JPH02289632A - Foamable polymer composition and foamed material - Google Patents

Abstract

PURPOSE:To provide a foamable polymer composition containing a specific cycloolefin polymer and a foaming agent as main components and capable of forming a foamed article having excellent heat-resistance, chemical resistance and electrical properties. CONSTITUTION:The objective foamable polymer composition contains (A) one or more kinds of cycloolefin resins selected from (i) a ringopened (co)polymer derived from a cycloolefin of formula (n is 0 or positive integer; R<1> to R<12> are H, halogen or hydrocarbon group; R<9> to R<12> may together form monocyclic or polycyclic group which may contain double bond; R<9> and R<10> or R<11> and R<12> may together form an alkylidene group), (ii) a hydrogenated product of said (co)polymer and (iii) an addition polymer of the cycloolefin of formula and ethylene, (B) a foaming agent at a weight ratio (A/B) of 100/(0.1-5) and, as necessary, (C) other polymers.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a foamable polymer composition and a foam, and more particularly, to a foamable polymer composition having heat resistance and chemical resistance containing a cyclic olefin polymer as the main resin component. The present invention relates to a foamable polymer composition capable of forming an excellent foam and a foam formed from this resin composition.

Polystyrene, polyethylene, etc. have traditionally been used as foamable polymers, and by using these polymers, it is generally possible to obtain foams with excellent rigidity. . Foaming methods generally include a method of foaming by mechanical stirring, a method of using reaction product gas, a method of using a blowing agent, a method of removing soluble substances, and a method of foaming by spraying. Methods using reaction product gas and methods using blowing agents are frequently used.

However, such conventional foams made of polystyrene, polyethylene, or the like may not have sufficient heat resistance or chemical resistance depending on the intended use.

An object of the present invention is to provide a foamable polymer composition for obtaining a foam having excellent heat resistance, chemical resistance, and electrical properties.

Another object of the present invention is to provide a foam that is formed using the foamable polymer composition and has excellent chemical resistance and electrical properties.

λriLtaka 1 The foamable polymer composition according to the present invention is a ring-opening polymer derived from a cyclic olefin represented by the following formula [E]; It is characterized by comprising an additive, at least one cyclic olefin resin selected from the group consisting of addition polymers of cyclic olefin and ethylene represented by the following formula [I], and a blowing agent.

... [l] However, in the above formula [I], it is nlko or a positive integer, and R1 to Rl2 are each independently an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. Table R9 to R l 2 11 may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond, mata, R9 and R1s or Rll and Rl2 may form a thealkylidene group.

Further, the foam according to the present invention is characterized in that the foamable polymer composition is foamed to a volume L:Q of 1.05 to 5 times that of the composition.

Cyclic olefin polymers inherently have excellent properties such as heat resistance, chemical resistance, solvent resistance, and impact resistance. According to the studies of the present inventors, this cyclic olefin resin has the above-mentioned excellent properties and also has the effect of allowing the foaming agent to be well dispersed in the resin during foam molding.

Therefore, by using the foamable polymer composition of the present invention using a cyclic olefin polymer, it is possible to form a foam having extremely excellent heat resistance and chemical resistance. becomes uniform. Furthermore, foams formed from this foamable polymer composition also have excellent electrical properties.

In the present invention, the foaming agent is inorganic foaming agent.
Organic blowing agents and evaporative blowing agents are used as appropriate.

B The foamable polymer composition and foam according to the present invention will be specifically explained below.

[Cyclic olefin] The resin constituting the foamable polymer composition according to the present invention is a ring-opening polymer derived from a cyclic olefin represented by the following formula [+], a ring-opening copolymer, the polymer, or a copolymer. The resin is at least one type of resin selected from the group consisting of a hydrogenated product of a combination and an addition polymer of a cyclic olefin and ethylene represented by the following formula [1].

It may have a cross-linked 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 Rl2 together form, for example, a polycyclic or monocyclic group as described below... [I
] However, in the above formula [1], n is O or a positive integer, and R1 to R I2 (1 each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group. Furthermore, R9 to Rl2 are mutually They may be combined to form a monocyclic or polycyclic group, and in the above formula, the carbon atoms to which l and 2 are attached are represented by R9 to R+2 in formula [I] Represents a carbon atom in an alicyclic chain to which a group is attached.

Furthermore, these groups may have a substituent such as a methyl group.

Also, between R- and R-port, or between R1e and R+2,
It may form an alkylidene group. Furthermore, R9~
An ester group or the like may be included in Rl2.

One preferred example of such a cyclic olefin is:
For example, a cyclic olefin represented by the following formula [■] can be mentioned.

The ring may have a double bond.

An alkylidene group may be formed by R1% and RI6, or by RIT and R1@.

In addition, in the present invention, the cyclic olefin 1 used as a raw material for preparing an olefin polymer having an alicyclic structure also includes a compound represented by the following formula [na].

...[nl However, in the above formula [n], n is O or 1, and m is 0 or a positive integer.

In addition, R I and R I1 each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group; may be formed, and the monocyclic or polycyclic ring...[
n-a] Just Fox In the above formula [m-a], p is 0 or 1
q and r are 0, 1, or 2, and R1 to RI5 each independently represent a group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an alkoxy group. Represents an atom or group selected from RS (or R 6 ) and R9 (or R?) may be bonded via an alkyl group having 1 to 3 carbon atoms, or may be bonded directly without any group. Good too.

