JPH03726A - Blow molded item - Google Patents

Abstract

PURPOSE:To improve chem. resistance, impact resistance and mechanical strength by blow-molding a specified cyclic olefin resin. CONSTITUTION:A cyclic olefin resin consisting of a (co)polymer (or hydrogenated product thereof), obtd. by performing ring opening polymn. of a cyclic olefin component of formula I (wherein R<1-12> are each H, a halogen or a hydrocarbon group; R<9-12> are bound to each other and a monocyclic or polycyclic group wherein double bonds may be incorporated or an alkylidene may be formed of R<9> and R<10> or R<11> and R<12>; n is 0 or a positive integer) or formula II (wherein lis 0 or larger; m and n are each 0-2; R<1-15> are each H, a halogen, an aliph. hydrocarbon group or an arom. hydrocarbon group and R<5> or R<6> and R<9> or R<7> may be bound together through a 1-3C alkylene or a direct bond) or a copolymer obtd. by addition-polymerizing said cyclic olefin component and ethylene component, is injected into a preform 10 consisting of a core and a cavity and having a bottom 12 and then transferred into a blow molding part, where the preform is put in between split molds and is drawn in a vol. ratio of 2-20 by blowing air.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to blow molded products.More specifically, the present invention relates to blow molded products made from a cyclic olefin polymer.Blow molded products with excellent chemical resistance and impact resistance. Regarding products.

I Mamedate Gogoe 11 One-turn extrusion blow, injection blow, two-stage blow, etc. are known as blow molding methods for synthetic resins, and the materials for these blow molded products include Hiroshima Polyester JI & Polycarbonate resin, etc. It has been known. In particular, in plastic containers obtained by stretching a parison (preform) made of polyester resin in the axial direction and expanding it in the circumferential direction with fluid in a mold based on injection blowing, the body of the container is The molecules are biaxially oriented and are widely used as containers with excellent transparency, gas barrier properties, heat resistance, etc.

These conventional blow-molded products made from polyester resin, polycarbonate resin, etc.
Depending on the application, chemical resistance such as acid resistance, alkali resistance, and boiling water resistance may become a problem.

OBJECT OF THE INVENTION It is an object of the present invention to provide a blow-molded product having chemical properties to solve the problems of conventional blow-molded products. Furthermore, another object of the present invention is to provide a blow molded product that not only has excellent chemical resistance but also excellent mechanical strength.

1 Plate Standing 1 Blow-molded product according to the present invention 1 A polymer obtained by ring-opening polymerization of a cyclic olefin component represented by the following formula [I] or the following formula [n], a copolymer, and its hydrogenation process; The following formula [I] or the following formula [
(2) It is characterized by being molded from a cyclic olefin resin selected from the group consisting of copolymers formed by addition polymerization of a cyclic olefin component represented by C and an ethylene component.

... [Eco [In the above formula [11], n130 or a positive integer, R1-R12 each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. R9-R1 214 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 R8 and R1@, Alternatively, RII and Rli may form a thealkylidene group. ]...[nl [In the formula, 9 is O or an integer of 1 or more, m and n
1 value is 0.1 or 2, and R1 to Rls each independently represent a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group.
An aromatic hydrocarbon group or an alkoxy group, which may be bonded to R6 (or Re) and R9 (or R?) through an alkylene group having 1 to 3 carbon atoms, or without any group. It may be directly linked to. ] Present invention j4 This invention is based on the knowledge that chemical resistance is significantly improved by using a cyclic olefin polymer as a material for blow-molded products.

Cyclic olefin polymer $ Gourd has excellent chemical resistance,
Blow molded products made from this material have excellent chemical resistance such as acid resistance, alkali resistance, and boiling water resistance. By selecting the cyclic olefin polymer to be used, blow-molded products made of cyclic olefin polymers can have even greater mechanical strength. Applications: Blow-molded products with especially excellent impact strength can be provided.

Furthermore, if the blow-molded product does not require transparency, etc., it is possible to further increase the impact strength by blending other resins such as elastomers within a range that does not impair the purpose of the present invention.

Hereinafter, the blow molded product according to the present invention will be specifically explained.

[Type of cyclic olefin component] The blow-molded product according to the present invention (gourd) is a polymer or copolymer obtained by ring-opening polymerization of a cyclic olefin represented by the following formula [1] or the following formula [II], or a hydrogenation process thereof. And/or it is formed from a copolymer formed by addition polymerization of a cyclic olefin represented by the following formula [1 or the following formula [, nl] and an ethylene component.

...[rl Takitsune In the above formula [xl, both n and m are O or a positive integer, and R1-R12i4 are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, or a hydrocarbon group, or represents an atom. Sara G;
R@-Rl 213 may be bonded to each other to form a monocyclic or polycyclic group, and this ring may have a bridged structure. Furthermore, this monocyclic or polycyclic group may have a double bond. Furthermore, it may be a group in which these rings are combined.

That is, the above R9 to RI2 may jointly form, for example, a polycyclic or monocyclic group as described below.

do not have.

