JPH03277638A - foamable polymer composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to expandable polymer compositions and foams, and more particularly to expandable polymer compositions and foams capable of forming homogeneous closed cell foams. Regarding the body.

Technical Background of the Invention Examples of materials for foams include polystyrene and polyethylene. In addition, the foaming method usually includes a method of foaming by mechanical stirring, a method of using a reaction product gas,
There are methods of using a blowing agent, methods of removing soluble substances, and foaming methods by spraying, and methods of utilizing reaction product gas and methods of using a blowing agent are particularly 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.

OBJECTS OF THE INVENTION In view of such prior art, an object of the present invention is to provide a foamable polymer composition that is heat resistant and chemical resistant and that can provide a foam having uniform closed cells. It is in.

Summary of the Invention The foamable polymer composition according to the present invention comprises [A] a polymer or copolymer obtained by ring-opening polymerization of a cyclic olefin represented by the following formula [I] or the following formula [11], and a copolymer thereof. A polymer selected from the group consisting of a hydrogenated compound and a copolymer obtained by copolymerizing ethylene with a cyclic olefin represented by the following formula [I] or the following formula [Ir], [B co-degradable blowing agent] and [C] a polyhydric carboxylic acid or a derivative thereof.

Further, the foam according to the present invention is characterized in that it is formed by foam-molding the above-described foamable polymer composition to a volume of 1.2 to 50 times the volume of the composition.

Detailed Description of the Invention Each component of the foamable polymer composition according to the present invention will be specifically explained below.

[Polymer [A]] The foamable polymer composition according to the present invention is a polymer or copolymer formed by ring-opening polymerization of a cyclic olefin represented by the following formula [1] or the following formula [II], or It contains a hydrogenated product thereof, and/or a polymer selected from the group consisting of a copolymer obtained by copolymerizing a cyclic olefin represented by the following formula [I] or the following formula [II] and ethylene.

However, in the above formula [n], n is 0 or 1, m is O or a positive integer, and R1 to R18 are each independently selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. represents an atom or group.

Furthermore, R15 to R18 may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond.

Furthermore, R15 and R16 or R17 and R18 may form an alkylidene group.

Further, as the polymer [A], for example, a ring-opening polymer obtained by ring-opening polymerization of a cyclic olefin represented by the formula [I] or the formula [Ir] alone or in the presence of the following formula. Alternatively, it may be a ring-opened copolymer. Furthermore, in the present invention, as the polymer [, A],
It is also possible to use a hydrogenated product obtained by hydrogenating at least a portion of the double bonds present in the ring-opened polymer or copolymer as described above.

The cyclic olefin represented by the above formula [I] or the above formula [n] can be easily produced by condensing a cyclopentadiene with a corresponding olefin or a cyclic olefin by a Diels-Alder reaction. can.

(Left space below) Specifically, the polycyclic olefin represented by the formula [N is the above compound, or 1,4.5.8-dimethano-1,2,3,4,4a, 5.8 In addition to .8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,34,4a,5. L8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1
, 2,3,4,4a, 5.8.8a-octahydronaphthalene, 2-propyl-1,4,5,8-dimethano,
2,3,4,4a,5,8,8a-octahydronaphthalene, 2-hekinru 1.4,5.8
-dimethano-1,,2,3,4,4a5.8.8a-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-1,2,3,4,4a,5
．． 8.8a-octahydronaphthalene, 2-chloro-1
, 4,5,8-dimethano-1,2,3,4,4a, 5.
8.8a-octahydronaphthalene, 2-brome to 1.
4.5.8-dimethano-1,2,3,4,4a,5.8
, 8a-octahydronaphthalene, 2-fluoro-1,
4,5,8-dimethano-1,2,3,4,4a,5,8
．． 8a-octahydronaphthalene, 2.3~dikuOO-
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-1,2,3,4,4
a, 5,8.8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,
Examples include octahydronaphthalenes such as 4a, 5.8, 8a-octahydronaphthalene.