The cyclic olefin represented by the above formula [I], or preferably formula [n], and further formula [■1a] can be obtained by condensing cyclopentadiene and the corresponding olefin or cyclic olefin by Diels-Alder reaction. It can be easily manufactured by

That is, the above formula [11,
The cyclic olefin represented by [n] or [na] is specifically takabicyclo[2, 2. 1] Heptose-2-ene-derived tetracycline [4, 4, 0, 12. S, 1
3-dodecene derivative hexacyclo[6l6,1, 13,e, 1+++.
+3.02. t, Qs. +4]-4-Heptadensene induction book t Ku9 ShikuO [8,8,0.1",1",II'
=8.1"1"Q3. @ , Ql 2・+71−
5-Docosen induction book pentasic mouth [6, 6, 1.
13.6, Q2.1. Q9. +4]-4-hexadecene derivative Heptacyclo-5-icosene derivative Heptacyclo-5-heneicosene derivative Tricyclo[
4,3,0.1251-3-decene-derived tricyclo[
4,3,0,12.5]-3-undecene derivative pentacyclo[6,5,1.13.6.02・7,09・+
3 ]-4-pentadecene derivative arc pentacyclobentadecadiene derivative pentacyclo[4, 7, 0, 12 . S,
O”・+3.
02. ? , 11th. +7, Qll. lI112.
Is Koh 4-Eikosen induction book and nonasik mouth [9, 10, 1, 1, 4. 7.
03・●Q2. IQ, Ql2. 2 1
113.29. QI4. +9, lls. +8]-5-
Mention may be made of he7tacocene derivatives.

Specific examples of such compounds are shown below.

Bicyclo[2,2.1]hept-2-ene derivatives such as 6-methylbicyclo[2; 5.10-dimethyltetra9-ethyl-11. 12-dime9-isobutyl11. 12 5, 8, 9. 10-tetrameth2, 7. 9-trimethyltetraC Hs 8-methyltetrasic 8-ethyltetrasic 1@]-3-dodeceneC * H ls 1●]-3-dodeceneC No.H. Te1●]-3-dodecene1m]-3-dodecene8-methyl-9-ethylte8-chlorotetracyc-3-dodecene8-promotetracyc-3-dodecenel]-3-dodecene+s]-3 -dodecene 8-ethylidene-9-iso-dodecene 12. s. 1 cho・1●]-3-dodecene 5.17 1I-co 3-dodecene 8-n-propylidene-9 1-dodecene s, p. +1! ]-3-dodecene+@]-3-dodecene-3-dodecene 1e-co 3 dodecene, 12 5.17・1e-co 3-dodecene 8-n-propylidene-9 [4, 4, 0. 12 5.17 1]-3 Dodecencro [4, 4, 0. 12 1●]-3-dodecene [4, 4, 0. 12 s4v. +e]-3-dodecene-dodecene-8-isopropylidene. +a]-4-heptadecene-dodecene 12-methylhexacyclodecene 1 @ ]-3-dodecene-dodecene and other tetracyclos [4, 4, 0. 12.5.1
7+s]-3-dodecene derivative (blank below) heptadecene 1 8 , Q3 10+2.1 Fuco 5-dococene derivative; + 3 ,
Q2. ? , QllIn]-4-heptadecene and other hexacyclo[6, 6, 1. 13.6, I
I●eye Q2. ? , Qll 14-heptadecene derivative; +S, Q3 ● Ql 2 . 1▼]-5- Dokosen+@, 14s 1 @, Os . ●． 01 7]-5-docosendecene 7]-pentacyclo[6, 6, 1. 13.6.0
octacyclo[8, 8, 0.2, 7, o9A]-4-, etc. 129.14 7.1st. 1. Hexadecene derivative; heptacyclo [8, 7. Trisic openings such as 0 [4, 3, 0. 125]-3-
Decene derivative 8, Ql2 +? ]-5-icosene derivatives such as -5-heneicosene or hebutacyclo-5-heneicosene derivatives: tricyclo-5-icosene derivatives such as methyl-trisic [4, 4, 0. 125] -3 undecene derivatives 1,3-dimethyl-benta1,6-dimethylbentacene and other pentacyclo[4, 7, 0, 12 . S, 082] -3-pentadecene derivative: 14. Pentacyclo[6, 5, 1. 13.6.0
2.7, Oe+ 3] -4- Pentadecene derivative; 15] -4-eicosene etc. heptase opening [7,8,0.1'',02.7,1 7.0 1f.+6,1+2 1s co-4-eicosene derivatives; diene compounds such as 2+,113.2+1,Q+4.19.11s.+e]
-5-pentacocene s 2e. 0+*. +e, l+s. +s] 5-pentacocene, etc. [9, IQ, l, l4. 7,
Q3.8, Q2. Ill, Ql 221, l
+3.29. QIj. l9,lls. Mention may be made of Ill-5-hentacocene derivatives.

(Margin below) can be mentioned.

Examples of the polycyclic olefin represented by the above formula [I] include {L of the above compound and 1, 4, 5.
8-dimethano-1. 2, 3, 4, 4a, 5,
8. 8a-Naphthalene, 2-methyl-
1. 4, 5. 8-dimethano-1. 2, 3,
4. 4a, 5. 8, 8a-octahyde naphthalene, 2-ethyl-1.4.58-dimethano-1. 2
, 3, 4, 4a, 5, 8. 8a-cutahydronaphthalene, 2-probyl-1. 4, 5. 8
-Dimethano-1. 2, 3, 4, 4a, 5, 8
．． 8a-Naphthalene, 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
-Octahyde naphthalene, 2-methyl-3-ethyl-
1. 4, 5. 8-dimethano-1. 2, 3,
4, 4a, 5, 8, 8a-octahyde naphthalene, 2-chloro-1.4, 5. 8-dimethano-1
．． 2, 3, 4, 4a, 5, 8, 8a-octahyde naphthalene, 2-bromo1. 4, 5.
8-dimethano-1. 2, 3, 4, 4a, 5,
8. 8a-octahyde naphthalene, 2-fluoro1. 4, 5. 8-dimethano-1. 2, 3,
4, 4a, 5, 8, 8a-octahyde naphthalene, 23-dichloro1. 4, 5. 8-dimethano-1. 2, 3, 4, 4a, 5, 8,
8a-octahyde naphthalene, 2-cyclohexyl-
1. 4, 5. 8-dimethano-1. 2, 3,
4, 4a, 5, 8. 8a-Naphthalene, 2-n-butyl 1, 4, 5. 8-dimethano-1. 2, 3, 4, 4a, 5, 8, 8
a-octahyde naphthalene, 2-isobutyl 1,
4, 5. 8-dimethano-1. 2, 3, 4,
Mention may be made of octahyde naphthalenes such as 4a, 5, 8, 8a-octahyde naphthalene.