In addition, in the above formula, carbon atom 1 to which 1 and 2 are added
4 In formula [E], represents a carbon atom of an alicyclic structure to which groups represented by R9 to RI2 are bonded.

Samo & Mi These groups may have a substituent such as a methyl group.

Additionally, +:=R@ and R11 or R1 and Re2 may form an alkylidene group. Sara 4;R
1-R12 may contain an ester group, etc. [
■ In the formula, 9 is O or an integer greater than or equal to 1, and m and n are 0. 1 or 2, R1 to RIS each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an alkoxy group, and R6 (
or Re) and R11 (or R?) are 1, carbon number 1
-3 may be bonded via an alkylene group, or may be bonded directly without any group.

Preferred examples of such cyclic olefins include cyclic olefins represented by the following formula [ml].

...[m] However, in the above formula [ml, n is 0 or 1, m is O or a positive integer, and R1 to R1 are each independently composed of a hydrogen atom, a halogen atom, and a hydrocarbon group. Represents an atom or group selected from the group.

Sara & Mi RI S x RI @ 14 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.

Also, between RIs and RIs, or R1? and Re8 may form an alkylidene group.

In addition, olefin polymer particles having an alicyclic structure, such as the formula [rl or the formula [ml, or preferably the formula [lII
] may be a ring-opening polymer or a ring-opening copolymer obtained by carrying out ring-opening polymerization as shown in the following formula either alone or in the coexistence.

Furthermore, in the present invention, a hydrogenated product obtained by hydrogenating at least a part of the double bonds present in the ring-opened polymer or ring-opened copolymer as described above can also be used. .

The above formula [rl or formula [■], or preferably the formula [
Cyclic olefin represented by rl1 can be easily produced by condensing cyclopentadiene and the corresponding olefin milk or cyclic olefin by Diels-Alder reaction.

The cyclic olefin represented by the above formula Ctl used in the present invention is specifically 14-bicyclo[2,2,11hept-2-ene-derived tetracyclo[4,4,0,1''・S, l 〒1 (3-dodecene derivative hexacyclo[6,6,1,13,6,111,13,
O2, 7, Qi order] -4-heptadensene induction book, t ri 9 Schiff C1 [8, 8, 0, L29.1',
" , 11 ', '",1"-'・Ql*
, O12,+7]-5-tococene derivative pentacyclo[
8, 6, 1, 13, @ , 02・), Italy・+4l-4
-Hexadecene derivative image Heptacyclo-5-icosene derivative Main heptacyclo 5-heneicosene derivative, tricyclo[4,3,0,12・s]-3-decene derivative Main tricyclo[4,3,0,1”・s]- 3-undecene derivative pentacyclo[6,5,1,13・6.02・7.09・
-4-pentadecene induction book pentacyclopentadecadiene induction arc pentacyclo [4, 7, 0, 12, 5. Oe・13.1
-・If]-3-pentadecene derived image pentacyclo['7.8tO+1"'102.'+1"
"'+0""@112.1s]-4-eicosene induced image and nonasif l:I [:9,10,1,1,4.7.O3
-”, 02.I@, 012.21113.2@, O14
, 1 town 1+s, +5l-5-/(:/9: Isen derivatives are mentioned.

Specific examples of such compounds are shown below.

hmm 5.10-dimethyltetra CH.

Bicyclo[2,2,11hept-2-ene derivatives such as 2,7.9-trimethylteCH.

8-methyltetrashif 8-ethyltetrashif +11]-3-dodecene C,,H,.

1m]-]3-dodese -isobutyl-11,12 5,8,9,10-tetramethy 1＠　]-]3-Dodese -Methyl-9-ethylte =3-dodecene -3-dodecene +-co-3-dodecene Ia]-3-dodecene CH.

[4, 4,0,12,s, lv, +@]-3-dodecenecro[4,4,0,12 +11]-3-dodecene8-n-propylidene-9 [4,4,0,12 5,1) 1@]-3-dodecene 5.17 i.]-]3-dodecene-dodecene, 12 5.17 1Q]-3-dodecene-dodecene 12,s,1teIa]-3-dodeceneS,1? 1@]-3-dodecene 8-n-propylidene-9 C11゜-dodecene 8-isopropylidene-dodecene 1.]-]3-dodece-dodecene and other tetracyclo[4,4,0,125,17 Li 3 -dodecene derivative; (blank below) 14]-4-hebutadecene+3. Q2. ? , Q9. +4] -4-heptadecene and other hexacyclo[6,6,1,13・8,111+
3. Q2.7. Q@decene+4]-4-hebutadecene derivative decentcocene ■, 1@, 113. +6. Q3.・, Ql heptadecene 1]-5-tococene 15-ethyl octashif 2.1 ma]-5-tococene and other octacyclo[8,8,0,129,14 〒11+e, 1+ 6.03・@, Ql 2,1 Te]-5-tocosene derivatives; 1,13・6.02・7
,0嘗+4]-4-hexadecene derivative; 5-methyl-tricyclo1,3-dimethyl-pentane, -゛ tricyclo[4,3,0,121-3-decene derivative; 10-methyl-tricif 14, To tricyclo[4,4,0,1”S]-3-undecene-derived nato (1) such as 15-dimethylben: /9 cyclo[6,5,1
,13・′,02〒,0”Is]-4-pentadecene derivatives; ,1!・S, Italy・13,1・1ffi] -3-pentadecene derivative; 3.2-, I14.lI, 1111 +1] -5-bentacocene and other nonacyclo[9,10,1,14・7. 03 @, I2. Electron-■ I2 double, 1st 2e, 0th, 19.11% I@] -5-bentacocene derived cocene body can be mentioned.