(Left space below) As the cyclic olefin represented by the above formula [J] used in the present invention, specifically (daibicyclo[2,2,11hept-2-ene derived arc tetracyclo[4,4,0,12, 5,1)・5I-co-3-dodecene expansion imitation hexacyclo[5,5,l, 13, 6, 11 @
, + 3, Q2.7, QQ, + 4
]-4-heptadensene derivative octacyclo[8,8,0,12,9,14,7,10
1@, 113.16.03・I, Ql 2・I? ]
-5-tococene derivative pentacyclo[6,6,1,11
1, @, 02), O” ”]-]4-hexadecene derivative heptacyclo-5-icosene derivative heptacyclo-5-heneicosene derivative tricyclo[
4,3,0,12,6]-]3-decene induced arc tricyclo4.3.0.12・6cor 3-undecene induced non-pentacyclo[6,5,1,13・6, Q2, ?
, QQ・I 3 ]-]4-pentadecene derivative pentacyclopentadecadiene derivative Book 9 Schiff O[4,7,0,12s, O"=', 1"
12]-3-pentadecene induction book 9 shi'y mouth [7,8,0,1'・',0'',I
Ie17. O"""112, 1 S to 4-eikosen induction book and / f Schiff D [9, 10, 1, 1, 4, 7, 0", 0
2-111.0112'11129, QQ4. I9.
l+s, +s]-5-pentacose:/ derivatives.

Specific examples of such compounds are shown below.

Bicyclo[2,2,1] such as Hept-2-ene induction conductor; CH.

5.10-DimethyltetraCHI 2.7.9 Trimethylte9-isobutyl-2,7-9,11,12-)dimethyl9-ethyl-11,12-dime9-isobutyl-11,12 5,8 ,9,10-tetramethy8-methyltetrasif8-edyltetrasic1.]-]3-dodecene-hexyltetracyc+al(st,I.]-]3-dodecene.]-]3-dodecene-methyl-9- Ethylte 8-chlorotetrasif 3 Dodecene 8-promotitrasif = 3-dodecene 8-fluorotetrasif 1.]-]3-dodecene.]-3-dodecene 1, l?, I@]-3-dodecene 11-3- dodecene-3-dodecene 1]-3-dodecene, 12 5.17・1 theft]-3-dodecene 8-ethylidene-9-ethyne 8-ethylidene 9-y sododecene 12,!,l?・11cor 3- dodecene i, lv, Il]-3-dodecene 8-n-propylidene-9 -dodecene 8-n-propylidene-9 [4,4,0,12,', 1 1 white]-3-dodecene 1-co 3-dodecene 8-n-propylidene-9 [4,4,0,12 s, 17.11]-3 1-dodecene 8-isopropylidene 8-impropylidene-dodecene 1e-3-dodecene-dodecene and other tetracyclo[ 4, 4, 0, 12, 5, 1, I
@ Coco-dodecene derivatives; (blank below) 14-4-hebutadecene 12-methyl hexacyfdecenedecene heptadecene Q2, 7, Qll 14-hexacyclo[6,6,1,1' such as 4-hentadecene 8.11 @ Q2, 7, □s]-4-hebutadecene derivative; tococene +8,111 1 m, Q3 8.01 +7-5-tococene 15-ethyl octase 2, +? ]-5-Tococene and other octacyclo[8,8,0,12114 7,10 1・1+ + 6, (p, @, Ql 2, +]]
-5-Tococene derivatives such as decene and pentacyclo [6,6,1,1"・6.02?
, Ql, eyes] -4-hexadecene derivatives; heptacyclo[8,7,0 Hebutacyclo-5-icosene derivatives such as cosene or hebutacyclo-5-heneicosene derivatives; tricyclo[4,3, 0,12.5]-3-decene derivatives; tricyclo[4,4,0,12 1-3-undecene derivatives such as 10-methyl-tricif; 1,3-dimethyl-penta1,6-dimethylbenta14,15 -pentacyclo [6,5,1,13,8,027,
O@+ 3 ] -4- Pentadecene derivatives; Diene compounds such as; Pentacyclo[4,7,0,12・5.08 31IQ 12] -3-pentadecene derivatives: Cosene 2.11 ] -4 such as methyl-substituted bentashicene - Hebutacyclo[7,8,Q, 1Il, Q2. T, lIl, +? ,Q1
6.112 15] -4-eicosene derivative; 21.113.2@, Q1m19.11s, +s] -5
- Bentacosen 3.211. Nonacyclo[9,10,1,14,7,03,+
1.02.1・, O12, 21, 113, 29, Q10
．． 19.11s, +s] -5-bentacocene derivatives.

(The following is a blank space) Further, as the cyclic olefin represented by the above formula [nl] used in the present invention, the following compounds may be specifically mentioned.

5-phenyl-bicyclo[ -2-en can be mentioned.

