention will be specifically described. The blow-molded article of the present invention is formed from a resin composition comprising a polyamide resin (A) and a modified cyclic olefin resin (B).

Polyamide resin (A) used in the present invention
Include polyamides formed by polycondensation of dicarboxylic acids and diamines, polyamides formed by ring-opening polymerization of lactams, and polyamides formed of dicarboxylic acids, diamines and lactams.

Such a polyamide resin (A) has a repeating unit represented by the following formula [II] or [III].

[0011]

[Chemical 3]

[II] In the above formula [II], R ^a and R ^b are each independently a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group or a divalent aromatic carbon group. Represents one of hydrogen groups, and p is a positive integer.

[0013]

[Chemical 4]

[III] In the above formula [III], R ^C is either a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. , Q is a positive integer.

Specific examples of the polyamide resin include ring-opening polymers of cyclic amides such as ramtams (for example, nylon 6 produced from ε-caprolactam) and polycondensates of aminocarboxylic acids (for example, ω- Nylon 11 produced from aminoundecanoic acid, Nylon 12 produced from ω-aminododecanoic acid), polycondensates of dicarboxylic acids and diamines (for example, nylon 66 produced from adipic acid and hexamethylenediamine, sebacine) Examples thereof include nylon 610 manufactured from an acid and hexamethylenediamine, nylon 612) manufactured from dodecanedioic acid and hexamethylenediamine, and the like.
These polyamides can be used alone or in combination.

This polyamide resin has an intrinsic viscosity [η] (3
The value measured in concentrated sulfuric acid at 0 ° C) is usually 0.3 to 4 dl /
g, preferably in the range of 0.4-3 dl / g. The modified cyclic olefin resin (B) used in the present invention is (Bi)
A cyclic olefin-based random copolymer prepared by addition-polymerizing ethylene and at least one cyclic olefin represented by the formula [I], (B-ii) formula [I]
A cyclic olefin ring-opening polymer prepared by ring-opening polymerization of at least one cyclic olefin represented by, and (B-iii) a hydrogenated product of the ring-opening polymer, a ring selected from the group consisting of It is a modified cyclic olefin resin obtained by modifying an olefin resin with an unsaturated carboxylic acid or a derivative thereof.

The cyclic olefin random copolymer (Bi) used here is a copolymer prepared by addition-polymerizing ethylene and a cyclic olefin represented by the following formula [I].

[0018]

[Chemical 5]

[I] In the above formula [I], n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. When q is 0, the bond defined by q is a single bond, and thus the ring formed here is a 5-membered ring.

In the above formula [I], R ^{1 to} R ¹⁸
R ^a and R ^b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. Here, as the halogen atom,
For example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be mentioned. As the hydrocarbon group, each independently, usually, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms and an aromatic group. Hydrocarbon group can be mentioned, and specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group and octadecyl group. As a specific example of the alkyl halide, a group in which at least a part of hydrogen atoms forming the alkyl group as described above is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom can be used. Can be mentioned. Further, specific examples of the cycloalkyl group include a cyclohexyl group, specific examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group, and these groups include a lower alkyl group. It may have a group.
Furthermore, in the above formula [I], R ¹⁵ and R ¹⁶ are R ¹⁷
And R ¹⁸ , R ¹⁵ and R ¹⁷ , R ¹⁶ and R ¹⁸ , R ¹⁵ and R ¹⁸ , or R ¹⁶ and R ¹⁷ are bonded (in cooperation with each other) to form a single group. It may form a cyclic or polycyclic group, and the monocyclic or polycyclic group thus formed may have a double bond.

Here, examples of the monocyclic or polycyclic group include:
The groups described below can be mentioned.

[0022]

[Chemical 6]

In the above-exemplified groups, the carbon atoms numbered 1 and 2 are the same as R in the formula [I].
It represents a carbon atom of an alicyclic structure to which a group represented by ^{15 to} R ¹⁸ is bonded.

In addition, R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸
And 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 an alkylidene group include an ethylidene group, a propylidene group and an isopropylidene group.