[Cyclic olefin resin] In the present invention, the cyclic olefin resin constituting the foamable polymer composition is (1-a) a ring-opening polymer or a ring-opening copolymer derived from the above-mentioned cyclic olefin. (1-b) At least one type of resin selected from the group consisting of hydrogenated products of these polymers or copolymers, and (2) addition polymers of cyclic olefin and ethylene as described above.

(1-a) Ring-opening polymer or ring-opening copolymer derived from the above-mentioned cyclic olefin (1-b) Hydrogenated product of these polymers or copolymers The cyclic olefin ring-opening polymer is The cyclic olefin represented by formula [I] or formula [II] can be prepared by ring-opening polymerization of the cyclic olefin represented by formula [I] or formula [II] by a method known per se. In the present invention, a cyclic olefin ring-opening polymer prepared using a single cyclic olefin as described above can be used, or a cyclic olefin ring-opening copolymer prepared by ring-opening polymerization of a plurality of cyclic olefins can be used. Can also be used.Give an example of such a ring-opened polymer or copolymer if, 1, 4, 5.
8-dimethanol 1, 2, 3, 4, 4a, 5,
8, 8a-Octahydronaphthalenes (co-)
Polymer book 1, 4, 5. 8-dimethano-1,2,
3. 4, 4a, 5, 8, 8a-Octahyde naphthalenes and norporene (picyclo[2.2.1]
Ring-opened copolymers with hept-2-ene) can be mentioned.

Double bonds remain in the cyclic olefin ring-opened polymer prepared as described above, and these double bonds can be easily hydrogenated by a known method. In the present invention, a hydrogenated product of the cyclic olefin ring-opened (co)polymer prepared as described above can also be used as the cyclic olefin resin. Such hydrogenation further improves thermal stability and weather resistance.

The ring-opening (co)polymer compound used as the cyclic olefin resin in the present invention and its hydrogenated product will be explained using the cyclic olefin represented by the formula [nl] as an example. Cyclic olefins are thought to react as described below to form ring-opening (co)polymers and their hydrogenated products.

↓Hydrogenation In the above formula, R l, R l @ and m
and n have the same meaning as in the formula [■].

In addition, in the case of ring-opening polymerization, the formula [D], the formula [n
], or a cyclic olefin other than the cyclic olefin represented by the formula [■-a] can be ring-opening copolymerized.

Examples of such other cyclic olefins include cyclobutene, cyclobentene, cyclohexene, 3,4-dimethylcyclobentene, 3-methylcyclohexene, 2-
(2-methylbutyl)-1-cyclohexene, 2. 3
．． 3a, 7a-tetrahydride 0-4,'7-j ta/-
IH-indene and 3a, 5, 6. Examples include 7a-tetrahydro-4,7-methanol IH-indene.

(2) Addition polymer of cyclic olefin and ethylene (hereinafter sometimes referred to as cyclic olefin addition polymer) The cyclic olefin addition polymer used as the cyclic olefin resin in the present invention has the above formula [ I], a cyclic olefin represented by formula [n] or [■-a], and ethylene.

In this cyclic olefin addition polymer, the repeating units derived from ethylene/the repeating units derived from cyclic olefin are usually in a molar ratio of 10/90 to 90/10, preferably 50/50 to 75/25. They are connected by ratio.

Cyclic olefin addition polymers can be produced by polymerizing ethylene and cyclic olefins 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 is disclosed in Japanese Patent Application Laid-Open No. 1986-
It has been proposed in Publication No. 168708 and the like.

In such a cyclic olefin addition polymer, for example, at least a part of the cyclic olefin represented by the above formula [n] has a structure represented by the following formula [[[1] and is derived from ethylene. It is thought that they are randomly bonded to repeating units.

...[[[+] However, in the above formula [[[l], RI-R1@, m and n have the same meanings as in formula [n].

In the above-mentioned cyclic olefin addition polymer used in the present invention, in addition to the cyclic olefin component and the ethylene component, in addition to the cyclic olefin component and the ethylene component, a olefin other than the cyclic olefin represented by the above formula It is also possible to use a polymer obtained by adding a cyclic olefin (another cyclic olefin) and carrying out addition polymerization.

The σ-olefin used herein may be linear or branched, and examples of such α-olefins include 1-propylene, 1-butene, 4-methyl-
α-olefins having 3 to 20 carbon atoms such as 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. can be mentioned. Among these, those having 3 to 15 carbon atoms, especially 3 to 15 carbon atoms
Preference is given to using lO alpha-olefins.

In addition, "other cyclic offreins" as used herein is a broad concept that includes unsaturated polycyclic hydrocarbon compounds, excluding cyclic olefins represented by formulas [I], [n], and [n-a]. It is indicated by.

More specifically, examples of other cyclic olefins include cyclobutene, cyclopentene, cyclohexene, 3.4
-dimethylcyclopentene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, styrene, a-methylstyrene, 2,3.3a, 7-tetrahydro-4,7-methanol IH-indene and 3a
, 5, 6, 7a-tetrahydro-4. Examples include 7-methanol IH-indene.