(The following is a blank space) To explain more specifically the polymer [A] used in the foamable polymer composition of the present invention, this polymer [A] is as follows: (1) Formula [I] or Formula [ A ring-opening polymer or a ring-opening copolymer of a cyclic olefin represented by [Ir] or a hydrogenated product thereof, or (2) addition polymerization of a cyclic olefin represented by the above formula [11 or formula [11]] and ethylene. Examples include copolymers obtained by

(1) Cyclic olefin ring-opening polymer and its hydrogenated product The cyclic olefin ring-opening polymer has the formula [1] or the formula [
11] is ring-opening polymerized by a method known per se, and is homopolymerized or copolymerized. For example, the copolymerization of 1.4.5.8-dimethano-1,2,3,4,4a,5,8.8a-octahydronaphthalenes, or the above-mentioned norbornene (bicyclo[2,2 , 1]] may be copolymerized with hept-2-ene.

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 [N has a structure represented by the following formula [m] considered to be a thing.

In addition, the ring-opening polymer described above can be hydrogenated to remove double bonds remaining in the container by a method known per se, and the hydrogenated product is a material for injection molding that has better thermal stability and weather resistance. It is.

In such a hydrogenated product, for example, at least a part of the cyclic olefin represented by the formula [1] is represented by the following formula [rV
] It is thought that it has a structure expressed as follows.

18 has the same meaning as in the formula [H.

In addition, when carrying out ring-opening polymerization of a cyclic olefin, the above formula [
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 formed from the cyclic olefins represented by N or the formula [U, l. Examples of such cyclic olefins include cyclobuteno, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2-(
2-Methylbutyl)-1-cyclohexene, 2,3.3
a, 7a-tetrahydro-4,7-methano-IH-indene and 3a, 5. [i,7a-tetrahydro-4,
Examples include 7-methano-1,11-indene.

(2) Addition polymerization of cyclic olefin and ethylene In the cyclic olefin addition polymer, the ethylene component/cyclic olefin component (molar ratio) is usually 10/90 to 90/10, preferably 50,150 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. 60168708 and the like.

In addition, in the cyclic olefin addition polymer, the above formula [
I] or the monomer copolymerized with the cyclic olefin compound represented by the formula [I[] to constitute a copolymer having an alicyclic structure is an olefin, and in the present invention, as an olefin, , usually ethylene. However, in the copolymer having an alicyclic structure used in the present invention, in addition to ethylene as the olefin, other olefin compounds may be copolymerized within a range that does not impair the properties of the composition of the present invention. .

In the present invention, examples of other olefin compounds that can be copolymerized with ethylene and the cyclic olefin compound represented by the above formula [11 or formula [11'l] include propylene, 1-butene, 4- Methyl-1-
Pentene, 1-hexene, J-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene,
α-olefins having 3 to 20 carbon atoms such as 1-octadecene and 1-eicosene cyclopentene, cyclohexene, 3-methylcyclohexene, cyclooctene and 3a,5,8,7a-tetrahydro-4,7-methano-IH ~cycloolefins such as indene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene −
Non-conjugated dienes such as 2-norbornene and 5-vinyl-2-norbornene; norbornene-2,5-methylnorbornene-2,5ethylnorbornene-2,5-isopropylnorbornene-2,5-n-butylnorbornene-2 , 5-i-butylnorbornene-2,5,6-dimethylnorbornene-2,5-chloronorbornene-2,2-fluoronorbornene-2 and 5,6-cyclonorbornene-2, and other norbornenes. be able to. Among these, α-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 represented by formula [1] or formula [1] having two or more double bonds in the molecule, it may be hydrogenated for the purpose of improving weather resistance. .

In such a cyclic olefin random copolymer,
For example, at least a portion of the repeating units derived from the cyclic olefin [1] is considered to have a structure represented by, for example, the following formula [v].

[V] In the above formula [V], R1-R18 are represented by formula [1
] have the same meaning as these.

For example, when the cyclic olefin has a structure such as [I[[] to [V] above, the obtained polymer can be
This is supported by analysis by R. 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 polymers and hydrogenated products thereof and (2) cyclic olefin addition polymers have an intrinsic viscosity [η of 0] measured in decalin at 135°C.
,01~20dρ/g, especially 0.05~10dl
/lr, more preferably 0.08 to 8 dl/g.

These cyclic olefin polymers generally have poor quality or low crystallinity, and are preferably non-grade.