Examples of the cyclic olefin represented by the formula [I] include bicyclo [2,2,1] hept-2-ene derivative, tetracyclo [4,4,0,1 ^2.5 , 1 ^7.10 ] -3- Dodecene derivative, hexacyclo [6,6,1,1 ^3.6 , 1 ^10.13 , 0 ^2.7 , 0 ^9.14 ] -4-Heptadensen derivative, octacyclo [8,8,0,1 ^2.9 , 1 ^4.7 , 1
^11.18 , 1 ^13.16 , 0 ^3.8 , 0 ^12.17 ] -5-dococene derivative, pentacyclo [6,6,1,1 ^3.6 , 0 ^2.7 , 0 ^9.14 ] -4-hexadecene derivative, heptacyclo-5-icosene derivative, heptacyclo-
5-heneicosene derivative, heptacyclo-5-eicosene derivative, pentacyclo [8,4,0,1 ^2.3 , 1 ^9.12 , 0 ^8.13 ] -3-hexadecene derivative, pentacyclo [7,4,0,1 ^2.5 , 1 ^9.12 , 0
^8.13 ] -3-Pentadecene derivative, pentacyclo [6.5.1.1
^3,6 .0 ^2,7 .0 ^9,13 ] -4-Pentadecene derivative, pentacyclo
[8,7,0,1,3,6,1 ^10.17 , 1 ^12.15 , 0 ^2.7 , 0 ^11.16 ] -4-Eicosene derivative, pentacyclo [8,8,0,1 ^4.7 , 1 ^11.18 , 1 ^13.16 , 0
^3.8 , 0 ^12.17 ] -5-Heneicosene derivative, pentacyclopentadecadiene derivative, tricyclo [4,3,0,1 ^2.5 ] -3-
Decene derivatives, tricyclo [4,3,0,1 ^2.5] -3-undecene derivative and Nonashikuro [9.10.1.1.4.7.0 ^3,8 .0
It may be mentioned ^2,10 .0 ^12,21 .1 ^13,20 .0 ^14,19 .1 ^15,18] -5-pentacosene derivatives.

Specific examples of such cyclic olefins are shown below.

[0027]

[Chemical 7]

[0028]

[Chemical 8]

[0029]

[Chemical 9]

[0030]

[Chemical 10]

[0031]

[Chemical 11]

[0032]

[Chemical 12]

[0033]

[Chemical 13]

[0034]

[Chemical 14]

[0035]

[Chemical 15]

[0036]

[Chemical 16]

[0037]

[Chemical 17]

[0038]

[Chemical 18]

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

Cyclic Olefin Random Copolymer (Bi)
In, the cyclic olefin represented by the above formula [I] and ethylene are randomly addition-polymerized. The content of repeating units derived from ethylene in the cyclic olefin random copolymer (Bi) is usually 40 to
It is in the range of 90 mol%, preferably 50 to 80 mol%, and the content of repeating units derived from a cyclic olefin is usually 10 to 60 mol%, preferably 20 to 50 mol%.
It is in the range of mol%.

This cyclic olefin random copolymer (B
-i) can be produced, for example, by polymerizing ethylene and a cyclic olefin in a hydrocarbon medium in the presence of a catalyst formed from a hydrocarbon-soluble vanadium compound and a halogen-containing organoaluminum compound.

The hydrocarbon solvent used here is
Examples thereof include aliphatic hydrocarbons such as hexane, heptane, octane and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene. Further, among the polymerizable unsaturated monomers that can be used when preparing the copolymer, a compound that is liquid at the reaction temperature can be used as the reaction solvent. These solvents alone,
Alternatively, they can be used in combination.

The catalyst used in the reaction of the above ethylene with the cyclic olefin represented by the formula [I] is
Examples of the catalyst include a vanadium compound soluble in a hydrocarbon solvent used as a reaction solvent and an organoaluminum compound.

The vanadium compound used as the catalyst here has the formula VO (OR) _a V _b or the formula
The compound represented by V (OR) _c X _d may be mentioned. However, in the above formula, R is a hydrocarbon group, and 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c
The relationship is ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c + d ≦ 4.