(Left below) y, 1+@, +t, 0th, 111.11+8] -4-Eicosene, etc., hebutacyclo[7,8,0,13 6, (p, 11111 17.0 +s, 142 5I -4- Eicosene derivative; Further, as the cyclic olefin represented by the above formula [■] used in the present invention, specifically, the following compounds may be mentioned.

Specifically, the polycyclic olefin represented by the formula [11] In addition to hydronaphthalene, 2-methyl-1,4,5,8-
Dimethano-1,2,3,4゜4a, 5.8.8a-octahydronaphthalene, 2-ethyl-1,4,5,8-
Dimethano-1,2,3,4,4a, 5.8.8a-octahydronaphthalene, 2-propyl-1,4,5,8
-Dimethano-1゜2, 3.4.4a, 5.8.8a-
Octahydronaphthalene, 2-hexyl-1,4,5,
8-dimethano-1,2,3,4,4a, 5.8.8a
-octahydronaphthalene, 2,3-dimethyl-1,4
,5,8-dimethano-1,2,3,4,4a, 5.8
．． 8a-octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5.8.8a-octahydronaphthalene, 2-chloro-1,4,5,8-dimethano-1,2,3,4,4
a, 5.8.8a-octahydronaphthalene, 2-bromo-1,4,5,8-dimethano-1°2, 3.4.4
a, 5.8.8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4,
4a, 5.8.8a-octahydronaphthalene, 2.
3-dichloro-1,4,5,8-dimethano-1,2,3
,4,4a, 5.8.8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1
, 2゜3, 4.4a, 5.8.8a-Octahydronaphthalene, 2-n-butyl-1,4,5,8-dimethano-1,2,3,4,4a, 5.8.8a Examples include octahydronaphthalenes such as -octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, and 5.8.8a-octahydronaphthalene. can.

[Cyclic olefin polymer] As the cyclic olefin polymer used in the blow-molded article of the present invention, (Dai (1) a ring-opening polymer of a cyclic olefin represented by the above formula [I] or formula [n], or Examples include a ring-opened copolymer or a hydrogenated product thereof, and (2) a copolymer obtained by addition polymerization of a cyclic olefin represented by the above formula [I] or formula [n] and ethylene.

It is a homopolymerized or copolymerized product. Even if 1,4,5.8-dimethano-1,2
, 3,4,4a, 5.8.8a- Octahydronaphthalenes copolymerized with each other, or the above-mentioned norbornene (bicyclo(2,2,1-cohept-2-ene)) copolymerized But that's fine.

In the ring-opening polymer or ring-opening copolymer of a cyclic olefin as described above, for example, at least a part of the cyclic olefin represented by the formula [[0] (having a structure represented by the following formula rrvl) considered to be a thing.

A cyclic olefin ring-opening polymer (Dai) A cyclic olefin represented by the above formula [I] or formula [■], preferably [[[l], is subjected to ring-opening polymerization by a method known per se... [■] , the ring-opening polymer itself can easily hydrogenate residual double bonds by a method known per se, and the hydrogenated product is an injection molding material with better thermal stability and weather resistance. .

In such a hydrogenated product, at least a part of the cyclic olefin represented by the formula [ml], for example, has the following formula [V]
It is thought that it has the structure expressed as follows.

Other cyclic olefins can be ring-opened and copolymerized within a range that does not impair the physical properties of the ring-opened (co)polymer.

Examples of such cyclic olefins include cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2-(2
-methylbutyl)-1-cyclohexene, 2.3.3a
, 7a-tetrahydro-4,7-methano-IH-indene and 3a, 5.6.7a-tetrahydro-4,
Examples include 7-methano-IH-indene.

- [V] In the above formulas [■] and [v], R+ to R+ * have the same meanings as in the formula [ml].

In addition, when carrying out ring-opening polymerization of a cyclic olefin, the above formula [
In a cyclic olefin addition polymer formed from a cyclic olefin represented by formula I] or formula [■, or preferably formula [III], the ethylene component/cyclic olefin component (molar ratio) is usually 1°/90 to 90/ 10 thea 1),
Good:! L< is 50150 to 75/25. The ethylene copolymer is produced 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 organoaluminium compound. Such a polymerization method is already known and has been proposed in Japanese Patent Application Laid-Open No. 168708/1983.