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 no melting point is observed using differential scanning calorimetry (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 50-23
0°C, mostly within the range of 100-200°C.

Therefore, when directly used as a molding material, the softening temperature is usually measured to be in the range of 70 to 180°C, and often in the range of 90 to 180''C.

As for mechanical properties, the bending modulus of this resin itself is usually in the range of 1 x 10 to 5 x 104 kg/c-, and the bending strength is also usually in the range of 300 to 1500 kg/cJ.

Furthermore, the foamable polymer composition according to the present invention can use, as a base polymer, a so-called polymer alloy obtained by blending various polymers with the above-mentioned polymer [A]. 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-1, poly(4-methyl) which may have a crosslinked structure Pentene-1, Polybutene-1
, polystyrene, 2. Halogen-containing vinyl polymers, specifically polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene, chlorinated rubber, etc. 3. Derived from α,β-unsaturated acids and their derivatives Polymers, specifically polyacrylates, polymethacrylates, polyacrylamides, polyacrylonitrile, or copolymers with monomers constituting the above polymers, such as acrylonitrile-butadiene-styrene copolymers, acrylonitrile-styrene copolymers Polymers, acrylonitrile/styrene/acrylic acid ester copolymers, 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, polyvinyl Allyl melamine or a copolymer with a monomer constituting the polymer, such as a copolymer with ethylene or vinyl acetate, etc. 5. A polymer derived from an epoxide, specifically a polymer derived from polyethylene oxide or bisglycidyl ether. 6. Polyacetals, specifically polyoxymethylene, polyoxyethylene, etc.
7. Polyphenylene oxide, 8. Polycarbonate, 9. Polysulfone, 10. Polyurethane and urea resin, 11. Diamine and dicarboxylic acid and/or aminocarboxylic acid or the corresponding lactam. Polyamides and copolyamides derived from nylon 6, nylon 66, nylon 11.
such as nylon 12, 12, polyesters derived from dicarboxylic acids and dialcohols and/or oxycarboxylic acids or the corresponding lactones, in particular polyester terephthalate, polybutylene terephthalate, poly 1,4-dimethylol cyclohexane terephthalate, 13 14. Polymers with a crosslinked structure derived from aldehyde and phenol, urea or melamine Specifically, phenol/formaldehyde resin, urea/formaldehyde resin, melamine/formaldehyde resin, etc. 14. Alkyd resin Specifically, glycerin/formaldehyde resin, etc. 6. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols and obtained using vinyl compounds as crosslinking agents, such as phthalic acid resins, and halogen-containing modified resins. Natural polymers, specifically cellulose, rubber, protein, or their derivatives such as cellulose acetate, cellulose propionate, cellulose ether, etc. 17. Soft polymers, lu Lower 11m Denotes (+) to (V) Rubber component The cyclic olefin polymer and these rubber components form a so-called "polymer alloy", and this polymer alloy can be used as it is, but it is also possible to add an organic superoxide to this polymer alloy. A crosslinked structure may be formed by performing a crosslinking reaction in the presence of an oxide, and impact resistance is improved by using such a crosslinkable polymer alloy.

(Soft polymer having a cyclic olefin structure (1)) The soft polymer having a cyclic olefin structure consists of an ethylene component and the same type of cyclic olefin (represented by formula [I]) used in preparing the cyclic olefin polymer. compound) and α-
It is a ternary or higher copolymer prepared by copolymerizing with an olefin. Examples of the α-olefin include propylene, l-butene, 4-methyl-1-butene, ■-hexene, 1-octene, 1-decene, l-dodecene, 1-tetradecene, l-hexadecene, and 1-octadecene. and 1-eicosene. Among these, olefins having 3 to 20 carbon atoms are preferred. Cyclic olefins and cyclic dienes such as norbornene, ethylidenenorbornene and dicyclopentadiene can also be used effectively.

In the soft polymer (i) having a cyclic olefin structure, the repeating unit derived from the ethylene component is usually contained in an amount of 30 to 98 mol%, preferably 40 to 90 mol%. The repeating unit derived from the α-olefin component is usually contained in an amount of 2 to 50 mol%, and the repeating unit derived from the cyclic olefin component is
It is contained in an amount of 2 to 20 mol%, preferably 2 to 15 mol%.

Unlike the cyclic olefin polymer, the soft polymer (1) 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 [ η is usually 0601~10dj? /
g, preferably within the range of 0.8 to 7 dl/g. Also.