Further, the vanadium compound may be an electron donor adduct of the vanadium compound represented by the above formula. Examples of the electron donor that forms an adduct with the vanadium compound include alcohols having 1 to 18 carbon atoms and phenols having 6 to 20 carbon atoms (these phenols have a lower alkyl group). Good), ketones having 3 to 15 carbon atoms, aldehydes having 2 to 15 carbon atoms, organic acid esters having 2 to 30 carbon atoms, acid halides having 2 to 15 carbon atoms, and 2 carbon atoms To 20 ethers, amines, nitriles and alkoxysilanes. These electron donors can be used alone or in combination.

Specific examples of vanadium compounds include:
VOCl₃, VO (OC₂H_Five) Cl₂, VO (OC₂H_Five)
₂Cl, VO (O-iso-C₃H₇) Cl₂, VO (O-n-C_Four
H₉) Cl₂, VO (OC₂H_Five)₃, VOBr₂, VCl_Four,
VOCl₂, VO (O-n-C_FourH ₉)₃And VCl₃・ 2
(OC₈H₁₇OH) can be mentioned. These ba
Nadium compounds used alone or in combination
be able to.

As the organoaluminum compound, a compound having at least one Al-carbon bond in the molecule can be used. Here, as examples of the organic aluminum compound, (i) formula _{^{R 1 m Al (OR 2)}} n H p X q ( wherein R ¹ and R ² are carbon atoms, usually from 1 to 15, preferably 1 Hydrocarbon groups of 4 to 4, which may be the same or different from each other, X is halogen, m is 0 ≦ m ≦ 3,
n is 0 ≦ n <3, p is 0 ≦ n <3, and q is a number of 0 ≦ q <3, and m + n + p + q = 3), (ii) Formula M ¹ AlR ¹ ₄
(Here, M ¹ is Li, Na, K, and R ¹ has the same meaning as described above.) A complex alkyl compound of a Group I metal and aluminum can be given.

Specific examples of the organoaluminum compound represented by the above formula (i) include the compounds described below. A compound represented by the formula R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² have the same meanings as described above, and m is preferably a number of 1.5 ≦ m <3).

Formula R ¹ _m AlX _3-m (wherein R ¹ has the same meaning as described above, X is halogen, and m is preferably 0 <m.
A compound represented by <3. A compound represented by the formula R ¹ _m AlH _3-m (wherein R ¹ has the same meaning as described above, and m is preferably 2 ≦ m <3).

The formula R ¹ _m Al (OR ² ) _n X _q (where R ¹
And R ² have the same meaning as described above. X is halogen, 0
<M ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3
Is a compound represented by the formula:

Specific examples of the organoaluminum compound represented by the above formula (ii) include trialkylaluminum, trialkylaluminum, dialkylaluminum alkoxide, alkylaluminum sesquialkoxide, formula R ¹ _2.5 Al (OR ² ) _{0.5 and the} like. A partially halogenated alkylaluminum such as a partially alkoxylated alkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide, dialkylaluminum hydride, alkylaluminum dialkyl having an average composition represented by Mention may be made of partially hydrogenated alkyl aluminums such as hydrides and partially alkoxylated and halogenated alkyl aluminums.

Examples of the organoaluminum compound represented by the above formula (ii) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ . Among these, it is particularly preferable to use an alkylaluminum halide, an alkylaluminum dihalide or a mixture thereof.

The organoaluminum compound may be a compound similar to the compound represented by the formula (ii), such as an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom. Specific examples of this compound include (C ₂ H ₅ ) ₂ AlOAl
(C ₂ H _{5) 2,} and the like _{(C 4 H 9) 2 AlOAl} (C 4 H 9) 2 and _{(C 2 H 5) 2 AlN} (C 6 H 5) Al (C 2 H 5) 2 it can.

The vanadium compound is used in an amount of usually 0.01 to 5 gram atom / liter, preferably 0.05 to 3 gram atom / liter as vanadium atom. The amount of the organoaluminum compound used is usually in the range of 2 or more, preferably 2 to 50, particularly preferably 3 to 20, when expressed as the ratio of aluminum atoms to vanadium atoms in the polymerization reaction system (Al / V). It is inside.