In addition, in the cyclic olefin addition polymer, the above formula [
A monomer (an olefin compound) that is copolymerized with a cyclic olefin compound represented by the formula [nl, or preferably [ml] to constitute a copolymer having an alicyclic structure; Ethylene is usually used as an olefin compound in the copolymer having an alicyclic structure used in the present invention. The compound can also be copolymerized.In the present invention, other olefins that can be copolymerized with ethylene and the cyclic olefin compound represented by the above formula [I] or formula [II], or preferably formula [III]. Examples of compounds include Idai propylene, 1-butene, 4-methyl-1-
α-olefin cyclopentenes having 3 to 20 carbon atoms, such as pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene;
Cyclohexene, 3-methylcyclohexene, cyclooctene and 3a, 5.6.7a-tetrahydro-4
, 7-methano-IH-indene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopenta 5-ethylidene-
Non-conjugated dienes such as 2-norbornene and 5-vinyl-2-norbornene; Norbornene-2,5-methylnorbornene 5-ethylnorbornene 5-isopropylnorbornene 5
-n-butylnorbornene-2,5-i-butylnorbornene to 5,6-dimethylnorbornene to 5-chloronorbornene 2-fluoronorbornene-2 and 5
, 6-cyclonorbornene-2, and other norbornenes. Among these, a-olefins having 3 to 15 carbon atoms, particularly 3 to 10 carbon atoms, are preferred.

These other olefins can be used alone or in combination.

When using a cyclic olefin other than the cyclic olefin of formula [I] or formula [I[] or [ml] having two or more double bonds in the molecule, hydrogen is added for the purpose of improving weather resistance. It can be added and used.

The iodine value of the cyclic olefin addition polymer is usually 5 or less, and most of them are 1 or less.

In such a cyclic olefin random copolymer,
For example, at least a portion of the repeating units derived from a cyclic olefin [DX] are considered to have a structure represented by the following formula [VI].

...[VI] In addition, in the above formula [VT], R1 to Rl 814
These have the same meaning as in the formula [m,].

Cyclic olefin 8 For example, the structure shown in [■] to [■] above is observed.The obtained polymer is subjected to +IC-NMR
This is supported by analysis. Such a cyclic olefin addition polymer has a chemically stable structure and is a polymer with excellent heat aging resistance.

The above-mentioned (1) cyclic olefin ring-opening polymer and its hydrogenated product and (2) cyclic olefin addition polymer have an intrinsic viscosity [V] of 0.01 to 20 dl/, measured in decalin at 135°C. g, especially 005 to 10
dl/g, more preferably 0.08 to 8 di/g.

These cyclic olefin polymers generally have poor quality or low crystallinity, and preferably have poor quality.

Therefore, transparency is good.

In general, the degree of crystallinity measured by X-rays is less than 5%, and in most cases it is 0.
In many cases, the melting point cannot be observed using a differential scanning calorimeter (DSC).

Other properties of such cyclic olefin polymers include high glass transition temperature Tg and high softening temperature (TMA). Glass transition temperature Tg is usually 50 to 230
°C, mostly measured within the range of 100-200 °C. Therefore, when directly used as a molding material, the softening temperature is usually measured within the range of 70 to 180°C, and in most cases, within the range of 90 to 180°C.

In addition, the thermal decomposition temperature is usually 350 to 420℃, often 3
It is within the range of 70 to 400°C.

As for mechanical properties, the bending modulus of the resin itself is usually in the range of 1xlO' to 5x10'Kg/cm2, and the bending strength is also usually in the range of 300-1500Kg/cm2.

In addition, the density of this resin itself is usually 0.86 to 1,
Log/ca? , most of which are 0.88-1.08g/c
It is in the range of m'. Also, the refractive index (ASTM D542
) is usually 1.47 to 1.58, mostly 1°48 to 1.5
6 and is substantially amorphous, so the haze (Haze: ASTM DIOo 3') iL
It is usually less than 20%, often less than io%.

As for electrical properties, the dielectric constant (IKHz) of this resin itself measured by ASTM D150 is usually 1. 5-3
．． 0, mostly 1. 9-2.6, dielectric loss tangent is usually 9X
10-4~8XIO-1 mostly 3x10-'~9X1
It is within the range of 0-'.

The blow-molded product of the present invention using such a cyclic olefin polymer has excellent chemical resistance. Even when the blow-molded product is immersed in sulfuric acid, ammonia, acetone, or ethyl acetate for 24 hours, there is no discoloration or decrease in transparency. Blow-molded product L according to the present invention can be made of a so-called polymer alloy obtained by blending various polymers with the above-mentioned cyclic olefin polymer. Examples of these polymers include the following 1 to 17.