In addition, when other cyclic olefins have two or more double bonds in the molecule, the remaining double bonds that are not used in addition polymerization are hydrogenated for the purpose of improving weather resistance. You can also do that.

For example, by carrying out addition polymerization as described above and hydrogenation if necessary, the iodine value of the cyclic olefin addition polymer used in the present invention is usually 5 or less, and most of them are 1 or less.

In the cyclic olefin addition polymer, it can be confirmed that the cyclic olefin used as a raw material has a structure represented by the above formula [m], for example, by measuring 13c-NMR of the cyclic olefin addition polymer. . Such a cyclic olefin addition polymer has a chemically stable structure and is a polymer with excellent heat aging resistance.

Cyclic olefin ring-opened (co)polymer (1-a) described above
The hydrogenated product (1-b) and the cyclic olefin addition polymer (2) usually have an intrinsic viscosity [V] of 0.01 to 20 di/g when measured in decalin at 135°C.
is within the range of In the present invention, especially 0.
05-10dl/g, even 0.08
It is preferable to use a cyclic olefin resin within the range of -8 dl/g.

These cyclic olefin-based resins have poor quality or low crystallinity, preferably poor quality, and therefore good transparency. Specifically, when the crystallinity of these cyclic olefin resins is measured using X-rays, the crystallinity is 5% or less, and most of them are 0%. Moreover, even if the melting point of these cyclic olefin resins is measured using a differential scanning calorimeter (DSC), in many cases no melting point is observed.

Another property of such a cyclic olefin polymer is,
Examples include high glass transition temperature (Tg) and high softening temperature (TMA). Glass transition temperature (Tg) is usually measured in the range 50-230<0>C, often in the range 70-210<0>C. Therefore, when directly used as a composition material, the softening temperature is usually measured in the range of 70 to 250°C, and in most cases, in the range of 90 to 230°C.

In addition, the thermal decomposition temperature is 350-420℃, and most of them are 370-420℃.
It is within the range of 400°C.

As for mechanical properties, bending breakage rate is usually IX10A~5X
The bending strength is usually within the range of 300 to 1500 kg/an2.

Density is 0.86-1.10g/■3, most of which is 0.8
8-1. It is in the range of 0.8 g/a, l3.

Also, the refractive index (ASTM D542) is 1.47 to 1.5.
8. Most of them are within the range of 1.48 to 1.56, and are substantially amorphous, so the haze (ASTM D)
1003) is usually zO% or less, often 10% or less.

As for electrical properties, the dielectric constant (IKHz) measured by ASTM D150 is 1. 5-3. O, mostly 1.9 ~ 2.6, dielectric loss tangent 9 x 1 0-4 ~
8X1. O-5 mostly 3x10-4~9X10-S
is within the range of

Molded bodies and foamed bodies formed from the composition according to the present invention using such a cyclic olefin polymer have excellent chemical resistance. Even when immersed for a long period of time, no deformation, deformation, etc. were observed.Furthermore, the foamable polymer composition of the present invention blends various polymers with the above-mentioned cyclic olefin polymer as a resin component. The material can be a so-called polymer alloy. Examples of these polymers include the following (1) to 0.

■Polymerization derived from hydrocarbons having one or two unsaturated bonds Specific examples include polyethylene, polypropylene,
polymethylbutene-1, poly4-methylpentene-1,
Polyolefins such as polybutene-1 and polystyrene (these polyolefins may have a crosslinked structure), ■ Halogen-containing vinyl polymers (specifically polyvinyl chloride, polyvinylidene chloride,
polyvinyl fluoride, polychloroprene, chlorinated rubber, etc. Polymers derived from a, β monounsaturated acids and their derivatives Specifically, polyacrylates, polymethacrylates,
Copolymerization with monomers constituting polyacrylamide, polyacrylonitrile, or the above-mentioned polymers For example, acrylonitrile/butadiene/styrene copolymerization Not acrylonitrile/styrene copolymerization Acrylonitrile/styrene/acrylic acid ester copolymer, etc. Unsaturated Polymers derived from alcohols and amines or their acyl derivatives or acetals, specifically polyvinyl alcohol, polyvinyl acetate,
Polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, polyallylmelamine, or copolymers with monomers constituting the above polymers, such as copolymers with ethylene and vinyl acetate, etc. ■ Polymers derived from epoxides, specifically polymers derived from polyethylene oxide or bisglycidyl ether, ■polyacetals, specifically polyoxymethylene, polyoxyethylene, and polysaccharides containing ethylene oxide as a comonomer. such as oxymethylene, ■polyphenylene oxide, ■polycarbonate, ■polysulfone, ■polyurethane and urea resins, ■polyamides and copolyamides derived from diamines and dicarboxylic acids and/or aminocarboxylic acids or the corresponding lactams, in particular ( nylon 6,
Polyesters derived from dicarboxylic acids and dialcohols and/or oxycarboxylic acids or corresponding lactones, such as nylon 66, nylon 1 1, nylon 12, etc., in particular polyester terephthalate, polybutylene terephthalate, poly-1.4 - Dimethylol cyclohexane terephthalate, etc. ■ Polymers with a crosslinked structure derived from aldehyde and phenol, urea or melamine. In terms of polymers, there are phenol formaldehyde resins, urea formaldehyde resins, melamine formaldehyde resins, etc. ] Alkyd resins include glycerin and phthalic acid resins, etc., unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols, and unsaturated polyester resins obtained using vinyl compounds as crosslinking agents; Halogen-containing modified resins, such as cellulose, rubber, protein, or their derivatives, such as cellulose acetate, propionic acid cellulose, cellulose ether, and soft polymers, especially the following: Rubber-like components selected from the groups (i) to (V) mentioned above can be mentioned.