Such a polymerization method itself is already known, and in the polymerization, for example, JP-A-60-168708 and 61-
120816, 61-115912, 61-115916, 61-27130
No. 8, No. 61-272216, No. 62-252406 and No. 62-252407
The method proposed in the gazette such as the issue can be used.

In such a cyclic olefin random copolymer, for example, at least a part of the cyclic olefin represented by the above formula [I] has a structure represented by the following formula [IA] and is derived from ethylene. It is considered that the repeating units are randomly bonded.

[0057]

[Chemical 19]

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

Cyclic Olefin Random Copolymer (Bi)
In, a repeating unit derived from ethylene,
The repeating unit derived from a cyclic olefin is randomly and substantially linearly arranged. This cyclic olefin-based random copolymer is substantially linear, and does not have a crosslinked structure forming a gel,
It can be confirmed that the copolymer is completely dissolved in decalin at 135 ° C.

In the above-mentioned cyclic olefin random copolymer (A) used in the present invention, in addition to the cyclic olefin and ethylene, α-
A copolymer obtained by adding and polymerizing an olefin (third monomer) and / or a cyclic olefin (other cyclic olefin) other than the cyclic olefin represented by the above formula [I] can also be used.

The α-olefin used herein may be linear or branched, and such α-olefin
Examples of olefins include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-
3 carbon atoms such as octadecene and 1-eicosene
.About.20 .alpha.-olefins can be mentioned. Among these, it is preferable to use an α-olefin having 3 to 15 carbon atoms, particularly 3 to 10 carbon atoms.

The "other cyclic olefin" is used in a broad concept including unsaturated polycyclic hydrocarbon compounds except the cyclic olefin represented by the formula [I]. More specifically, examples of other cyclic olefins include cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, styrene and α-methyl. Styrene and 3a, 5,6,7a-tetrahydro-4,7-methano-1H-
Indene, Bicyclo [2,2,1] hept-2- having aromatic ring
Ene derivative, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene derivative, 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene derivative and cyclopentadiene-acenaphthylene adduct And so on.

The repeating unit derived from the above α-olefin in the cyclic olefin random copolymer is 0 to
The repeating unit derived from 50 mol%, another cyclic olefin can be contained in an amount of 0 to 50 mol%. The softening temperature of the copolymer can also be controlled by adjusting the content of these repeating units.

When the other cyclic olefin has two or more double bonds in the molecule, the double bond remaining in the copolymer without contributing to the addition polymerization is hydrogenated. It can also be added.

After the addition polymerization is carried out as described above, hydrogenation is carried out if necessary so that the iodine value of the cyclic olefin random copolymer used in the present invention is usually 5 or less.
Below, in many cases, it can be set to 1 or less.

Cyclic Olefin Random Copolymer (Bi)
In, the cyclic olefin used as a raw material,
For example, having the structure represented by the above formula [IA] means that the ¹³ C--N
It can be confirmed from the MR measurement result. The structure as described above in the cyclic olefin-based random copolymer has high chemical stability.

Next, the cyclic olefin ring-opening polymer (B-ii) and hydrogenated ring-opening polymer (B-iii) used as the cyclic olefin resin in the present invention will be explained. Among cyclic olefin resins, cyclic olefin ring-opening polymer (B-ii)
Is a cyclic olefin represented by the above formula [I], for example, ruthenium, rhodium, palladium, osmium,
Indium or metal halide such as platinum,
A catalyst consisting of a nitrate or an acetylacetone compound and a reducing agent; a (co) polymerization while ring-opening in the presence of a catalyst consisting of a halide of a metal such as titanium, palladium, zirconium or molybdenum or an acetylacetone compound and an organic aluminum It can be manufactured by

In this cyclic olefin ring-opening polymer, at least a part of the cyclic olefin represented by the formula [I] is considered to have the structure represented by [IB].

[0069]

[Chemical 20]

[IB] In the above formula [IB], R ^{1 to} R ¹⁸ , R ^a and R ^b , and m, n and q have the same meanings as in formula [I].