1. Polymers derived from hydrocarbons having one or two unsaturated bonds, specifically polyolefins, such as polyethylene, polypropylene, polymethylbutene, poly4-methylpentene, which may have a crosslinked structure -Polybutene-L
Polystyrene, 2. Halogen-containing vinyl polymers, specifically polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene, chlorinated rubber, etc. 3. Polymerization derived from a, β-unsaturated acids and their derivatives Example 1: Specifically, polyacrylate, polymethacrylate, polyacrylamide, polyacrylonitrile, or copolymers with monomers constituting the above polymers.
4 Acrylonitrile/butadiene/styrene typical combination Acrylonitrile/styrene typical combination Acrylonitrile/styrene/acrylic acid ester copolymer, etc.
4. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, specifically polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate 5. Polymers derived from epoxides, specifically polyethylene oxide or bisglycidyl ether. 6. Polyacetals, specifically polyoxymethylene, polyoxyethylene, etc.
7. polyoxymethylenes containing ethylene oxide as comonomer, 7. polyphenylene oxide, 8. polycarbonates, 9. polysulfones, 10. polyurethanes and urea resins, 11. derived from diamines and dicarboxylic acids and/or aminocarboxylic acids or the corresponding lactams. polyamides and copolyamides, specifically nylon 6, nylon 6
6, Nylon 11, Nylon 12, etc.; ■ Polyesters derived from dicarboxylic acids and dialcohols and/or oxycarboxylic acids or corresponding lactones, specifically polyester terephthalate, polybutylene terephthalate, poly 1,4-dimethylol cyclohexane terephthalate. Polymers with a crosslinked structure derived from n aldehyde and phenol, urea or melamine, specifically, phenol-formaldehyde resin, urea-formaldehyde resin, melamine-formaldehyde resin, etc. 14 Alkyd resin, specifically glycerin・Phthalic acid resins, etc. δ derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols, unsaturated polyester resins obtained using vinyl compounds as crosslinking agents, and halogen-containing modified resins, Nagi natural type Specifically, cellulose rubber, protein, or their derivatives such as cellulose acetate, cellulose propionate, cellulose ether, etc. In addition, the cyclic olefin polymer, these rubbery components, and IL
This polymer alloy forms a so-called "polymer alloy" and can be used as is.This polymer alloy may be subjected to a crosslinking reaction in the presence of an organic peroxide to form a crosslinked structure. By using such a crosslinkable polymer alloy, the rigidity and impact resistance of the blow molded product are improved.

(Soft polymer having a cyclic olefin structure (1)) Soft polymer having a cyclic olefin structure; Cyclic olefin of the same type used in preparing the ethylene component and the cyclic olefin polymer (represented by formula [I]) It is a tertiary or higher copolymer prepared by copolymerizing a compound (compound) and an a-olefin. Examples of α-olefins include propylene, 1-butene, 4-
Methyl-1-butene, 1-hexene, 1-octene,
1-decene, 1-dodecene, 1-tetradecene, 1
-hexadecene, 1-octadecene, 1-eicosene, and the like. Among these (Dai, number of carbon atoms is 3)
-20 olefins are preferred. Also, norbornene,
Cyclic olefins and cyclic dienes such as ethylidene norbornene and dicyclopentadiene can also be used effectively.

In the soft polymer (i) having a cyclic olefin structure, the number of repeating units derived from the ethylene component is usually 40 to 98 mol%, preferably 50 to 90 mol%. The repeating unit derived from the α-olefin component is usually contained in an amount of 2 to 50 mol%, and
Repeating units derived from cyclic olefin components
It is contained in an amount of 2 to 20 mol%, preferably 2 to 15 mol%.

Soft polymer (i) iL Unlike the above-mentioned cyclic olefin polymer, it has a glass transition temperature (Tg) of usually 0°C or lower, preferably -10°C or lower, and an intrinsic viscosity measured in decalin at 135°C [1 ] is usually 0.01 to 10
The d1 momme of the copolymer is preferably within the range of 08 to 7 dl/g. The soft polymer (i) is a copolymer whose crystallinity as measured by X-ray diffraction is usually in the range of 0 to 10%, preferably 0 to 7%, particularly preferably 0 to 5%. It is.

Soft polymer (i) ink, e.g. JP-A-60-1
No. 68708 Public Corporation JP-A-61-120816 Public-Grudge JP-A-61-115912 Public-Private JP-A-61-1159
Publication No. 16 Public Corporation No. 61-271308 Publication Publication JP-A-61-272216 and JP-A-62-2524
It can be manufactured by selecting appropriate conditions based on the method proposed by the present applicant in Japanese Patent No. 06 and the like.

(α-olefin copolymer (ii)) α-olefin copolymer (ii) used as a soft polymer in the present invention
HL A non-quality to low crystallinity copolymer formed from at least two kinds of α-olefins. Specific examples include ethylene/a-olefin copolymers and propylene/a-olefin copolymers.

The α-olefins constituting the ethylene/a-olefin copolymer are usually α-olefins having 3 to 20 carbon atoms. Specific examples of such α-olefins include propylene, 1-butene, etc. , 4-methyl-1-butene, 1-hexene, 1-octene, 1-
and mixtures thereof.

Of these, a-olefins having 3 to 10 carbon atoms are particularly preferred.

The molar ratio of the ethylene/a-olefin copolymer (ethylene/me olefin) (force f1, which varies depending on the type of α-olefin) is generally preferably 40/60 to 9515. When is propylene, it is preferably from 40/60 to 90/10, and when the a-olefin has 4 or more carbon atoms, it is preferably from 50,150 to 9,515.

As the a-olefin constituting the propylene/a-olefin copolymer, those having 4 to 20 carbon atoms are usually used. Specific examples include 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-
Mention may be made of decene and mixtures thereof. Of these, α-olefins having 4 to 10 carbon atoms are particularly preferred.