This 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%. .

The soft polymer (i) is, for example, disclosed in JP-A-80-168708.
Publication No. 81-120816, Japanese Patent Application Laid-open No. 1981-120816
-115912, JP 61-11.5918, JP 81-2713011, JP 81
It can be manufactured by selecting appropriate conditions based on the method proposed by the present applicant in JP-A-272218 and JP-A-1-252408.

(α-olefin copolymer (j)) The α-olefin copolymer (i) used as a soft polymer in the present invention is a non-quality or low-grade copolymer formed from at least two types of olefins. It is a crystalline copolymer. Specific examples include ethylene/α-olefin copolymers and propylene/α-olefin copolymers.

As the α-olefin constituting the ethylene/α-olefin copolymer, α-olefins having 3 to 20 carbon atoms are usually used, and specific examples of such α-olefins include propylene, -butene, 4-methyl-1
-butene, -hexene, I-octene, -decene, etc., and mixtures thereof. Among these, α-olefins having 3 to 10 carbon atoms are particularly preferred.

The molar ratio of the ethylene/α-olefin copolymer (ethylene/α-olefin) varies depending on the type of α-olefin, but is generally preferably 40/60 to 9515. Further, the above molar ratio is preferably 40/60 to 90/10 when the α-olefin is propylene, and preferably 50,150 to 9,515 when the α-olefin has 4 or more carbon atoms. .

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

In the above propylene-α-olefin copolymer, the molar ratio of propylene to α-olefin (propylene/α-olefin) varies depending on the type of α-olefin, but is generally 50,150 to 9,515. is preferred.

(α-olefin/diene copolymer (i)) The α-olefin/diene copolymer (i) used as the soft polymer in the present invention includes ethylene/α-olefin/diene copolymer rubber and Propylene/α-olefin/diene copolymer rubber may be mentioned.

The α-olefin constituting these copolymer rubbers is usually an α-olefin having 3 to 20 carbon atoms (4 to 20 in the case of propylene/α-olefin), such as propylene, l-butene, l-pentene, etc. , 4-methyl-1-pentene, 1-hexene, 1-octene, -decene, and mixtures thereof.

Among these, α-olefins having 3 to 10 carbon atoms are preferred.

In addition, the diene component that makes up these copolymer rubbers is
linear non-conjugated dienes such as 1,4-hexadiene, 1,8-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-hebutadiene and 7-methyl-1,8-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/
α-olefin) is generally 40/60 to 90/10, although it differs depending on the type of α-olefin.

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

(Aromatic vinyl hydrocarbon/conjugated diene soft copolymer (IV)) The aromatic vinyl hydrocarbon/conjugated diene soft copolymer used as the soft polymer in the present invention is an aromatic vinyl hydrocarbon/conjugated diene soft copolymer (IV). Hydrogen, a conjugated diene-based random copolymer, a block copolymer, or a hydride thereof. Specifically, styrene-butadiene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber, styrene-isoprene block copolymer rubber, styrene-butadiene block copolymer rubber,
Isoprene/styrene block copolymer rubber, hydrogenated styrene/butadiene/styrene block copolymer, 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. 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.

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

The properties of the copolymers (i) to (V), which are soft polymers, are similar to those of the cyclic olefin-based soft polymer (i), and the intrinsic viscosity [η
] is usually 0.01 to 10 di)/lr, preferably 0
．． The glass transition temperature (
Tg) is usually 0°C or less, preferably -10°C or less, particularly preferably -20°C or less. Further, the degree of crystallinity measured by X-ray diffraction is usually in the range of 0 to 10%, preferably 0 to 7%, particularly preferably 0 to 5%.

Polymer alloys containing such rubbery components and crosslinkable polymer alloys treated with organic peroxides are available in various types (
The total amount of the soft copolymers i) to (V) is 5 to 150 parts by weight, preferably 5 to 100 parts by weight, particularly preferably 10 parts by weight, based on 100 parts by weight of the cyclic olefin addition polymer.
~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 01238 conditions) is preferably 0.1 to 1oo.