The hydrogenated product (hydrogenated ring-opening polymer) (B-iii) of this ring-opening polymer is obtained by using the cyclic olefin ring-opening polymer (B-ii) obtained as described above, It can be produced by reduction with hydrogen in the presence of a hydrogenation catalyst.

The hydrogenation catalyst used here is
The catalysts usually used in hydrogenating olefins can be used. Such hydrogenation catalysts include heterogeneous catalysts and homogeneous catalysts. Specific examples of the heterogeneous catalyst used herein include nickel, metals such as palladium and platinum, or carbons of these metals,
A solid catalyst supported on a carrier such as silica, diatomaceous earth, alumina or titanium oxide can be mentioned. Representative examples of such carrier-supported solid catalysts include nickel / silica, nickel / diatomaceous earth, palladium / carbon, palladium / silica, palladium / diatomaceous earth and palladium / alumina. Further, the homogeneous catalyst is generally a catalyst based on Group VIII metal of the periodic table, and specific examples include nickel naphthenate / triethylaluminum, cobalt octenoate / n-
Examples of the catalyst include butyllithium, nickel acetylacetonate / triethylaluminum, a Ni compound or a Co compound, and an organometallic compound of a metal of groups I to III of the periodic table, and a catalyst containing an Rh compound.

Although various reaction conditions can be set in the hydrogenation reaction of the cyclic olefin ring-opening polymer, it is usually under a hydrogen pressure of 1 to 150 atm, and the reaction temperature is usually 0 to
The temperature is set to 180 ° C., preferably 20 to 150 ° C., and the reaction is performed. The hydrogenation rate can be adjusted in consideration of hydrogen pressure, reaction temperature, reaction time, catalyst concentration, etc.
In the present invention, 50 mol% or more, preferably 80 mol% or more, and particularly preferably 90 mol% or more of the double bond contained in the main chain of the ring-opening polymer is hydrogenated (Bi
By using ii), the blow molded article of the present invention has particularly good heat resistance and heat aging resistance.

In the hydrogenated product (B-iii) of this ring-opening polymer, at least a part of the cyclic olefin represented by the formula [I] has a structure represented by [IC]. it seems to do.

[0075]

[Chemical 21]

[IC] In the above formula [IC], R ^{1 to} R ¹⁸ , R ^a and R ^b , and m, n and q have the same meanings as in formula [I].

The modified cyclic olefin resin (B) used in the present invention is the above-mentioned cyclic olefin resin (Bi) or (Bi).
It is prepared by modifying i) and (B-iii) with an unsaturated carboxylic acid or a derivative thereof.

Examples of unsaturated carboxylic acids used herein include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, undecylenic acid, nadic acid. ^TM (endocis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid) can be mentioned. Furthermore, examples of the above-mentioned unsaturated carboxylic acid derivative include unsaturated carboxylic acid anhydrides, unsaturated carboxylic acid halides, unsaturated carboxylic acid amides, unsaturated carboxylic acid imides, and unsaturated carboxylic acid ester compounds. .
Specific examples of such derivatives include maleenyl chloride, maleimide, maleic anhydride, citraconic anhydride,
Mention may be made of monomethyl maleate, dimethyl maleate, glycidyl maleate, glycidyl acrylate and glycidyl methacrylate.

These grafting monomers can be used alone or in combination. Among the above graft monomers, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid ^TM or acid anhydrides thereof, or glycidyl methacrylate or glycidyl acrylate is particularly preferable, and more specific Most preferred compound is maleic anhydride.