In the above-mentioned propylene/α-olefin copolymer, the molar ratio of propylene and a-olefin (propylene/me olefin) varies depending on the type of olefin.Generally, 50150 to 9515
It is preferable that

(a-olefin/diene copolymer (iii)) As the a-olefin/diene copolymer (iii) used as a soft polymer in the present invention, 1-turn ethylene/a
-Olefin/diene copolymer rubber and propylene/
Examples include a-olefin/diene copolymer rubber.

A-olefin that constitutes these copolymer rubbers
Usually, a-olefins having 3 to 20 carbon atoms (4 to 20 in the case of propylene/a-olefin), such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1- Examples include octene, 1-decene and mixtures thereof. Among these
A-olefins having 3 to 10 carbon atoms are preferred.

In addition, the diene component 14 constituting these copolymer rubbers
1.4-hexadiene, 1.6-octadiene, 2-
Methyl-1,5-hexadiene, 6-methyl-1,5-
linear nonconjugated dienes such as hebutadiene and 7-methyl-1,6-octadiene, cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-
Vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene and 6-chloromethyl-5
- Cyclic non-conjugated dienes such as isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene, etc. can be mentioned.

In the above ethylene/α-olefin/diene copolymer rubber, the molar ratio of ethylene to α-olefin (ethylene/
(Olefin) is generally 40/60 to 90/10, depending on the type of α-olefin.

Furthermore, the content of repeating units derived from the diene component in these copolymer rubbers is usually in the range of 1 to 20 mol%, preferably 2 to 15 mol%.

(Aromatic vinyl hydrocarbon/conjugated diene soft copolymer (iv)) Aromatic vinyl hydrocarbon/conjugated diene soft copolymer it used as a soft polymer in the present invention, aromatic vinyl carbonized It is a conjugated diene-based random block copolymer or a hydride thereof.

Specifically, styrene/butadiene block copolymer rubber, styrene/butadiene/styrene block copolymer rubber, styrene/isoprene block copolymer rubber,
Styrene/isoprene/styrene block copolymer rubber, hydrogenated styrene/butadiene/styrene block typical arc hydrogenated styrene/isoprene/styrene block copolymer rubber, styrene/butadiene random copolymer rubber, etc. are used.

In these copolymer rubbers, the molar ratio of aromatic vinyl hydrocarbon to conjugated diene (aromatic vinyl hydrocarbon/conjugated diene) is preferably from 10/90 to 70/30. Also, a hydrogenated copolymer rubber and a copolymer rubber in which part or all of the double bonds remaining in the above copolymer rubber are hydrogenated.

(Soft polymer or copolymer (V) consisting of isobutylene or isobutylene/conjugated diene) As the isobutylene-based soft polymer or copolymer (V) used as the soft polymer in the present invention, specifically, polyisobutylene Rubber, polyisoprene rubber, polybutadiene rubber, isobutylene/isoprene copolymer rubber, etc. are used.

The characteristics of the copolymers (11) to (v), which are soft polymers, are similar to those of the cyclic olefin soft polymer (1), and the intrinsic viscosity [V] measured in decalin at 135°C is usually 0.01 to 1061 momme, preferably 0.
It is within the range of 08-7 dl/g, and the glass transition temperature (
T g) is usually below 0°C, preferably below -10°C,
Particularly preferably, the temperature is -20°C or lower. Further, the degree of crystallinity measured by X-ray diffraction is usually in the range of 0 to 10%, preferably 0 to 79&S, and particularly preferably 0 to 5%.

With a polymer alloy containing such a rubbery component and a crosslinkable polymer alloy treated with an organic peroxide, 14 soft polymer component sections of various (1) to (V) per 100 parts by weight of the cyclic olefin addition polymer, 5-150 weight clothes
Preferably 5-100 weight clothes, particularly preferably 10-8
It is present in 0 parts by weight. By satisfying such a compounding ratio, a polymer alloy with well-balanced impact strength, rigidity, heat distortion temperature, and hardness can be obtained.

And also the melt flow index (M
FR, ASTM D1238 conditions) is 0. 1-1
Preferably it is 00.

In addition, as organic peroxides used when crosslinking polymer alloys with organic peroxides (ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide), 1,1-bis(t-butyl peroxide) Peroxyketals such as cyclohexane 2.2-bis(t-butylperoxy)octane, t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroxyperoxide and 1.1 .3. Hydroperoxides such as 3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, 2,5-dimethyl-2,
5-di(t-butylperoxy)hexane and 2.5
- dialkyl peroxides such as dimethyl-2,5-di(t-butylperoxy)hexyne-3, diacyl peroxides such as lauroyl peroxide and benzoyl peroxide, and i-22.5- Peroxy esters such as dimethyl-2,5-di(benzoylperoxy)hexane and the like can be mentioned.

The above organic peroxide component ↓ Dai is usually 0.01 to 1 weight part of paper, preferably 0.05 to 0.5, per 100 parts by weight of the total amount of the cyclic olefin addition polymer and the soft polymer component.
Used in parts by weight.