In addition, in polymer alloys of cyclic olefin polymers and these rubber-like components, a crosslinking reaction may be performed in the presence of organic peroxides, and such crosslinkable polymer alloys can be foamed with excellent rigidity and impact resistance. The present invention provides a synthetic polymer composition.

The soft polymer containing cyclic olefin component units is composed of ethylene and the same type of cyclic olefin (represented by formula [I], [n] or [ml) used in the cyclic olefin polymer. It can be prepared by copolymerizing a cyclic olefin) and an α-olefin. As the a-olefin, α-olefins having 3 to 20 carbon atoms are preferably used. Preferred examples of the a-olefins used in the present invention include propylene, 1-butene, 4-methyl-1-
Mention may be made of butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. Also, see the other α-olefin numbers above.
Alternatively, cyclic olefins or cyclic dienes such as norbornene, ethylidenenorbornene, dicyclopentadiene, etc. are also preferably used in addition to the σ-olefin.

In the soft polymer (i) containing a cyclic olefin component,
The repeating units derived from ethylene are contained in an amount ranging from 40 to 98 mol%, preferably from 50 to 90 mol%. The repeating unit derived from a σ-olefin is contained in an amount within the range of 2 to 50 mol%, and the repeating unit derived from a cyclic olefin is further contained. It is contained in an amount within the range of 2 to 20 mol%, preferably 2 to 15 mol%.

The soft polymer (i) differs from the above-mentioned cyclic olefin polymer in that it has a glass transition temperature (Tg) of 0°C or lower, preferably -10°C or lower, and has an intrinsic viscosity measured in decalin at 135°C [ 1] is 0.01-10dl
/i preferred L< is o. 08 to 7 dl/gt'.

The degree of crystallinity of the soft polymer (i) measured by X-ray diffraction is usually in the range of 0 to 10%, preferably 0 to 7%, particularly preferably 0 to 5%.

Such a soft polymer (i) is disclosed in Japanese Patent Application Laid-Open No. 1687-1987.
No. 08, No. 61-120816, No. 61-115
No. 912, No. 61-115916, No. 61-27
No. 1308, No. 61-272216, No. 62-2
According to the applicant's proposal described in publications such as No. 52406, it can be manufactured by appropriately selecting conditions.

σ-Olefin System, Polymerization 11 The a-olefin copolymer (ii) used as the soft polymer is a non-quality or low-crystalline copolymer consisting of at least two types of a-olefins.

Examples of low-crystalline copolymers include ethylene/α-olefin copolymers and propylene/a-olefin copolymers.

The α-olefin constituting the ethylene/α-olefin copolymer is usually an α-olefin having 3 to 20 carbon atoms.
Examples of olefins used include propylene, 1-butene, 4-methyl-1-butene, 1-hexene, 1-octene, 1-decene, and mixtures thereof. Among these, especially α- with 3 to IO carbon atoms
Olefins are preferred.

Molar ratio of repeating units derived from ethylene and repeating units derived from a-olefin in the ethylene/a-olefin copolymer (ethylene/a-olefin) lL Although it varies depending on the type of a-olefin, 40 It is preferable to adjust within the range of /60 to 95/5. Next, the above molar ratio is the α-
If the olefin is propylene, 4 0/6
It is preferable that the ratio is 0 to 90/10, and when the a-olefin is an a-olefin having 4 or more carbon atoms,
The ratio is preferably 50/50 to 95/5.

It is common to use a-olefins having 4 to 20 carbon atoms as the a-olefin constituting the propylene/a-olefin copolymer. 1-bentene, 1-
Hexene, 1-octene, 1-decene and mixtures thereof are used. Among these, especially a having 4 to 10 carbon atoms
-Olefins are preferred.

In the above-mentioned propylene/a-olefin copolymer (a repeating unit derived from propylene and a
- molar ratio with repeating units derived from olefins (
Propylene/α-olefin) varies depending on the type of a-olefin, but is preferably in the range of 5o/50 to 95/5.

α-olefin/gen polymerization iii) α-olefin/diene copolymers (iii) used as soft polymers include ethylene/a-olefin/gen copolymer rubber and propylene/a-olefin/gen copolymer rubber. Polymer rubber is used.

As the a-olefin constituting such a copolymer rubber, an alpha-olefin having 3 to 2 carbon atoms (4 to 20 in the case of propylene/a-olefin) is usually used. For example, propylene, l-butene, 1-bentene,
These include 4-methyl-1-bentene, 1-hexeth 1-octene, 1-decene, and mixtures thereof. Among these, a-olefins having 3 to 10 carbon atoms are particularly preferred.

For example, E l4 1.4-hexadiene, 1
．． 6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-
1. Chained non-conjugated diene such as 6-octadiene cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene- 2-norbornene,
Cyclic non-conjugated dienes such as 6-chloromethyl-5-imbropenyl-2-norbornene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2
．． Examples include 2-norbornadiene.

In the above ethylene/α-olefin/diene copolymer rubber, the molar ratio of repeating units derived from ethylene to repeating units derived from a-olefin (ethylene/α-olefin) varies depending on the type of α-olefin. Preferably, the different forces τ are generally in the range 40/60 to 90/10.

In addition, the content of repeating units derived from diene in these copolymer rubbers (usually 1 to 20 mol%)
, preferably within the range of 2 to 15 mol%.

Aromatic vinyl hydrocarbons used as soft polymers
As the conjugated diene-based soft copolymer, aromatic vinyl-based hydrocarbon milk, conjugated diene-based random copolymerized block copolymers, or hydrides thereof are used.

Specific examples include styrene/butadiene block copolymer rubber, styrene/butadiene/styrene block copolymer rubber, styrene/isoprene block copolymer rubber, styrene/isoprene/styrene block copolymer rubber, and hydrogenated rubber. Examples include styrene/butadiene/styrene block copolymerized hydrogenated styrene/isoprene/styrene prosodic copolymer rubber, styrene/butadiene random copolymer rubber, and the like.