The graft-modified cyclic olefin resin used in the present invention can be produced, for example, by modifying the above-mentioned graft monomer and cyclic olefin using various conventionally known methods. For example, there is a method of melting the cyclic olefin and adding a graft monomer to carry out graft polymerization, or a method of dissolving the cyclic olefin in a solvent and adding a graft monomer to carry out graft copolymerization. Further, as a method for producing a graft-modified cyclic olefin resin, a method in which an unmodified cyclic olefin resin is mixed with a graft monomer so as to have a desired graft modification rate, and a graft modification with a high graft modification rate is performed in advance. There is a method of preparing a cyclic olefin resin and diluting the cyclic olefin resin having a high modification rate with an unmodified cyclic olefin resin to produce a graft-modified cyclic olefin resin having a desired modification rate. In the present invention, the graft-modified cycloolefin resin produced by any method can be used. In the present invention, the graft-modified cycloolefin resin has a modification rate of usually 0.001 to 5% by weight, preferably 0.05 to 4% by weight, particularly preferably 0.1 to 2% by weight. Graft modified copolymers within the range are used.

In order to efficiently graft-copolymerize the above-mentioned graft monomer, it is preferable to carry out such a reaction in the presence of a radical initiator. The graft reaction is usually performed at a temperature of 60 to 350 ° C. The ratio of the radical initiator to be used is the unmodified cyclic olefin resin 1
The amount is usually 0.001 to 5 parts by weight with respect to 00 parts by weight.

As the radical initiator, organic peroxides and organic peresters are preferably used. Specific examples of such radical initiators include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide and di-tert-. Butyl peroxide, 2,5-dimethyl-2,5-di (peroxide benzoate) hexyne-
3,1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butylperacetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5- Dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylperbenzoate, t
ert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate,
Mention may be made of tert-butyl perpivalate, cumyl perpivalate and tert-butyl perdiethyl acetate. Further, in the present invention, an azo compound can be used as a radical initiator, and specific examples of the azo compound include azobisisobutyronitrile and dimethylazoisobutyrate.

Of these, radical initiators such as benzoyl peroxide, dicumyl peroxide,
Di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (t
ert-Butylperoxy) hexyne-3,2,5-dimethyl-2,5
-Di (tert-butylperoxy) hexane, 1,4-bis (te
Dialkyl peroxides such as rt-butylperoxyisopropyl) benzene are preferably used.

The graft-modified cycloolefin resin (B) thus obtained can be used alone or
It can also be used in combination. The graft-modified cyclic olefin resin (B) used in the present invention is 135
The intrinsic viscosity [η] measured in decalin at ℃ is 0.05 ～
It is necessary to be 10 dl / g, and it is preferable to use a graft-modified cyclic olefin resin (B) having an intrinsic viscosity [η] in the range of 0.08 to 5 dl / g. Blow molding can be efficiently performed by using the graft-modified cycloolefin resin (B) having an intrinsic viscosity within the above range.

The softening temperature (TMA) of the graft-modified cycloolefin resin (B) used in the present invention measured by a thermo mechanical analyzer is usually 70 ° C or higher, preferably 90 to 250 ° C. And more preferably in the range of 100 to 200 ° C. Further, the glass transition temperature (Tg) is usually 50 to 230.
℃, preferably in the range of 70-210 ℃, X
The crystallinity measured by the line diffraction method is usually 0 to 10
%, Preferably 0 to 7%, particularly preferably 0 to 5%.

The blow-molded article of the present invention comprises the polyamide resin (A) and the graft-modified cycloolefin resin (B) as described above in a weight ratio of 98/2 to 2/98, preferably 95/5 to 5. It is produced from a composition containing a weight ratio of / 95.