In addition, as the organic peroxide used when crosslinking polymerizing the polymer alloy with an organic peroxide, ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, 1,1-bis(t-butyl peroxide), etc. ) Peroxyketals such as cyclohexane 2,2-bis(t-butylperoxy)octane, t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroxyperoxide and 1 .1.8. ! Hydroperoxides such as l-tetramethylbutylhydroberoxide, di-t-butylperoxide, 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, t-butylperoxybenzoate, and 2.5- Peroxy diesters such as dimethyl-2,5-di(benzoylperoxy)hexane and the like can be mentioned.

The organic peroxide component is usually 0.01 to 1 part by weight, preferably 0.05 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 component. used in amounts of

When treating with an organic peroxide for the purpose of further increasing crosslinking efficiency, if a compound having two or more radically polymerizable functional groups in the molecule is further included in the reaction system, excellent impact resistance can be achieved. Preferred examples of compounds having two or more 0° radically polymerizable functional groups in the molecule include divinylbenzene, vinyl acrylate, and vinyl methacrylate because they yield a polymer alloy with a high temperature. These compounds 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.

Blowing Agent The decomposable blowing agents used in the present invention 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, azide compounds, sodium hydride, and light metals.

Examples of organic blowing agents include azodicarbonamide, barium azodicarboxylate, N,N'-dinitrosopentamethylenetetramine, 4,4-oxybis(benzenesulfonylhydrazine), diphenylsulfone-33-disulfonylhydrazide, p-toluene. Examples include sulfonyl semicarbazide, trihydrazinotriazine, and villarea, and the high-temperature blowing agents mentioned therein are also used appropriately.

In addition, in order to appropriately select a blowing agent, the decomposition temperature, gas generated, and decomposition rate of the blowing agent are important factors.

The foaming method for decomposable foaming agents is to melt and knead the material at a temperature above the melting point of the material resin and below the decomposition temperature of the blowing agent, then heat it above the decomposition temperature of the blowing agent and foam at normal pressure. Pressure foaming method, extrusion foaming method in which the material resin containing the foaming agent is extruded from a die in a molten state, changing the pressure from high pressure to normal pressure and foaming, and the material resin containing the foaming agent is filled into a closed mold. , the pressure foaming method, in which the foaming agent is decomposed by heating under pressure and rapidly expanded due to the pressure change caused by pressure release, and the injection foaming method, in which a uniformly foamed core layer and a non-foamed skin layer are formed. . Further, in the pressure foaming method, a crosslinking agent, a radical generator, etc. may be used as appropriate.

Polyhydric carboxylic acid or derivative thereof The foamable polymer composition according to the present invention comprises [A] as described above.
] Polymer, [B] In addition to the decomposable foaming agent, [C] contains a polyhydric carboxylic acid or a derivative thereof.

Such polyhydric carboxylic acids or derivatives thereof include:
Specifically, citric acid, succinic acid, or salts, esters, and amides of these acids are used.

Such [C] polyhydric carboxylic acid or its derivative,
By including it in a foamable composition, a foam having homogeneous closed cells can be obtained.

Blending ratio of each component In the foamable polymer composition according to the present invention, the polymer [A
/Blowing agent (weight ratio) varies depending on the type of blowing agent, but is usually preferably in the range of 10010.1 to 10015.

[C] polyhydric carboxylic acid or its derivative is [C]
Polyhydric carboxylic acid/[B] Decomposable blowing agent (weight ratio) is 0
．． It is desirable to use an amount of 1 to 10, preferably 0.5 to 5.

The foaming agent in such a composition is appropriately mixed and dispersed by the foaming method described above, and the foaming ratio is preferably in the range of 1.2 to 50 times, although it varies depending on the purpose of the secondary molded product.

The foam thus obtained is a lightweight foam with excellent heat resistance, chemical resistance, and electrical properties.

Other additives The foamable polymer composition according to the present invention includes heat-resistant stability, weather-resistant stability, antistatic agents, slip agents, anti-blocking agents, antifogging agents, and lubricants within the range that does not impair the purpose of the present invention. ,
Dyes, pigments, natural oils, synthetic oils, waxes, organic or inorganic fillers, etc. can be blended.