The molar ratio of repeating units derived from aromatic vinyl hydrocarbons and repeating units derived from conjugated dienes in these copolymer rubbers (aromatic vinyl hydrocarbon/conjugated diene) is usually 10/90 to 10/90. It's in the 70/30 range. Further, the hydrogenated copolymer rubber is a copolymer rubber in which part or all of the double bonds remaining in the above copolymer rubber are hydrogenated.

As the isobutylene-based soft polymer or copolymer (V) as the soft polymer, specifically used are polyisobutylene rubber, polyisoprene rubber, polybutadiene rubber, isobutylene-isoprene copolymer rubber, and the like.

The properties of the copolymers (11) to (V), which are soft polymers, are similar to those of the cyclic olefin polymer (i), and the intrinsic viscosity [wa] measured in decalin at 135°C However, usually o. 01-10dl/g1 preferably 0.
The glass transition temperature (Tg
) is usually 0°C or lower, preferably -10°C or lower, particularly preferably -20°C or lower. In addition, the crystallinity measured by X-ray diffraction is usually 0 to 10%, preferably 0 to 10%.
7%, particularly preferably in the range from 0 to 5%.

Such soft polymers can also be used as they are. After forming a crosslinked structure, they can be blended into a cyclic olefin resin. Moreover, after blending with the above-mentioned cyclic olefin resin, a crosslinked structure can be formed.

Polymer alloys containing such rubber-like components and crosslinkable polymer alloys treated with organic peroxides are used to prepare 14 parts by weight of various cyclic olefin addition polymers.
The total amount of soft polymers i) to (V) is 5 to 150% by weight, preferably 5 to 100% by weight, particularly preferably 10 to 100% by weight.
It is present in an amount of 80 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 to 100
It is preferable that

In the present invention, an organic peroxide is usually used to form a crosslinked structure. Examples of organic peroxides used in crosslinking polymerization include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, 1,1-bis(t-butylperoxy)cycloxane, 2,2-bis(t-butyl Peroxyketals such as octane, t-butylhydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroxyperoxide, 1,1,3,3-tetramethylbutylhydroperoxide Hydroperoxides such as oxides
butyl peroxide, 2,5-dimethyl-2.5 di(t
-butylperoxy)hexane, 2,5-dimethyl-2
, 5-di(t-butylperoxy)hexyne-3 and other dialkyl peroxides; lauroyl peroxide, penzoyl peroxide and other dialkyl peroxides; t-butylperoxyacetate, t-butylperoxybenzoate, 2. Peroxy esters such as 5-dimethyl-2,5-di(penzoylperoxy)hexane and the like can be mentioned.

The amount of the organic peroxide component is based on 100 parts by weight of the total amount of the cyclic olefin addition polymer and the soft polymer.
Usually 0.01 to 1 weight @ limit, preferably 0.05 to 0
．． 5 parts by weight.

By further containing a compound having two or more radically polymerizable functional groups in the molecule during treatment with an organic peroxide, a polymer alloy with excellent impact resistance can be obtained. That is, the crosslinking efficiency is improved by performing the crosslinking reaction while using a compound having two or more radically polymerizable functional groups in the molecule.

The radically polymerizable functional group used here is contained within the molecule.
Examples of compounds having more than 1 divinylbenzene,
Examples include vinyl acrylate and vinyl methacrylate. These compounds are usually used in an amount of 1 part by weight or less, preferably 0.91 to 0.5 part by weight, based on 100 parts by weight of the total amount of the cyclic olefin resin and the soft polymer.

1 Agent The blowing agents used in the present invention are categorized into (1) decomposable blowing agents and (2) evaporative blowing agents.

A decomposable blowing agent is a blowing agent that utilizes gas generated by chemical decomposition, and an evaporative blowing agent is a liquid or gas physical blowing agent that evaporates without chemical change.

(1) Decomposable blowing agents Decomposable blowing agents include inorganic blowing agents and organic blowing agents, and both blowing agents are appropriately used in the present invention.

Examples of inorganic blowing agents include sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, sodium azide borohydride, and light metals.

Examples of organic blowing agents include azodicarbonamide, barium azodicarboxylate, N,N'-dinitrosopentamethylenetetramine, 4.4-oxybis(benzenesulfonylhydrazine), diphenylsulfone-3.3-
Examples include disulfonyl hydrazide, p-toluenesulfonyl semicarbazide, trihydrazinotriazine and biurea. Further, the high-temperature foaming agents mentioned above are also used as appropriate.

In selecting a blowing agent, the decomposition temperature, amount of gas generated, and decomposition rate of the blowing agent are important factors. Therefore, in order to adjust the foaming conditions, a foaming aid may be added to adjust the decomposition temperature, gas generation, and decomposition rate of the foaming agent. As blowing aids, conventional blowing aids such as oxalic acid, succinic acid, citric acid, urea, borax and ethanolamine can be used.

The method of foaming the decomposable blowing agent is to melt and knead the resin and the blowing agent at a temperature that is above the melting point of the resin and below the decomposition temperature of the blowing agent, and then mix the resulting mixture into a mixture that is above the decomposition temperature of the blowing agent. The normal pressure foaming method involves heating to a high temperature and foaming at normal pressure.Extrusion involves extruding the material resin containing a foaming agent through a die in a molten state, changing the pressure applied to the molten material from a high pressure state to normal pressure to foam it. Foaming method, a pressurized foaming method in which a material resin containing a foaming agent is filled into a closed mold, heated under pressure to decompose the foaming agent, and then released to change the pressure to rapidly expand the resin. and an injection foaming method in which a uniformly foamed core layer and a non-foamed skin layer are formed using an injection molding method. In the present invention, any of the foaming methods described above can be used.