Other components may be added to this composition within a range that does not impair the characteristics of the blow-molded article of the present invention. Examples of other components include resins obtained by graft-polymerizing maleic anhydride with an unsaturated carboxylic acid such as a graft copolymer ethylene propylene random copolymer or any derivative thereof, and a rubber component blended to improve impact strength. .. A heat resistance stabilizer, a weather resistance stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, a lubricant, a dye, a pigment, a natural oil, a synthetic oil, a wax and the like can be mentioned. Examples of stabilizers added as optional components include tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and β- (3,5-di-t-butyl). -4-Hydroxyphenyl) propionic acid alkyl ester and 2,2'-oxamide bis [ethyl-3 (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate and other phenolic antioxidants; fatty acid metal salts such as zinc stearate, calcium stearate and 12-hydroxy calcium stearate; glycerin monostearate.
Examples thereof include polyhydric alcohol fatty acid esters such as glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate and pentaerythritol tristearate. These can be used alone or in combination. An example of this combination is the combination of tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, zinc stearate and glycerin monostearate. Further, a filler may be added to the above composition within a range that does not impair the surface smoothness of the blow-molded product. Examples of fillers used here are silica powder (silica), diatomaceous earth, titanium oxide, alumina, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, dolomite, barium sulfate, calcium sulfite, talc. , Clay, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminium powder, molybdenum sulfide, boron fiber, silicon carbide fiber,
Polyethylene fiber, polyamide fiber, attabalgite, kaolin clay, carbon black, iron oxide, magnesium hydroxide, slate powder, sericite, quartz powder, calcium carbonate, magnesium carbonate, feldspar powder, barite,
Examples include fillers or reinforcing materials such as wax stone clay, gypsum, glass balloons, shirasu balloons, and thermosetting resin powders.

The resin composition used for producing the blow-molded article of the present invention can be obtained by mixing and kneading the above components. For the blow-molded article of the present invention, using the resin composition as described above, a molded article produced by an extrusion blow molding method, a molded article produced by an injection blow molding method, and a two-stage blow molding method are produced. There is a molded body that is processed. Conventional molding conditions can be adopted when manufacturing a molded product by using these blow molding methods. That is, by blending a specific graft-modified cycloolefin resin with a polyamide resin, a blow molded article can be produced from a polyamide resin, which has been difficult to blow-mold by using a conventional blow method.

The blow-molded article of the present invention is used for, for example, automobile interior parts (for example, instrument panel, automobile exterior parts (for example, bumper fender, bonnet spoiler,
Trunk tailgates, etc.), other automobile parts (ducts, hoses, pipes, etc.), office equipment, tools, various containers for home appliance housings, various toys such as floats, various leisure products,
It can be used as parts for leisure vehicles and daily parts for baths or kitchens.

[0090]

The blow-molded article of the present invention is formed of a resin composition containing a polyamide resin (A) and a specific graft-modified cycloolefin resin (B). The resin composition is a polyamide resin. Since the melt tension is significantly increased as compared with (A), it is possible to obtain a blow-molded article that cannot be produced by using only the polyamide resin (A). When a resin composition composed of a polyamide resin and a modified polyethylene is used, the high temperature rigidity is significantly reduced, and when an inorganic filler is added to compensate for this high temperature rigidity, the high temperature rigidity is improved, but a blow molded product is obtained. The surface smoothness (broth) of the resin deteriorates significantly and the appearance is impaired. On the other hand, by using the specific graft-modified cyclic olefin resin (B), both improvement of high temperature constitution and surface smoothness are satisfied at the same time. It is possible to obtain a blow molded product.

[0091]

EXAMPLES The present invention will be specifically described below 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 tension The composition obtained in the example melted by heating to 260 ° C. was melt tension tester (manufactured by Toyo Seiki, nozzle length = 8).
mm, nozzle diameter = 2 mm), and the tension (melt tension) applied to the filament when the extruded strand was taken at a speed of 15 mm / min was measured.

(2) Bending test A test piece was cut out from the blow-molded body obtained in the example,
It was performed according to ASTM D790. Test piece shape: 1
2.5 × 7.5 × 2 ^t mm, span distance 51 mm Test speed: 20 mm / min Test temperature: 80 ° C. (3) Gloss A test piece was cut out from the blow-molded body obtained in the Example.
For this test piece, set the angle to 60 ° C and
It measured according to MD523.

[0094]

Example 1 A maleic anhydride modified resin which is a modified cyclic olefin addition polymer (B) was prepared by the following method.