Then, when treating with an organic peroxide for the purpose of further increasing crosslinking efficiency, this reaction system and compound containing two or more radically polymerizable functional groups in the molecule can be used to improve impact resistance. This is preferred because a polymer alloy can be obtained.

Examples of compounds having two or more radically polymerizable functional groups in the molecule include divinylbenzene, vinyl acrylate, and vinyl methacrylate. These compounds 14 are usually used in an amount of 1 part by weight or less, preferably 0.1 to 0.5 part by weight, based on 100 parts by weight of the total amount of the cyclic olefin addition polymer and the soft polymer.

(Other additives) Cyclic olefin ring-opening polymers and hydrogenated cyclic olefin addition polymers used as raw materials in producing the blow-molded products of the present invention, cyclic olefin addition polymers, and polymers blended with these and various polymers. Heat resistance stability, weather resistance stability, antistatic IPL slip 41. Anti-blocking port Before anti-fogging Sliding dyes, pigments, natural sources Synthesis method Waxes, organic or inorganic fillers, etc. can be added.

Even if E, as a stabilizer added as an optional ingredient, 1
Dai Tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate comethane, β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid alkyl ester and 2,2
°-oxamidobis[ethyl-3-(3,5-di-t-
Phenolic antioxidants such as butyl-4-hydroxyphenyl) propionate, stearite, calcium stearate, and 1.
2- and fatty acid metal salts such as calcium droxystearate, polyhydric alcohol fatty acid esters such as glycerin monostearate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate and pentaerythritol tristearate, etc. I can do it. These may be blended alone (or may be blended in combination. For example, tetrakis[methylene-3-(3,5-di-t-butyl-4-
Examples include a combination of hydroxyphenyl)propionate comethane, zinc stearate, and glycerin monostearate.

We also use +4 silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice particles, pumice balloons, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, titanic acid as organic or inorganic fillers. Potassium, barium sulfate, calcium sulfite, talc, clay Mica, asbestos, glass woven rim Glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber Silicon carbide woven rim Polyethylene fiber polypropylene fiber kite
Examples include polyester fibers and polyamide fibers.

As a method for mixing the cyclic olefin polymer according to the present invention and other components, a method known per se can be applied, for example, each component can be mixed simultaneously.

(Blow molding method) Blow molded product 1 according to the present invention is molded using extrusion blow, injection blow, and two-stage blow method.

Figure 1 shows a cross-sectional view of a preform used in the injection blowing method for blow molded products according to the present invention. The preform 10 shown in FIG. 1 is molded by injecting molten resin into a mold consisting of a core mold and a cavity mold. The molten resin is made of a cyclic olefin polymer. The preform 10 has a bottom 12. The wall thickness A of the preform (for example, about 4.5 mm') can be easily controlled and there is no uneven thickness. In addition, the container opening 1
4 has sufficient accuracy required for sealing and cabling.

Condition 1 when forming a preform by injection etc.
The resin temperature varies depending on the TMA or MFH of the cyclic olefin copolymer.
Mold temperature 50-150'C1 injection pressure; - Pope 600
~1500 kg/cut, secondary pressure 400-1200k
The temperature of the preform is preferably within the range of ±50°C of the TMA of the resin used.

After such a preform 10 is transferred to a blow molding section, it is sandwiched between split molds and blow molded by blowing air into it. Moreover, the stretching ratio of the preform 10 is preferably in the range of 2 to 20 times in volume ratio.

(Application) The molded product of the present invention blow-molded in this way (a joke!
1 It can be used for the following purposes.

1. Detergent K Bleach L Shampoo Pharmaceutical Cosmetic Makeup &
Antifreeze method Various chemical containers such as acids and alkaline liquids2, various food containers such as 1A flavorings, beverages, foodstuffs, etc.3, bottle containers4, air ducts, demister nozzles, sun visor consoles, radiator tanks5, various toys 9. Toys and leisure goods such as floating floats for surfing; 6. Posts, wide mouths; Housings for electrical appliances, lighting gloves, bathtubs, and other daily necessities. [Examples] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.