Further, in the pressure foaming method, a crosslinking agent, a radical generator, etc. can also be used as appropriate.

(2) Evaporative foaming agent As the evaporative foaming agent, aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons, fluorinated aliphatic hydrocarbons, inert gases, and the like are used. Specific evaporative blowing agents include readily volatile organic liquids such as pentane, hexane, heptane, isohebutane, benzene, toluene, methylene dichloride, trichloroethylene, dichloroethane, dichlorotetrafluoroethane, and trichlorofluoroethane; Examples include helium.

As a foaming method using an evaporative foaming agent, for example, a fine particulate polymer containing an evaporative foaming agent is filled into a desired mold,
Examples include an in-mold foaming method in which a porous molded body is produced by heating at a temperature higher than the boiling point of the foaming agent and to a temperature at which the polymer softens, and the extrusion foaming method described above.

In the present invention, any of the foaming methods described above can be used.

Blending ratio of cyclic olefin polymer and foaming agent In the foamable polymer composition according to the present invention, the cyclic olefin resin and foaming agent differ depending on the type of foaming agent, but the weight ratio (cyclic olefin resin / blowing agent) usually 10070
．． It is blended in an amount within the range of 1 to 100/5.

Such a blowing agent is mixed or dispersed into the cyclic olefin resin using a known method.

The expansion ratio when producing a foam using the foamable polymer composition of the present invention produced in this way can be set as appropriate depending on the purpose of use of the foam molded product to be obtained. It is usually set within a range of 1.2 to 50 times the volume of the foamable polymer composition.

The foam thus obtained is both metric and
It has excellent properties such as heat resistance, chemical resistance, and electrical properties.

soil! The foamable polymer composition according to the present invention has a force f formed from the specific cyclic olefin resin and the blowing agent as described above, and the composition of the present invention has a Heat resistance stability, weather resistance stability, antistatic property 01, within the range that does not impair the purpose of the present invention.
Slip II, Anti-blocking Qi L Anti-fog Qi L Smooth Qi L Dyes, pigments, natural ponds, synthetic waxes, organic or inorganic fillers, etc. can be blended.

Even if (!, as a stabilizer added as an optional ingredient (!)
Dai Tetrakis [methylene-3- (3.5-dit
-butyl-4-hydroxyphenyl)probionate]
Methane, β-(3,5-di-t-butyl-4-hydroxyphenyl)probionic acid alkyl ester, 2.2
'-oxamidobis[ethyl-3-(3.5-di-t-
Phenolic antioxidants such as butyl-4-hydroxyphenyl) propionate; Fatty acid metal salts such as zinc stearate, calcium stearate, and calcium 1,2-hydroxystearate: Glycerin monostearate, glycerin distearate, bentaerythritol monostearate , polyhydric alcohol fatty acid esters such as pentaerythritol distearate and pentaerythritol tristearate. These may be blended alone or may be blended in combination. For example, an example combination is tetrakis[methylene-3-(3,5-di-t-butyl-4-
Examples include a combination of hydroxyphenyl)propionate comethane, zinc stearate, and glycerin monostearate.

Additionally, examples of organic and inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, and sulfuric acid. Calcium, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber , polyethylene fibers, polypropylene fibers, polyester fibers, polyamide fibers, and the like.

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, and for example, each component can be mixed simultaneously.

The foam obtained from the foamable polymer composition according to the present invention may be used after being subjected to secondary processing.
Vacuum adult pigs Press adult pigs Slip adult pigs Pressure adult pigs Mark 8
1k Can be used for painting, plating, flocking, embossing, laminating with metal or other resins, etc.

The foam according to the present invention has the following usage methods, for example.

(1) Examples of applications using insulation properties: Insulating and preventing condensation on roofs, ceilings, walls, and floors of buildings; Insulating warehouses; Insulating pipes, tanks, etc.; heating, cooling, and electric refrigeration; Bathtubs, air-conditioning equipment, showcases, and thermal insulation. Cold storage containers Automotive Tencho Door lining, food containers (tea, ramen, soup).

(2) Examples of applications that utilize impact resistance Precision machinery Buffer packaging for foods, food containers (trays), automobile instrument panels, armrests, side pillars Sun visors Hard hats, headgear, protectors Judo halls For sports such as tatami mats and (3) Examples of applications that utilize compression properties: container packing, sealing materials, back amplifier materials.

(4) Examples of applications that take advantage of buoyancy and light weight Lifesaving devices for ships Buoyancy structure books Floats, various water games Parabolic antennas and flat antennas (5) Examples of applications that take advantage of acoustic characteristics Machine rooms, acoustics Sound absorbing materials for rooms, broadcasting rooms, etc.

The foam formed from the foamable polymer composition of the present invention is
Due to its excellent heat resistance and chemical resistance, it can be used in a wider range of applications than conventional foams.

As explained above, the foamable polymer composition and foam thereof according to the present invention contain a cyclic olefin polymer as the main resin component, so the foam has excellent properties. It has excellent heat resistance, chemical resistance, and electrical properties. Therefore, this foam can be used in a wider range of applications than conventional foams.

[Example] The present invention will be specifically described below with reference to Examples. The present invention is not limited to these examples.