The ethylene content measured by ¹³ C-NMR was 62 mol%, MFR ₂₆₀ ^° _C. was 35 g / 10 min, intrinsic viscosity [η] measured in decalin at 135 ° C. was 0.47 dl / g, TM
A with 170 ° C and Tg of 159 ° C, ethylene, 1,4,5,
8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene (ie, tetracyclo [4,4,0,12.517.10] -3-dodecene, abbreviated as "DMON" hereinafter. Sometimes)) (Ethylene / DMON random copolymer)
50 g of maleic anhydride dissolved in 60 g of acetone, organic peroxide (manufactured by NOF CORPORATION)
After adding 10 g of Perhexin 25B (trademark) and mixing them well, they were melted and reacted at a cylinder temperature of 250 ° C. using a twin-screw extruder (PCM 45, manufactured by Ikegai Tekko Co., Ltd.), and then pelletized using a pelletizer. ..

The maleic anhydride content in the obtained maleic anhydride modified resin was 0.4% by weight (0.3% by weight as the acid anhydride group content). Next, as the component (A), a polyamide resin (6 nylon CM10 manufactured by Toray Industries, Inc.)
41 LO (trademark) pellets (6.0 kg) and, as the component (B), 4.0 kg of maleic anhydride-modified resin pellets prepared by the above-mentioned method were thoroughly mixed, and then the cylinder temperature was adjusted by a twin-screw extruder (same as above). The mixture was melt-blended at 250 ° C. and pelletized with a pelletizer.

The melt tension was measured using the pellets thus obtained, blow moldings were prepared, and the physical properties of the blow moldings were evaluated according to the methods described above. The results are shown in Table 1.
Shown in.

[0098]

Example 2 Pellets were prepared in the same manner as in Example 1 except that the blending amounts of the components (A) and (B) were as shown in Table 1, and blow molded articles were prepared from these pellets. It was manufactured, and its physical properties were evaluated in the same manner as in Example 1.
The results are shown in Table 1.

[0099]

Comparative Example 1 Melt tension was measured in the same manner as in Example 1 except that only 6 nylon CM1041LO used as the component (A) in Examples 1 and 2 was used and no graft-modified cyclic olefin resin was used. It was The results are shown in Table 1.

This composition had a large drawdown, a blow molded product was not obtained, and the physical properties of the blow molded product could not be evaluated.

[0101]

Comparative Examples 2 and 3 In Example 1, instead of the graft-modified cycloolefin resin as the component (B), a polypropylene resin (B200 manufactured by Mitsui Petrochemical Industry Co., Ltd.,
Trademark) and polyethylene resin (8000F, trademark manufactured by Mitsui Petrochemical Industry Co., Ltd.) were modified with maleic anhydride in the same manner as in Example 1.

A maleic anhydride-modified polypropylene [C] component (Comparative Example 2) and a maleic anhydride-modified polyethylene [D] component (Comparative Example 3) thus obtained were used as components (B) of a graft-modified cyclic olefin resin. A composition was prepared in the same manner as in Example 1 except that it was used instead, a blow-molded article was produced from this composition, and the physical properties of this composition and the blow-molded article were measured. The results are shown in Table 1.

[0103]

Comparative Example 4 A composition was prepared in the same manner as in Comparative Example 3, except that 20 parts by weight of talc (Matsumura Sangyo Co., Ltd., High Filler 15DS trademark) was blended, and a blow molded product was produced from this composition. The physical properties of this composition and the blow-molded article were measured. The results are shown in Table 1.

[0104]

[Table 1]

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display area B29L 22:00 4F C08L 77:00

Claims (1)

[Claims] 1. A cyclic olefin-based random prepared by addition polymerizing (A) a polyamide resin, (B) (Bi) ethylene and at least one cyclic olefin represented by the following formula [I]: A copolymer, (B-ii) a cyclic olefin ring-opening polymer prepared by ring-opening polymerization of at least one cyclic olefin represented by the following formula [I], and (B-iii) the ring-opening Hydrogenated polymer, cyclic olefin resin selected from the group consisting of modified with unsaturated carboxylic acid or its derivative, the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.05 to 10 dl /
2/9 with modified cyclic olefin resin in the range of g
A blow-molded article formed from a resin composition containing 8 to 98/2 in a weight ratio; [I] (In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a and R are ^b's each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are each
R ¹⁵ and R ¹⁶ may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond. Alternatively, R ¹⁷ and R ¹⁸ may form an alkylidene group).