For example, stabilizers that can be added as optional ingredients include:
Tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate comethane,
β-(3,5-di-1-butyl-4-hydroxyphenyl)propionic acid alkyl ester, 2,2'-oxamidobis[ethyl-3-(3,5-di-mybutyl-4)
- Phenolic antioxidants such as hydroxyphenyl) propionate, fatty acid metal salts such as zinc stearate, calcium stearate, calcium 12-hydroxystearate, glycerin monostearate, glycerin distearate, pentaerythritol monostearate, pentaerythritol di Examples include polyhydric alcohol fatty acid esters such as stearate and pentaerythritol tristearate. These may be blended alone or in combination. For example, tetrakis[methylene-3-(3,5-di-t-butyl-
Examples include a combination of 4-hydroxyphenyl)propionate comethane, zinc stear phosphate, and glycerin monostearate. Examples of organic or inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate,
Dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber, Examples include silicon carbide fibers, polyethylene fibers, polypropylene fibers, polyester fibers, and polyamide fibers.

As a method for mixing the polymer [A] 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.

Applications The foam obtained from the foamable polymer composition according to the present invention may be used after being subjected to secondary processing, and secondary processing methods include vacuum forming, press forming, slip forming, air pressure forming, printing,
It can be used for painting, plating, flocking, embossing, laminating with metal or other resins, etc.

Finally, there are the following usage methods.

(1) Utilization of insulation properties Insulating and preventing condensation on roofs, ceilings, walls, and floors of buildings, insulating warehouses, keeping pipes, tanks, etc. warm and cold, electric refrigerators, bathtubs,
Air-conditioning equipment, showcases, heat/cold containers, automobile ceilings, door linings, food containers (tea, ramen, soup) (2) Use of cushioning properties Cushioning packaging for home appliances, precision equipment, food, etc., food containers (trays), Sports equipment such as automobile instrument panels, armrests, side pillars, sun visors, hard hats, headgear, protectors, judo dojo bones, etc. (3) Container packing using compressive properties, sealing materials, back up materials (4) Buoyancy, Utilizing lightweight marine lifesaving equipment, buoyancy structures, floats, various water play equipment,
Parabolic antennas and flat antenna substrates, (5) Utilization of acoustic properties Sound absorbing materials for machine rooms, sound rooms, broadcasting rooms, etc. The foam of the foamable polymer composition obtained in this way has excellent heat resistance and chemical resistance. It has excellent characteristics and can be applied to a wider range of applications than conventional foams.

DETAILED DESCRIPTION OF THE INVENTION As described in the detailed description of the invention, the foamable polymer composition and foam thereof according to the present invention contain the polymer [A] as a blended component, and the foam has homogeneous closed cells. It has excellent heat resistance, chemical resistance, electrical properties, insulation properties, and mechanical strength, and can be applied to a wide range of applications.

EXAMPLES The present invention will be specifically explained below with reference to Examples. The present invention is not limited to these examples.

Incidentally, methods for measuring and evaluating various physical properties in the present invention are shown below.

(1) Melt flow index (MFTr) According to ASTM-D1238, a predetermined temperature (T°C),
Measurement was performed with a load of 2.16 kg.

(2) Softening temperature (TMA) Thermo Mechanical manufactured by DuPont
The thermal deformation behavior of a 1 mm thick sheet was measured using alBe+. Place a quartz needle on the sheet and apply a load of 49
g and raise the temperature at a rate of 5℃/min until the needle reaches 0.635+
The temperature at which ++m penetrated was defined as TMA.

(8) Glass transition temperature (Tg) Measured at a temperature increase rate of 10° C./min using DSC-20 manufactured by SEIKO Electronics Industry ■.

(4) Expansion ratio Calculated by comparing the specific gravity before and after foaming, measured by the underwater substitution method.

(5) Chemical resistance The foam molded product obtained in the example was immersed in the specified test solution below and left at 23°C for 7 days, and the case where there was no change in appearance such as dissolution, cracking, or hue was considered to have passed. .

Test liquid acid resistance, 20% sulfuric acid aqueous solution Alkali resistance: 20% sodium hydroxide aqueous solution Example 1 As a cyclic olefin copolymer, ethylene and 1.4,
5.8-dimethano-1,2,3,4,4a, 5.8,8
a-octahy measured ethylene content 71mol1%, M
Intrinsic viscosity [η] measured in decalin at 135°C for 10 minutes at FR26°・C20g/10 minutes is 0.6dj! /g, softening temperature (TMA) 115°C, Tg 103°C) and 10g of a 1/1 (weight ratio) mixture of citric acid and sodium bicarbonate were thoroughly mixed to prepare a foamable polymer composition. is. Using this composition, extrusion foam molding was carried out under the following conditions. The foaming state of the obtained molded product was observed under a microscope, and the foaming ratio and chemical resistance were examined.

The results are shown in Table 1.