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

(1) Melt flow index (MFRT) Predetermined temperature (T'C) according to ASTM-D1238
, measured at a load of 2.16 kg (2) Softening temperature (TMA) Thermo Mechanical manufactured by Dubosi
The thermal deformation behavior of a sheet of thickness 11 was measured using an analyzer. A quartz needle was placed on the sheet, a load of 49 g was applied, and the temperature was raised at a rate of 5°C/min.
35l1. (3) Glass transition temperature (Tg) Measured at a heating rate of 1oC/min using DSC-20 manufactured by SEIKO Electronics Co., Ltd. (4) Foam molding obtained in the tensile test example From the product, ASTM TYP
E■ A dumbbell-shaped test piece was punched out, and the test piece was measured according to the method of ASTM-D638 at a test temperature of 23°C. Cut a 5-inch test piece L, ASTM-D79
A test piece with a width of 1/2 inch and a length of 3 inches was cut out from the foamed molded product obtained in the (6) Izod impact test example, which was measured at a test temperature of 23 ° C and a test speed of 20 m - / min according to O. (no sochi), AST
(7) Rockwell hardness Measured at a test temperature of 23°C according to M-D256.
85 (R scale) and 9 (8) Expansion ratio determined by comparison of specific gravity after foaming (9) Chemical resistance The foamed molded product obtained in the example was immersed in the following prescribed test liquid - After being left at 23°C for 7 days, there is no change in the appearance of the test piece, and the tensile breaking strength measured by the method shown in (4) is 90% or more of the value measured before this test. Acid resistance; 20% sulfuric acid aqueous solution alkali resistance: 20% sodium hydroxide aqueous solution soaked in a cyclic olefin-based copolymer, a random copolymer with ethylene (measured by C-NMR) With an ethylene content of 71 mol%, MFR 2sa'c, 20g/
minutes, intrinsic viscosity measured in decalin at 135°C [77]
0.6di/fu Softening temperature (TMA) 115℃) 1k
g was thoroughly mixed with 10 g of a mixture of azodicarbonamide and sodium bicarbonate as blowing agents at a weight ratio of 674 to prepare a foamable polymer composition. Then, a plate-shaped molded product of injection foam molding LA 350 x 100 °C, injection pressure (primary/secondary) 700
/500kg/. 2. Mold temperature: 70°C) In Example 1, a random copolymer of ethylene and DMON was substituted for the cyclic olefin copolymer (1
Intrinsic viscosity [q] 0.47 d determined in decalin at 135 °C with M F R 2ss'C% 35 g/min at 62 mol% ethylene content determined by 3C-NMR
A molded product was obtained using the same method as in Example 1 (however, the molding conditions were as follows). A test piece was made from the molded product. The physical properties were measured and the results are shown in Table 1 under the molding conditions. Cylinder temperature 250℃, injection pressure (primary/secondary) 7 0
0/500 kg/012, mold temperature 90℃
Forked lid 1” As a cyclic olefin copolymer, ethylene and DMON
Random copolymer with +30-ethylene content of 67 mol% determined by NMR, M F R 2as'e
, 17 g/min, intrinsic viscosity [η] measured in decalin at 135°C 0. 6dl/drop Softening temperature (TMA)
135°C, glass transition temperature Tg 123°C] pellet 3.4t. g, and an ethylene/propylene random copolymer (ethylene content 80 mol%:
Glass transition temperature Tg -54℃, intrinsic viscosity ['7 1
2.2dl/g) 0. After mixing 6 kg, they 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.The resulting pellets were used instead of the cyclic olefin copolymer in Example 1. A molded product was obtained using the same method as in Example 1 (however, the molding conditions were as follows).
A test piece was made from the molded product and its physical properties were measured.9 The results are shown in Table 1 under the molding conditions; cylinder temperature 240°C, injection pressure (primary/secondary) 70
0/5 00kg/an2, mold temperature 80℃ 1" As a cyclic olefin copolymer, ethylene and DMON
Random copolymer with ('3C-NMR determined ethylene content 62 mol%, MFR 26@'c, 3
Intrinsic viscosity measured in decalin at 5 g/min at 135°C [
1 piece 0.47dl/g, softening temperature (TMA) 14
8℃, glass transition temperature Tg 137℃) 4kg pellets
and ethylene-propylene random copolymer (ethylene content 80 mol%: glass transition temperature T
g-54°C, intrinsic viscosity [η] 2. After mixing 1 kg of pellets of 2 dl/g), they 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. Add 1 g of Verhexin 25Bs manufactured by Verhexin and 3 g of divinylbenzene and mix well.The mixture is melt-blended using a twin-screw extruder at a cylinder temperature of 230°C, pelletized using a pelletizer, and foamed into 1 kg of pellets. A foamable polymer composition was prepared by blending 10 g of the agent.
Using this composition, injection foam molding was performed under the following conditions: 350 x 100 x 5 @II
A plate-shaped molded product was obtained. A test piece was made from the molded product and its physical properties were measured. The results are shown in Table 1. Molding conditions:

Claims (3)

[Claims] (1) Ring-opened polymers, ring-opened copolymers, and hydrogenated products of the polymers or copolymers derived from cyclic olefins represented by the following formula [I]; A foamable polymer composition comprising at least one type of cyclic olefin resin selected from the group consisting of addition polymers of cyclic olefin and ethylene, and a foaming agent; ▲Mathematical formula, chemical formula, table etc. ▼...[I] [In the above formula [I], n is 0 or a positive integer, and R^1 to R^1^2 each independently represent a hydrogen atom, a halogen atom, and a carbonized atom. Represents an atom or group selected from the group consisting of hydrogen groups, R^9 and ~R^1^2 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^9 and R^1^0 or R^1^1 and R
may form an alkylidene group with ^1^2]. (2) The foamable polymer composition further comprises 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, polymers derived from epoxides,
Polyacetal, polyphenylene oxide, polycarbonate, polysulfone, urea resin, polyamide resin,
2. The foamable resin composition according to claim 1, comprising at least one resin selected from the group consisting of polyester resins, formamide resins, and natural polymers. (3) A foam obtained by foaming the foamable polymer composition according to claim 1 or 2 to a volume of 1.05 to 5 times the volume of the composition.