The methods for measuring and evaluating various physical property values in the present invention are shown below. (1) Melt Flow Index (MFR)
), measured at a load of 2.16 kg (2) Softening temperature (TM
A) Thermo Mechanical A manufactured by DuPont
The thermal deformation behavior of a 1 mm thick sheet was measured using a nalyzer.
The temperature after 5 mm penetration was measured using TMA Tojishima (3) glass transition temperature (T g) SEI KOtoko Kogyo* DSC-20 at a heating rate of 10°C/min (4) Tensile test example From the obtained blow molded product, ASTM TYPE
(5) Annealing shrinkage rate measured by punching out dumbbells using the method of ASTM-D638. From the blow-molded product obtained in the example, a test piece of about 3 cm square was cut out and annealed at t-95°C for 10 minutes. (6) Cut out a test piece from the blow molded product obtained in the haze example and measure it according to ASTM D1003 (7) Blow molded product obtained in the gloss example For this test piece, set the angle to 60- and set the AS
Measured according to TM-D523, the blow molded product obtained in Example 9 (8) Chemical resistance was immersed in the following specified test solution and left at I-23°C for 7 days, there was no change in appearance.
If the tensile breaking strength measured by the method shown in (4) shows 90% or more of the value before the test, it is considered a pass. Test solution acid resistance; 20% sulfuric acid aqueous solution alkali resistance; 20% sodium hydroxide aqueous solution ( 9) Boiling water resistance After immersing the blow-molded product in boiling water for 24 hours, a random copolymer (13C-N
Ethylene content 71 mo1% measured by MR, MFR28
@'C20FI 1 minute, Intrinsic viscosity measured in decalin at 135℃ [7] 0.6dl Softening temperature (TMA)
The island was made by injection blow molding using
The molding conditions and physical properties of the blow-molded product are shown in Table 1.Random copolymer formed from W-random ethylene and DMON (ethylene content 62mol1% as measured by 13cm NMR)
, MF R2s, Oc 35g 7 min, intrinsic viscosity measured in decalin at 135°C [1] 0.47 dl/g
A random copolymer formed from ethylene and DMON (130-NMR Ethylene content 67 mo1% measured at
At M F R2go 'c 1787 minutes, 135℃
The intrinsic viscosity measured in decalin [vlo, 6 dl
Softening temperature (TMA) 135℃, glass transition temperature (T
g) 123°C) pellets3. 4 kg and ethylene.
Propylene random copolymer (ethylene content 80mol
%, the intrinsic viscosity [η
] 2. 2dl/i Glass transition temperature (Tg) -5
0℃) and 0.6kg of pellets were melt-blended using a twin-screw extruder (PCM45 manufactured by Ikegai Iron Works) at a cylinder temperature of 220℃, and pelletized using a pelletizer.The resulting pellets were then injection blow molded. The molding conditions and physical properties of the blow molded product are shown in Table 1.
Random copolymer formed from ethylene and DMON (ethylene content 62 mol measured by 13C-NMR)
% MFR2ss 'e3587 min, intrinsic viscosity measured in decalin at 135 °C [? ]0.47dl/g
, Softening temperature (TMA) 148℃, Glass transition temperature (
3.4 kg of pellets with Tg) of 137°C and ethylene.
Propylene random copolymer (ethylene content 80mol
%, MFRR,,Oco, 7g, 135℃
Intrinsic viscosity measured in decalin [η] 2, 2 dlm Glass transition temperature (Tg) -54°C pellet o, a
kg were melt-blended using a twin-screw extruder (PCM45 manufactured by Ikegai Iron Works) at a cylinder temperature of 220°C and pelletized using a pelletizer.For 1 kg of the obtained pellets, 1 g of Nippon Oil Co., Ltd. Hexyne 25TN was added to 1 g of divinylbenzene. The mixture was melt blended using a twin-screw extruder at a cylinder temperature of 230°C and pelletized using a pelletizer.The resulting pellets were then injection blow molded.9 Molding conditions and blow molded products The physical properties of are shown in Table 1.Table 1 (Note) *The physical property values of I are vertical/horizontal.

As explained above, by constructing the blow molded product according to the present invention from a specific cyclic olefin copolymer, the blow molded product has properties such as acid resistance, alkali resistance, and boiling water resistance. It has improved chemical properties.

Furthermore, since a cyclic olefin copolymer is selectively used as a material under certain conditions, mechanical strength, particularly impact strength, is improved.

[Brief explanation of drawings]

FIG. 1 is a sectional view of a preform used for molding a blow-molded product according to the present invention. 10... Preform, 12... Bottomed clothing 14.
・Container opening

Claims (2)

[Claims] (1) Polymers, copolymers and hydrogenated products thereof formed by ring-opening polymerization of cyclic olefin components represented by the following formula [I] or the following formula [II], and the following formula [I] or the following formula [ Blow molded products made from a cyclic olefin resin selected from the group consisting of copolymers formed by addition polymerization of a cyclic olefin component and an ethylene component represented by [II]; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the above formula [I], n is 0 or a positive integer, and R^1 to R^1^2 are each independently an atom or an atom selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. represents a group, and R^9 to R^1^2 may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group has a double bond. Also, R^9 and R^1^0 or R^1^1 and R
may form an alkylidene group with ^1^2]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [II] [In the formula, l is an integer of 0 or 1 or more, m and n
is 0, 1 or 2, R^1 to R^1^5 are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, and R^5
(or R^8) and R^9 (or R^7) may be bonded via an alkylene group having 1 to 3 carbon atoms,
Alternatively, they may be directly bonded without any group intervening. ] (2) The blow-molded product contains a polymer derived from a hydrocarbon, a chlorine-containing polymer, a polymer derived from an unsaturated acid, a polymer derived from an unsaturated alcohol, or an amine, in addition to the above cyclic olefin resin. , polymers derived from epoxides, polyacetals, polyphenylene oxides,
A claim characterized in that it is formed from a resin composition blended with at least one polymer selected from the group consisting of polycarbonate, polysulfone, urea resin, polyamide resin, polyester resin, formamide resin, and natural polymer. The blow molded product according to item 1.