Molding conditions: Extruder: 5E-40 screw manufactured by Toshiba Machinery Co., Ltd.;
Slow compression Full flight compression ratio 3.3, L/D-22 Die: Round die, lip opening 2.5 degrees Setting temperature Niji Linder/Die adapter/Dice-230/190/
160℃ Resin pressure crab 160kg/cd Extrusion amount +96g/min.

Example 2 Ethylene and DMON as a cyclic olefin copolymer
Random copolymer with (ethylene content 62 mo1% measured by 13C-NMR, M F R2e ).

・C35g/10min, intrinsic viscosity [η] measured in decalin at 135°C 0.47dN/g, softening temperature (TMA)
A molded article was obtained in the same manner as in Example 1, except that 148° C.) was used instead of the cyclic olefin copolymer of Example 1 and the cylinder temperature was changed to 250° C., and its physical properties were measured.

The results are shown in Table 1.

Molding conditions; Cylinder temperature: 250°C, Example 3 As a cyclic olefin copolymer, ethylene and DMON were used.
A random copolymer with ethylene content (67 mo1% as measured by C-NMR), M F R2e.

・C17g/l 0 minutes, intrinsic viscosity [η] measured in decalin at 135°C 0.6dR/g, softening temperature (TMA)
1.35°C, pellet with glass transition temperature Tg1233.
4 kg, and an ethylene/propylene random copolymer as a rubber component (ethylene content 80 mo1%, glass transition temperature Tg -54°C, intrinsic viscosity [η] 2.2 dg/g)
) with 0.6 kg of pellets, then the twin screw extruder (
Cylinder temperature 220℃ by Ikegai Iron Works PCM45)
The mixture was melt-blended using a pelletizer and pelletized using a pelletizer.

A molded article was obtained in the same manner as in Example 1 except that the obtained pellet was used in place of the cyclic olefin copolymer of Example 1 and the cylinder temperature was changed to 240°C, and its physical properties were measured. .

The results are shown in Table 1.

Example 4 Ethylene and DMON as a cyclic olefin copolymer
Random copolymer with
Intrinsic viscosity [η
]0.47dj2/r, softening temperature (TMA) 148°C,
4 kg of pellet with a glass transition temperature Tg of 137) and an ethylene-propylene random copolymer as a rubbery component (ethylene content 80111o1%; glass transition temperature T
After mixing 1 kg of pellets with g-54°C and intrinsic viscosity [η of 2.2 dl/g], they were melt-blended using a twin-screw extruder (PCM45 manufactured by Ikegai Tekkobun) at a cylinder temperature of 220°C, and then using a pelletizer. Pelleted.

To 1 kg of the obtained pellets, 1 g of Perhexin 25B■ manufactured by NOF ■ and 3 g of divinylbenzene were added and thoroughly mixed. This mixture was melt-blended using a twin-screw extruder at a cylinder temperature of 230°C, and pelletized using a pelletizer.

10 g of a foaming agent was blended with 1 kg of the obtained pellet to prepare a foamable polymer composition. A molded article was obtained in the same manner as in Example 1 except that the cylinder temperature was changed to 250° C. in place of the cyclic olefin copolymer of Example 1, and its physical properties were measured.

The results are shown in Table 1.

Comparative Example The same operation as in Example 1 was carried out except that only sodium bicarbonate was used instead of the mixture of citric acid and sodium bicarbonate used as the blowing agent in Example 1.

The results are shown in Table 1.

/ / / table

Claims (2)

[Claims] (1) [A] A polymer formed by ring-opening polymerization of a cyclic olefin represented by the following formula [I] or the following formula [II], a copolymer, and its hydrogenated product, and the following formula [I] or the following A polymer selected from the group consisting of a copolymer obtained by copolymerizing a cyclic olefin and ethylene represented by formula [II], [B] a decomposable blowing agent, and [C] a polycarboxylic acid or a derivative thereof. A foamable polymer composition characterized by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, n is 0 or 1, m is 0 or a positive integer, and R^2 to R^1^8 are each independently a hydrogen atom, A halogen atom or a hydrocarbon group, and R^1^5 to R^1^8 may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring has a double bond. Also, R^1^5 and R^1^6, or R^1^7
and R^1^8 may form an alkylidene group). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [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^6) 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 using any group. ] (2) A foam formed by foam-molding the foamable polymer composition according to claim 1 to a volume of 1.2 to 50 times the volume of the composition.